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Analysis of copper azide in ammunition using FTIR

Conference Paper · January 2001

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 Analysis of copper azide in ammunition using FTIR
Symp. Chem. Probl. Connected Stabil. Explos. (2001), 12th

Torbjörn Lindblom and Hans Malmberg

Bodycote CMK AB
Box 431 SE-691 27 Karlskoga, Sweden
Abstract
Fuses containing lead azide and copper or brass are in a moist environment always prone to formation
of copper azide, a most sensitive material. Using fuses containing copper azide has caused a number
of accidents caused by premature ignition. A well-known method to determine the presence of copper
azide in low concentration is to use iron(III)chloride.

FTIR has been used to directly and non-destructively detect copper azide on a surface. This method
gives a higher sensitivity than the iron(III)chloride test. The FTIR method also gives information
about other types of corrosion products on the surface. It does not give false signals as the
iron(III)chloride test can do.

A method has also been developed for field use when analysing object, which can not be analysed due
to their physical dimensions or because they can not be brought to the instrument. Here a drop of an
EDTA solution is placed on a suspect sample surface. After a few minutes the sample solution is
absorbed into a paper patch which thereafter is dried. The paper can later be analysed with FTIR in
the laboratory and the amount of copper azide can be quantified.

Formation of copper azide

Copper azide is a most sensitive compound, which might explode upon the slightest
mechanical touch. This has initiated several accidents with ammunition over the years. Copper
azide is not present from the beginning in the ammunition but is formed in the reaction
between hydrogen azide, NH3, and copper or brass. The hydrogen azide, a most poisonous
gas, is formed when water e.g. in the atmosphere at a humidity >50% RH reacts with lead
azide, a very common primary explosive in igniter systems.

Brass reacts more slowly than copper and zinc present in the brass forms preferably Zn(N3)2,
which is not dangerous. The primary reaction between Cu, and HN3 creates copper(I)azide,
CuN3 and copper(II)azide, Cu(N3)2.
Copper(I)azide is not stable and is, in the presence of oxygen, oxidised to copper(II)azide.

2Cu + 3HN3  2CuN3 + NH3 + N2

3CuN3 + ½O2 + 2HN3  2Cu(N3)2 + H2O

The copper azide is rapidly hydrolysed in moist air to basic copper azides. These have the
general formula
Cu(N3)2•XCuO•YH2O

At the reaction between HN3 and Cu in moist air CuN3 is formed closest to the copper.
Outside this layer one basic Cu(II)azide is formed protecting the Cu(I)azide eventually.
Some data on copper azides
Name Formula Colour, crystal structure
Copper(I)azide CuN3 Glass clear needles, plates. Gets red
when illuminated
Copper(II)azide Cu(N3)2 Green black needles, prismatic
One basic Cu(II)azide Cu(N3)2•CuO•H2O Yellow brown powder
Two basic Cu(II)azide Cu(N3)2•2CuO•2H2O Yellow green crystals
Three basic Cu(II)azide Cu(N3)2•3CuO•3H2O Blue green plates
Eight basic Cu(II)azide Cu(N3)2•8CuO•7(?)H2O Dark green crystals, initially light green

Analysing copper azide using iron(III)chloride

This has been the method of choice for many years. For this purpose a 30% solution of FeCl3
is used.
A drop of the solution is applied to the suspected area. If copper azide is present a red colour
is developed due to the formation of iron azide. This compound decomposes under the
formation of iron oxide hydrate and HN3, hydrogen azide. This reaction is visualised by the
disappearance of the red colour. The intensity of the red colour and the time to the colour
change is a measure of the amount of copper azide present.

From the following graph the amount of azide can be judged.

0,45
C r i t ic a l l im i t
0 ,4

0,35
HN3 conc (mg/cm )
2

0 ,3

0,25
B la c k / r e d

0 ,2
D a rk re d

0,15
" B lo o d "
0 ,1
B rig h t re d
0,05
R ed
P a le r e d
0
0 2 4 6 8 10
T im e (m in )

Colour and time to colour change when using Fe(III)Cl-solution for detecting azide

2
The problems with this method are:
 Which is the colour of the droplet?
 The time to decolouration is difficult to establish. When is the colour change complete?
 The Fe(III)Cl-solution also gives colour changes with other compounds present on the
surface.
 The reactant does not always wet the surface due to presence of oil.

Analysing copper azide using FTIR. Direct analysis

Analysing copper azide with FTIR gives very distinct peak at about 2100 cm-1 , This is in an
area where only few compounds, mostly nitrogen containing ones, absorb.

Reference
A reference of copper azide was synthesised in that a piece of copper was enclosed in a glass
jar together with sodium azide and a few drops of sulphuric acid. After 5 minutes of reaction
the copper plate was analysed with FTIR using a Diffuse Reflection accessory.
0,045
Cu-azide formed during 5 minutes reaction

0,040

0,035 2068 (Azide peak)

0,030

0,025
Absorbance

0,020

0,015

0,010

0,005

0,000

4000 3500 3000 2500 2000

2000 1500 1000 500
cm-1

IR-spectrum of Copper azide

This sample when tested with Fe(III)Cl-solution gave colour and colour change
corresponding to 0.17 mg copper azide/ cm2. This is about 42% of the critical amount,
0.4 mg/ cm2. This corresponds to 0.037 Absorbance Units (AU).
Amount of copper azide on an unknown sample can thus be calculated from:

Amount Cu(N3)2 = 4.57·AU (mg/ cm2)

FTIR offers a sensitive method to accurately detect copper azide.

Method applied to a real sample

The copper cone in a shaped charge shell, stored for about 30 years, was suspected to contain
copper azide as the igniter contained lead azide. There was also a direct connection between
the igniter through a tube connecting the igniter and the tip of the copper cone. The sample
is illustrated with a photo and a "drawing" below.

3
 TNT
Copper
cone "Tube"

Pb-azide

Booster
Photo and drawing of Copper cone in shaped charge with indications of where stripes were taken

Four stripes were cut from the copper cone according to the illustration and each stripe
was cut into small pieces, as indicated on one of them. These were analysed with FTIR
using the DRIFTS accessory.
Analysis of these small copper pieces gave an interesting result, examples of which is
shown in the two spectra below.
Not only is copper azide detected but also a lot of inorganic material together with an aliphatic
hydrocarbon.
Copper cone. Sample 1:1
0,14 1551
0,12

0,10 1408
3353 -OH
Abs

0,08 CH-stretch
0,06

0,04

0,02 2091
0,00
0,20
Copper cone. Sample 2:4
1543
0,15
1400
Abs

0,10

0,05
2164
2091
0,00
3500 3000 2500 2000 1500 1000
cm-1

IR-spectra from the surface of copper cone from shaped charge

0,012 Copper cone. Sample 1:1 Expansion of the azide area clearly shows
the azide peak at 2091 cm-1.
0,010 2091
0,008

The second peak at 2164 cm-1 probably

Abs

0,006

0,004

0,002
comes from one of the higher copper
0,000 azides, Cu(N3)2•XCuO•YH2O.
0,016 Copper cone. Sample 2:4 2091
0,014

0,012

0,010 2164
The huge peaks around 1545 and
1405 cm-1 probably comes from a
Abs

0,008

0,006

0,004 carboxylate and/or basic copper carbonate.

0,002

0,000 A spectrum with these two references is

2400 2300 2200 2100 2000 1950
cm-1 shown below
Expanded part of azide region of spectrum

4
 0,15 Copper cone. Sample 1:1 1551

0,10 1408
3353 -OH
Abs

CH-stretch
0,05

2091
0,00
Basic copper carbonate
0,6
Abs

0,4

0,2

Ref.: Acetic acid, Na salt

0,8

0,6
Abs

0,4

0,2

3500 3000 2500 2000

2000 1500 1000
cm-1

Deposit on copper cone from shaped charge with references

Analysing the samples from the four bands taken from the copper cone reveals that the highest
amount of copper azide is found close to where the tube enters the cone. The lowest values are
found at the opening of the cone.

Maximum amount of copper azide was around 40% of critical value, 0.4 mg/ cm2.
Minimum amount of copper azide was around 3% of critical value.
3
The findings expressed
as % of critical value 23
at tip and opening of the Copper
cone in
copper cone is shaped
HN3
summarised in the charge
Figure to the right.
40

24

Schematic of distribution of copper azide on copper cone in a

shaped charge. Amounts in % of critical value, 0.4 mg/ cm2

Discussion
The heavy HN3 (M= 43) enters the cone and roles down the "slope". As it roles down it
reacts with the copper. Less HN3 reaches at the upper entrance of the tube. Very little of the
hydrogen azide reaches the upper part of the cone at the opening.
From the analysis made the storage position of the shaped charge can be judged.
Analysing a corroded copper surface without azide using the Fe(III)Cl-solution gave a colour
change corresponding to 0.05 mg azide/ cm2. Time to colour change ~2 minutes.
No critical concentration of copper azide was detected. Instead a lot of inorganic corrosion
material was found which should act as a flegmatising material and lower the sensitivity of the
copper azide.

5
Analysing copper azide using FTIR. Field use
Not always the item to be analysed can be brought to the laboratory or it does not fit into the
equipment. To overcome this problem a field method was developed where the following
criteria were fulfilled.
 The sampling was done by desolution of the sample in an aqueous reagent. (Solid
sampling is out of question due to the high risk of ignition.)
 The reagent has to have a pH of about 10 to avoid liberation of hydrogen azide an acid
with pKa 4.8.
 Copper compounds in the deposit be transformed into soluble ions/ complexes, including
azides.

An aqueous solution of Ethylene Diamine TetraAcetate (EDTA) fulfils these criteria.

Verification of complete reaction

A surface containing copper azide 0,60
2133 2049
was analysed in the DRIFTS mode. 0,55

To the area analysed a drop of 0,50

Copper azide on copper
0,45

EDTA solution was added. After 0,40

the drop had acted on the surface for Before EDTA

Absorbance

0,35

a couple of minutes the drop was 0,30

soaked into a filter paper and the 0,25

0,20

surface was analysed again. 0,15 After

From the spectra to the right it is 0,10 EDTA
obvious that the azide has 0,05

0,00
disappeared from the copper surface 2400 2200 2000 1900 1800 1700
cm-1

Use of EDTA on surface with copper azide to verify a complete

reaction. Common scale is used for the spectra.

Preparation of reagent
5.6 g of EDTA is added to 25 ml water. A magnetic stirrer is used and about 1 g of solid
NaOH is added. The solution is stirred till it gets clear. pH is adjusted to 10 with 0.5 M NaOH
and is diluted to 50 ml. The reagent should be stored in a closed bottle.

Use of reagent
On the suspected surface 3 l of the reagent solution is added. After 3 minutes it is soaked
into a circular filter paper (diameter 5.5 mm), type Munktell 00H. Time allowed for soaking
the solution into the paper is about 1 minute. After 10 minutes drying in air the sample is
ready for analysis or transportation in a polyethylene bag or a small glass jar to the laboratory
for analysis. The azide is due to the NaOH converted to sodium azide.

Analysis of collected sample

The small filter papers are analysed in the transmission mode with FTIR. Preferably an
IR-microscope is used. The use of a cellulose filter paper, which itself has a strong infrared
adsorbtion, one thinks should cause problems. From the spectra below, however, it is obvious
that the azide absorbs in an area where organic materials have few absorbance bands.

6
 1,4 1,4
Cellulose in Filter paper Cellulose in Filter paper with Sodium azide
1,3 1,3

1,2
Cellulose 1,2

1,1 1,1

1,0 1,0

0,9 0,9

Azide
Azide
Absorbance

Absorbance
0,8 0,8

0,7 0,7

0,6 0,6

0,5 0,5
Cellulose
0,4 0,4
used as
0,3 0,3
background
0,2 0,2

0,1 0,1
3000 2000 1500 1000 3000 2000 1500 1000
cm-1 cm-1

Spectrum of cellulose Spectrum of cellulose and sodium azide

soaked into the cellulose

Using a clean piece of filter paper 0,60

Sodium azide in cellulose

as background produces a very nice 0,55

-1
IR-spectrum of azide when
0,50

0,45
2025 cm
analysing a filter paper into which 0,40
Abs
orb
0,35
anc

sodium azide has been soaked. e

0,30

0,25

0,20

0,15

0,10

0,05

0,00
2300 2200 2100 2000
2000 1950 1900 1850
cm-1

Spectrum of sodium azide soaked into a filter paper.

Filter paper is used as background.

Interference 0,80

Only a few substances 0,75 2068 KCN

0,70 2045 KSCN
absorb in this area. Those, 0,65
2091 CuN3

which have absorbtion here, 0,60 2025 NaN3

can usually be distinguished 0,55

0,50

from azide, as shown from

Absorbance

0,45

the examples given. 0,40

0,35

0,30

0,25

0,20

0,15

0,10

0,05

2300 2250 2200 2150 2100 2050 2000 1950

cm-1

Different substances absorbing in the "azide window"

7
 Calibration
A standard solution was prepared from 130 mg sodium azide plus 0.1 mg NaOH in 25 ml of
water. Successive dilution gave lower amount of azide. 3 l of each concentration was added
to a circular filter paper (diameter 5.5 mm) and was analysed after drying. 6 analyses on each
sample gave the calibration curve below, where amount NaN3 has been converted to amount
of HN3/ cm2.

1 ,2
-1
Absorbance at 2040 cm

0 ,8

0 ,6

0 ,4

0 ,2

0
0 0 ,0 1 0 ,0 2 0 ,0 3 0 ,0 4 0 ,0 5
2
A m o u n t o f H N 3 o n s u r fa c e (m g / c m )

Calibration curve: Sodium azide solution soaked into filter paper

(converted to mg HN3)/cm2 )

Standard deviation between measurements is around 10%. This should give a good safety
margin as risk for initiation occurs at concentrations above 0.1 mg HN3/ cm2.

Discussion
Using FTIR for detection of copper azide gives a high specific sensitivity for this very
sensitive compound. Direct detection is possible.
Also the wet chemical method described is very useful as it makes is possible to take samples
outside the laboratory and still get a quantitative value of the amount of copper azide on a
surface suspected to contain copper azide.
As the test is specific for azide there is no risk for a false value as has been observed with the
Iron(III)chloride test. Also protecting layers of e.g. oil, which inhibit wetting, does not
interfere.
As the method, on direct analysis of the surface, also gives information of other corrosion
products on the surface a much more complete evaluation can be done.

Acknowledgement
Mr Nils-Erik Petersson at FMV (Defence Material Administration) is thanked for financial
support, which made it possible to carry through this investigation.

References
1. S. Lamnevik, Kopparazidkorrosion, FOA 1 Rapport 1 1461- 43(40, 41) 1969
2. A. Alm, Detektering och analys av explosivämnen. FOA Rapport C20133-D1
Aug 1976.
3. B.T. Federoff, Encyclopedia of explosives and Related Items. Volume 1 page
A520 - A627 (Picatinny Arsenal, Dover, New Jersey, USA, 1960.

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