IAEA-TECDOC-465

ISOTOPIC NEUTRON SOURCES

FOR NEUTRON ACTIVATION ANALYSIS
USER'S MANUAL
PREPARED BY J. HOSTE
UNIVERSITY OF GHENT

A TECHNICAL DOCUMENT ISSUED BY THE

INTERNATIONAL ATOMIC ENERGY AGENCY, VIENNA, 1988
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ISOTOPIC NEUTRON SOURCES FOR NEUTRON ACTIVATION ANALYSIS
IAEA, VIENNA, 1988
IAEA-TECDOC-465

Printed by the IAEA in Austria

June 1988
 FOREWORD

Neutron activation analysis (NAA) is a well established analytical

technique in countries where a nuclear reactor is available. However, many of
the developing countries have neither a nuclear reactor nor other sources of
neutrons, but have still a strong interest in this technique.

Through its Technical Co-operation Programme, the Agency has been

promoting the use of nuclear analytical techniques such as Neutron Activation
Analysis and X-ray Fluorescence Analysis in many governmental and university
laboratories in developing Member States. Instrumentation is often provided
for such purposes, e.g., gamma spectrometry systems and other radioactivity
counting equipment.

In many developing countries, one of the major drawbacks is the lack of

appropriate neutron sources, either a nuclear research reactor or a neutron
generator. With the purpose to assess the feasibility of using other
alternative neutron sources, a Consultants' Meeting on Isotopic Neutron
Sources for Neutron Activation Analysis was organized in May 1985. It was
concluded that Isotopic Neutron Sources of an appropriate design and
characteristics in terms of neutron flux and spectra, could allow small
research centers and university laboratories to carry out interesting and
meaningful training and research oriented projects based on neutron activation
and radiochemistry.

The present User's Manual is an attempt to provide with a series of well

thought demonstrative experiments in NAA based on the utilization of an
isotopic neutron source, for teaching and training purposes. In some cases,
these ideas can be applied to the solution of practical analytical problems.

The Agency wishes to thank all scientists who participated in the

Consultants' Meeting, and particularly Professor Dr. J. Hoste, who undertook
the task to write the present manual.
 EDITORIAL NOTE
In preparing this material for the press, staff of the International Atomic Energy Agency
have mounted and paginated the original manuscripts and given some attention to presentation.
The views expressed do not necessarily reflect those of the governments of the Member States
or organizations under whose auspices the manuscripts were produced.
The use in this book of particular designations of countries or territories does not imply any
judgement by the publisher, the IAEA, as to the legal status of such countries or territories, of
their authorities and institutions or of the delimitation of their boundaries.
The mention of specific companies or of their products or brand names does not imply any
endorsement or recommendation on the part of the IAEA.
 CONTENTS
INTRODUCTION ............................................................................................. 9

1. ISOTOPIC NEUTRON SOURCES ................................................................. 12

1.1. Alpha (a,n)-sources .............................................................................. 12

1.1.1. The (a,n)-reaction ...................................................................... 12
1.1.2. Type of alpha-sources ................................................................. 13
1.1.3. Neutron yields and energy ............................................................ 13
1.1.4. Source choice ........................................................................... 17
1.1.5. Source arrangement .................................................................... 18
1.1.6. Transport container .................................................................... 24
1.1.7. Safety aspects ........................................................................... 25
1.1.8. Source installation ...................................................................... 25
1.1.9. General safety ........................................................................... 28
1.2. Spontaneous fission sources .................................................................... 29
1.3. Photoneutron sources ............................................................................ 31
1.4. Neutron multipliers .............................................................................. 33

2. PRINCIPLES OF ACTIVATION ANALYSIS ................................................... 35

2.1. General equation .................................................................................. 35

2.2. Activation in an isotopic neutron source ..................................................... 38
2.2.1. Fast flux .................................................................................. 39
2.2.2. Thermal flux ............................................................................. 40
2.2.3. Epithermal neutron flux ............................................................... 41
2.2.4. Reaction rate for (n,7) reactions .................................................... 41
2.3. Standardization .................................................................................... 42
2.3.1. Absolute method ........................................................................ 42
2.3.2. Relative method ......................................................................... 42
2.3.3. Single comparator ...................................................................... 44
2.3.4. ko-standardization ....................................................................... 44
2.4. Sources of error .................................................................................. 46
2.4.1. Flux gradients ........................................................................... 46
2.4.2. Neutron shielding ....................................................................... 47
2.4.3. Nuclear interference ................................................................... 48
2.4.3.1. Threshold reactions .......................................................... 48
2.4.3.2. Fission reactions ............................................................. 48

3. PROMPT GAMMA NEUTRON ACTIVATION ANALYSIS (PGNAA) ................... 50

4. THERMAL NEUTRON ABSORPTION ANALYSIS ........................................... 52

4.1. Principle ............................................................................................ 52

4.2. Detection of the thermal flux .................................................................. 54
4.3. Standardization .................................................................................... 54
4.4. Other applications ................................................................................ 55
5. TRANSPORT SYSTEMS ............................................................................. 57

6. MEASURING EQUIPMENT ........................................................................ 59

6.1. General ............................................................................................. 59

6.2. Sodium iodide detectors ......................................................................... 59
6.3. Germanium semi-conductor detectors ........................................................ 64
6.4. Detector calibration .............................................................................. 65
6.4.1. Resolution and efficiency ............................................................. 66
6.4.2. Energy calibration ...................................................................... 68
6.4.3. Evaluation of the gamma spectra .................................................... 69

7. SAMPLE PREPARATION ........................................................................... 72

8. APPLICATIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74

8.1. Determination of silver in lead ................................................................ 74

8.1.1. Introduction .............................................................................. 74
8.1.2. Nuclear data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
8.1.3. Equipment ................................................................................ 76
8.1.4. Sample and standard preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
8.1.5. Irradiation and counting conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
8.2. Determination of manganese in pyrolusite and ferromanganese ........................ 77
8.2.1. Introduction .............................................................................. 77
8.2.2. Nuclear data ............................................................................. 78
8.2.3. Interferences ............................................................................. 79
8.2.4. Neutron and gamma-ray attenuation effects ....................................... 81
8.2.5. Measuring and irradiation conditions ............................................... 81
8.2.6. Calculations .............................................................................. 83
8.3. Determination of silicium and aluminium in bauxite ...................................... 84
8.3.1. Introduction .............................................................................. 84
8.3.2. Nuclear data ............................................................................. 84
8.3.3. Sample preparation, irradiation and measurement ............................... 89
8.4. Determination of silicium and aluminium in aluminium-silicium alloys .............. 92
8.4.1. Introduction .............................................................................. 92
8.4.2. Principle .................................................................................. 93
8.4.3. Standardization and calculation ...................................................... 93
8.5. Determination of tin in cassiterite ............................................................. 95
8.5.1. Introduction .............................................................................. 95
8.5.2. Nuclear data ............................................................................. 97
8.5.3. Sample preparation, irradiation and measurement ............................... 98
8.5.4. Standardization .......................................................................... 100
 8.6. Determination of fluorine in fluorites and ores ............................................ 100
8.6.1. Introduction .............................................................................. 100
8.6.2. Nuclear data ............................................................................. 100
8.6.3. Irradiation, counting and calculation .............................................. 102
8.7. Determination of manganese in plants ....................................................... 104
8.7.1. Introduction .............................................................................. 104
8.7.2. Nuclear data ............................................................................. 104
8.7.3. Procedure ................................................................................ 105
8.8. Determination of cadmium in zinc ore by neutron absorption .......................... 106
8.8.1. Introduction .............................................................................. 106
8.8.2. Nuclear data ............................................................................. 106
8.8.3. Sample and standard preparation .................................................... 107
8.8.4. Irradiation and measuring conditions ............................................... 108
8.8.5. Interferences and calculation of the results ........................................ 108
8.9. Determination of boron in steel by neutron absorption ................................... 110
8.9.1. Determination ........................................................................... 110
8.9.2. Procedure and results .................................................................. 110
8.10.Other applications of INS ....................................................................... 112

REFERENCES ................................................................................................ 113

 INTRODUCTION

Neutron activation analysis (N.A.A.) was proposed half a century

ago by G. von Hevesy and H. Levy for the analysis of dysprosium in rare

earths using an isotopic neutron source.

Since this historical experiment neutron activation analysis was

developed as a highly valuable analytical technique especially since

the advent of nuclear reactors. These offer indeed high neutron fluxes

so that extremely small quantities of a large number of elements can be

determined. Consequently N.A.A. was mainly applied to the determination

of trace elements in a variety of matrices e.g. high purity materials,

biological, environmental and geological specimens etc.

Apart from the high sensitivity for many elements N.A.A. has the

advantage that it is a purely nuclear method of analysis, i.e. the

results are not influenced by the chemical state of the elements under

investigation. Moreover contaminations after irradiation are not to be

feared, a major advantage in trace analysis.

In its initial stage of development, say up to the begin of the

Fifties, simple techniques were used to measure the induced activities,

usually a Geiger-Müller counter. This measuring technique having no

selectivity whatsover, chemical separations were in many cases unavoid-

able. At best identification of a nuclide could be carried out by anal-

ysis of a not too complex decay curve.

A major step forward occured with the introduction of the NaKTl)

scintillator used for gamma spectrometry together with single or

multichannel analysers. Due to the poor resolution of this type of

detector, chemical separations were still often required. Truly

instrumental methods of neutron activation analysis became really

 possible with the advent of germanium semi-conductor detector of the

Ge-Li type or more recently with the hyperpure germanium, coupled for

instance to 4000 channel analyzers to take full advantage of the high

resolution. In many cases instrumental analysis thus became possible

for over 40 elements in certain matrices if together with the high

resolution advantage is taken of the difference of half-lifes of the

produced radioactive species, i.e. short- medium- and long-lived

isotopes.

Other sources of neutrons than the nuclear reactor have been

developed namely the so called neutron generator. By bombardment of a

tritium target with low energy deuterons, for instance 150 keV.

Practically more energetic 14 MeV neutrons are produced at a rate which

can reach some 10 neutrons per second. These machines are mainly

applied for the determination of oxygen and silicon, as the sensitivity

and selectivity is quite high. Activation analyses have also been

described by cyclotron produced neutrons, mainly by deuteron irradia-

tion of a beryllium target. The high intensity continuous energy

spectrum of high energy neutrons induce mainly threshold reactions and

allow a sensitive determination of a number of elements which are

difficult to determine by (n,y)reactions induced by thermal neutrons.

Neutron activation in a reactor does not allow an easy and

sensitive determination of light elements as for instance 8, C, N and

0. nor of heavy elements as Pb and Tl. This can be successfully

achieved by charged particle analysis with protons, deuterons or

hélions with energies of up to some 20 MeV.

From the above considerations it appears that sensitive and in

many cases instrumental analyses can be achieved for many elements by

applying reactor irradiation, mainly with thermal neutrons, although

epithermal and fast fission neutrons are occasionally also applied, the

10
most important characteristic being the high neutron flux and conse-

quent high sensitivity.

Neutrons can also be produced from isotopic sources. Usually

however the neutron production is many orders of magnitude smaller than

in reactors. Thus trace analysis is only possible for elements with

adequate nuclear characteristics and is limited to a small number of

elements. Up to now isotopic neutron sources (I.N.S.) have not been

thoroughly explored, except perhaps in geological prospection, although

they offer interesting analytical perspectives for accurate determina-

tions of minor and major constituants in ores, concentrates. alloys

etc. It is also obvious that, for pedagogic purposes. I.N.S. are also

interesting as the basic principles are obviously also valid and not

source intensity dependent. For institutions who cannot for financial

or other reasons dispose of a nuclear reactor, I.N.S. offers interest-

ing possibilities. As pointed out by J. Op De Beeck (1) they offer a

number of intrinsic advantages over other neutron sources namely

extremely small size, relatively low purchase and maintenance costs,

long and short term stability of the neutron output, possibility to use

thermal and fast neutron fluxes. The ease and low cost of shielding can

also be added to this list of advantages and have thus a negligible

health hazard.

11
 1. ISOTOPIC NEUTRON SOURCES

Three main types of isotopic neutron sources can be distinguished

namely alpha-emitters, which produce neutrons through an (a,n)-reac-

tion, gamma-emitters through a (y, n)-reaction and isotopes of heavy

elements which undergo spontaneous fission. The properties of these

sources have been discussed in detail by K.W. Geiger (2) and M.V.

Blinov (ibidem) at the Debrecen meeting in 1980 of the IAEA Consult-

ants' meeting on neutron source properties. It was also reviewed by

K.W. Geiger at the IAEA Meeting in Vienna in May 1985. This Consultants

Meeting had as subject "Isotopic Neutron Sources for Neutron Activation

Analysis (3 ) .

1.1. Alpha (a,n)-sources.

1 . 1 . 1 . The («,n)-reaction.

Radioactive alpha emitters can be used as neutron sources as they

induce (a,n)-reactions on a number of target nuclides. Usually

beryllium is used as a target material through the reaction

9 12
Be(«,nJ C

which has a Q-value of 5.70 MeV. As shown in Table 1.1 for the alpha
210
emitter Po, other nuclides can be used as target material but with

neutron yields which are substancially lower than with beryllium.

It is thus quite clear that for activation analytical purposes only

beryllium should be considered. The other target materials are only

used for special purposes, e.g. to simulate a fission spectrum.

12
 21 0
TABLE 1.1 : (a,n)-Reactions of Po on Light Nuclei

Target Nuclide Q-value Neutron yield

per 10 alphas

7
Li - 2.79 2.6

Be 5.70 80
10. 1 .06 13
11. 0. 16 26
13. 2.22 10
18.
- 0.70 29
19. - 1 .95 12

1.1.2. Type of alpha-sources.

A number of alpha emitting nuclides can in principle be chosen as

a possible source. A survey of their characteristics is given in Table

1 .2.

1.1.3. Neutron yields and energy.

The neutron spectra can be calculated from the relevant nuclear

data. e.g. alpha energies, stopping power in beryllium, energy level

diagrams etc. These calculations are however somewhat obscured by the

fact that a absorption can occur in the alpha-emitter itself and not

only in the infinite thick beryllium target. Thus the continuous alpha-

energy distribution gives a broadening of the lines corresponding to

the energy diagrams. Changes of energy also occur as a function of

13
 U)

C ,_
4J •^ r- o -- -- ^- r-~
Cti •*£> J2 O O O O O O u l O
O \ • • • • • • • •
CU
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o
>S o o o o o o o o
V VU V V \t
O ^-i S
TJ O
4-1 C
1 -H
>- S

C
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M
4-1
>Q)
3 S
CU v-' O^ ~J" vO ^~~ ^o "vf r^>
Z O ' - O u ^ i - < f r o ^ — o ^ 0 0
CU M ^<T *^ ^d" ^r •<)" <d" ro ro
00 i-i
n) CU
P C
<U W

t—\ o o
r - ^ L n ^ — o o c o ^ — r * - c ^
T o o o o o o o o
13 00
r— 1
CU «- U~] CN T— LO LO {p U"l f*^
•H 1 « • • • • • •
>^ W "•Cf T—• T—• >iO CN ^~ r—*

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*o o o o o o o o o o
r-l T T r T T
0) r- ^ " I ~ I * " " I ~ I * ~ i " T ~ I ~ ^
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>-, CO • • • • • •
• CN *— CN CN T— T-
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14
solid angle. The yield and energy depends also on source construction,

e.g. its cylindrical geometry, its composition, presence of «-emitting

daughter isotopes etc.

An approximate idea of the neutron energies obtained from the

12 9 12
energy levels of C of the reaction Be{a,n) C is given in Fig. 1 . 1 .

Be + a -n
Q = 5.7 MeV

9 12
Fig. 1.1 : The Be(a,n) C reaction

A line spectrum is thus expected from the neutron group n to n .

o 3
However an energy continuum is also observed experimentally below 3.5
12
MeV, partly caused by broad levels in C above 9.6 MeV but mainly by

the b r e a k - u p reaction

9 9 * 8
Be(a,a') Be > Be + n

involving levels at 1.67, 2.43 and 3.06 MeV of Be.

In an idealized source where a-particles are only slowed down in

the Be-matrix the distribution of neutrons per unit energy interval for

a-particles of energy between E and E + AE is given by

a ft a

15
 27/sin O d e AE
F(E ) = cr(9) (1.1 )
n dE

where a(9) is the center of mass (c.m.) cross section for neutron pro-

duction and € the stopping power cross section for beryllium at E .

a
The neutron energy in the laboratory system may be expressed as a

function of the c.m. angle in the form

E = a + b cos 6 1.2)
n
and
irr AE
F(E 1 .3
E (0=0) - E (9=n) e
n n

A comparison of the calculated and mesured spectrum for Am-Be is shown

in Fig. 1.2.

4 -
241
Am-Be
proportional counter

stilbene counter

calculated

10
E (MeV)
n

Fig. 1.2 : Comparison with measured spectra.

16
The neutron yield given in Table 1.2 is calculated from

Y - 0.95 + 0.152 E ' neutrons per 10 «.particles (1.4j

a

In general one should keep in mind that the following causes can

deform the energy spectra and the neutron yield

1. elastic and inelastic neutron collisions in the source

2. neutron induced fission within the « - e m i t t e r

Neutron spectra of other Be(«,n)-source are shown in Fig. 1 . 3 .

242
Cm
244
Cm

0 4 8 12

Neutron Energy (MeVJ

Fig. 1.3 : Neutron spectra of isotopic Be(«,n) sources.

9
3. the Be(n,2n) reaction

4. the Be (r,n) reaction

5. reduction of the effective «-energy within the «-emitting cluster

6. daughter équilibra of «-emitting species.

1.1.4. Source choice.

For activation analytical purposes a number of considerations

determine the choice of the source namely price, half-life, neutron

17
 yield, required shielding from gamma rays, toxicity and small volume

and of course availability.

210 242
From table 1.2 it appears that Po and Cm are too short lived
239 238
to be of practical value. Pu and Pu are considered too toxic and

too dangerous to be easily accepted in many countries. R a d i u m , which

has often been used in the past is difficult to shield due to its high

level of gamma radiation but is still an acceptable choice if available

227
and has a very long half life and thus stable neutron output Ac is

an excellent choice as it combines high neutron yield with reasonable

long half life Its production from neutron irradiation of

997
Ra(n,y) Ra ———— > Ac has however been stopped and is probably
no longer available in sufficient quantities.
244
The Cm not being readily available y e t , one is left as choice
24 1
with only Am which combines long half-life with reasonable high

neutron yield and low gamma radiation dose.

244
It is however possible t h a t Cm sources become important in the

future as this isotope is produced in copious quantities in fast

reactor fuel.

1 . 1 . 5 . Source arrangement.

The neutron yields shown in Table 1.2 are calculated from equation

(1.4) and expressed in neutrons per second. For activation analysis

however a thermal neutron flux is usually required although fast

neutrons are also sometimes applied. Consequently the source is

usually installed in a moderating medium such as paraffin wax, water or

water expanded polyester. The most convenient is perhaps the former as

a purification system is not needed as in the case with water, where it

is desirable to remove the corrosion products which gradually dissolve

into the water and are activated by the source. Water expanded

polyester can also be considered.

18
 One has to keep in mind that the actual flux given by a source

with a yield of 10 n.s will give a thermal neutron flux density two
5 - 2 - 1
orders of magnitude lower i.e. appr. 10 n.cm .s , with a fast flux

density of approximtely one order of magnitude higher.

5 -2 -1
Considering that 10 n.cm ,s is a minimum to carry out useful

analyses a source strength corresponding to at least 10 n.s is

necessary.

Several types of source arrangements are possible namely a single

cylindrical source, an array of sources or an annular one.

It is obvious that the former will give rize to considerable

l a t e r a l flux gradients so that the activation is not Isotropie and lead

to serious complications, affecting the accuracy of the analysis.

An array of sources placed symmetrically around the irradiation

place can yield a reasonably uniform flux. The arrangement is

certainly to be preferred if the source is rather short lived, as is

252
the case with Cf (see further), so that additional sources can be

added to compensate for the d e c a y .

For long lived sources a single annular source is the most

advantageous arrangement as the lateral flux is homogeneous. The

complexity of maintenance and wipe test procedures is also greatly

simplified. Alaerts e.a. (4) described the neutron flux distribution

228
measured experimentally from a cylindrical 1g R a - B e source (height

36 mm. diameter 17 mm). The arrangement and flux distribution is shown

in Fig. 1.4. One can see that a steep axial flux gradient can be

observed.

The same authors (5) studied the flux distributions from an

? ?7 R —1
annular Ac-Be source with a neutron yield of appr. 10 n.s

A drawing of the source is shown in Fig. 1.5.

The thermal, epithermal and fast fluxes were measured by means of

19
 80 cm

Compressed
air

10 cm

Cadmium foi
( 1 mm)

50 cm

4. 10 5. 10" 6. 10"
Counts/Gram Cu.10 sec

226
Fig. 1 . 4 : C y l i n d r i c a l R a - B e source a n d a x i a l f l u x d i s t r i b u t i o n .

20
 Ac-Be mixture
Monel metal
304L stainless steel

9 O *7 O _ 1
Fig. 1.5 : Annular Ac-Be source of 10 n.s

respectively a gold-aluminum wire, from a manganese activation with and

OQ OQ
without cadmium shield and from the Si(n.p) Al reaction. For the

latter the fast flux distribution of the source and the excitation

function were taken into account.

The results are shown in Fig. 1.6.

It can be seen that the optimal distributions of thermal and fast

flux are situated at different heights and can thus be optimized for

the thermal or fast neutron activation.

Similar results can of course be expected from the recommended

source at the IAEA-Meeting in 1985, namely a 25 curie americium-241-

beryllium annular source with 52 mm inside diameter, 75 mm outside

diameter and 135 mm overall length a shown in Fig. 1 . 7 .

21
 4. 10

2.10
CM
I
eu
in
G
O

3
01
Z

.x50
épi

section of the source

Ac-Be mixture

axis of the ir adiation tube

2 4 6
Height from bottom of the irradiation tube (cm)

227
Fig. 1 . 6 : A x i a l flux d i s t r i b u t i o n s o f a n a n n u l a r Ac-Be source.

22
 76.0 dia
—*
52.0 dia

!
fci

•:••:

o
<r ro

l
^ \\\N v \ \ ft\
S 1 v h \\u i
i

/ C
Weld

Dimensions mm
Material : AISI 316
stainless steel

Fig. 1.7 : 25 C u r i e A m e r i c i u m - 2 4 1 - B e r y l l i u m A n n u l a r Source.

23
 This source is closed at one end with a flange containing a tapped hole

for the handling rod.

1 . 1 . 6 . Transport container.

2^1
The transportation of a 25 curie Ann-Be- source must conform to

the IAEA regulations, Safety Series N * 6 , 1973. These specify that the

source encapsulation must be of special form and that the transport

container be of Type B(u). The surface dose rate must be less than

200 mRem/h and the dose rate at one meter from the surface must be less

than 10 mRem/h. Such a container is shown in Fig. 1.8.

eal
ap
Closure sealing
plate

hielding plug

Container body

Source retention
packing

Shielding plug

Sealing plate

Cap

10 cm

Fig. 1.8 : Transport Container

24
1.1.7. Safety aspects.

It is necessary to consider all aspects of safety including

general aspects such as adequate lifting and handling equipment as well

as radiological safety, catering also for possible exposure due to ac-

cidental, negligent or criminal action.

Americium-241 as wel as other possible «-emitters are in the highest

class of radiotoxic nuclides. It is essential therefore that the source

is designed and manufactured to the highest possible standards. Also

that the facility as a whole contributes to this safety and that main-

tenance is carried out conscientiously during service.

The International Organisation for Standardisation (ISO) has

produced a system of classification of sealed radioactive sources based

on safety requirements for typical uses. For activation analysis pur-

poses the following requirements should be met :

Temperature : - 75'C (20 min) + 400'C/1h) and thermal shock 400*C

to 20'C

Pressure : 25 k N/m 2 - 2MN/m 2

Impact : 200 g from/m

Vibration : 30 min 25 to 500 Hz at 5g peak amplitude

Puncture : 10 g from/m

1.1.8. Source installation.

The activation analysis facility should be installed in accordance

with local and international regulations into an area with controlled

access. There should be barriers with adequate warning signs erected

along the 0.75 mRem/hr isodose line with the source in the working

position. This is the maximum permissible dose rate for a

25
 non-classified worker or a member of the general public. For

classified personnal the maximum dose rate is 2.5 mRem/hr assuming a

t>0 hour working week. Ttie necessary shielding precautions should be

taken to comply with this requirement. Care should be taken at all

time to ensure that any adjacent rooms or corrid.ors to which people

have access do not h a v e dose rates in excess of those mentioned.

A suitable installation would have the activation analysis

facility supported on a framework approximately one and a half meters

above round level. The transport container can then be placed

underneath the facility and the source transferred vertically from the

container into the facility using a suitable long handling rod as shown

in Fig. 1.9.

Neutron Activalion
Facility

Source Handling
Rod

Transport Container

25 Ci 241Am/Be
Neutron Source

Support SLand

Fig. 1.9 : Source Transfer Procedure.

26
 The bottom screening plug is then replaced and locked in position

in the facility. The handling rod is unscrewed and the top screening

plug placed in position until the pneumatic sample transportation tube

is ready to be placed in position inside the annular source.

Once the source has been located in position a surface contamina-

tion wipe test should be performed of the source and empty transport

container. This wipe test should be repeated each time the source is

reinstalled or be checked at least once every two years by wipe testing

the source.

The neutron and gamma dose rates should be measured around the

facility to ensure the screening integrity. These measurements should

be repeated from time to time to assess the integrity of the screening.

The neutron activation facility shown in Fig. 1.8 has been desig-

ned to have a total surface dose rate of appr. 2.5 mRem/h. Paraffin or

expanded polyester is preferred to water on account of possible

leakage.
a „. 1
Alaerts e.a. (I.e.) installed an annular Ac-Be-source of 10 n.s

directly in a watertank of 50 cm by 50 cm, the source being placed

directly near the pneumatic tube near the bottom. The lead shield of 10

cm together with the cadmium foil insures a dose-rate at the surface of

appr. ImRem/hr except in the prolongation of the pneumatic tube.

Unacceptable dose rates of neutrons and associated gamma's can of

course be avoided by installing a beam catcher on the ceiling. A scheme

of the installation is given in Fig. 1.10.

It is obvious that the water can be replaced by either paraffine

or water expended polyester. A water purification system is then no

longer required.

27
 7.5x7.5 Nal(Tl)
detector in
6cm lead castle
holder
Printer

Pneumatic Transport

Photoelectric control of
the presence of the
irradiation container

Cd shield

Pb shield

Ion exchanger Containerstop ?27

Ac-Be source
Pump

Fig. 1 . 1 0 : General scheme of irradiation and measuring facility.

1 . 1 . 9 . General safety.

It is obvious that the general environment should be clean and

free of grease, dirt and grit, that the floor has an adequate covering

and that good house keeping is maintained. If compressed air is used

28
for a pneumatic transport system the lines should be kept free from oil

and dust by means of properly maintained filters.

Access to the area should be strictly controlled and wherever

possible a lockable room should be provided to prevent unlawful entry.

1.2. Spontaneous fission sources.

A number of transuranium elements not only desintegrate by a

decay, but also by spontaneous fission releasing several neutrons in

252
the process. Among these only Cf is widely applied. The properties

of this isotope is summarized in Table 1.3.

252
TABLE 1.3 : Nuclear properties of Cf

Decay Mode

«-emission 96.9 I

spontaneous fission 3.12

Half-life

«-decay 2.731 y

spontaneous fission 85.5 y

effective 2.646 y
12 -1 -1
Neutron emission rate 2.34x10 n. s .g

Neutrons emitted per fission 3.75

Average neutron energy 2.14 MeV

Gamma emission rate 1.3.10 photons.s .g

Dose rate at 1 meter in air

3 -1 ~1
neutrons 2.2.10 rem.h .g

gamma s 1.6.10 2 rad. h' 1 .g" 1

Heat generation 39 W/g" 1

3 -1
Source volume < 1 cm .g

29
 252
A neutron spectrum of Cf is shown in Fig. 1 . 1 1 .

100
oo
^
01
C
01

4J
•r-l
C
3

en
C
o

01
C

(-1
01

n)
,—i
o)

0 2 4
ENERGY (MeV)
252
Fig. 1.11 Cf fission neutron spectrum.

252
From these properties it appears that Cf has a number of advantages

over (a.n)-sources : small size of the source, close similarity of the

neutron spectrum with one obtained from fission of uranium. The main

disadvantage is obviously due to its relatively short effective

half-life of 2.65 y. Thus source replacement has to be planned for.

This can best be accomplished by starting for instance with one source

and increasing the number of source by one unit every one or two years.

One has of course also two consider the financial implicatons of these
24 1
replacements compared for instance with a single purchase of Am-

Be-source. At the time of the Consultants' meeting on "Isotopic Neutron

30
 Sources for Neutron Activation Analysis" in May 19fl5 at the IAEA the
p _ 1
price of a source of 10 n.s were respectively £ 3.500 and 1 £ 26.000
rt f» *J O / 4 i

for Cf and Am so that over 7 replacement would lead to the same

expenditure. Other aspects have of course also to be considered as for

instance the neutron energy spectrum, which might in fact depend on the

considered type of applications.

1.3. Photoneutron sources.

When the y-energy exceeds the binding energy of the neutron in the

nucleus a (y,n ) -reaction can take place. Only beryllium (Q = - 1.665

MeV) and deuterium (Q = - 2.225 MeV) need to be considered since most

nuclei have a neutron binding energy above 8 MeV. In practice only

124
Sb is used as a gamma source. This isotope has a half life of 60.2

d, a gamma of 1.691 MeV and 2.091 MeV with intensities of respectively

;9 I and 6 I.
124
In an assembly as represented in Fig. 1 . 1 3 one curie of Sb will
6
result in an emission of about 3 x 10 neutrons per second. The y-dose

rate is quite high namely of about 10 mGy/h at one meter and can cause

Sb-Be (r = 0.5 cm)

0.3 r„ = 1.0 cm r„ = 1.6 cm . r„ = 2.5 cm

I
0.2

0. 1

10 20 10 20 10 20

Fig. 1 . 1 2 : A Be(y.n) neutron source.

31
 1 24
serious handling problems. The Sb is produced by neutron activation

of natural antimony in a nuclear reactor. In a thermal flux of 10 n.

-2 -1
cm .s one obtains 4 Ci/g from natural antimony. Since the half-life

is only 60 d. reactivation is required 2 or 3 times a year.

For a single y-energy the spectrum is a near monoenergetic neutron

line at 24 keV although some broadening takes place caused by the fact

that all neutron emission angles occur (see equation 1.2).

A Sb-Be photoneutron facility, specifically designed for neutron

activation at thermal energies is shown in fig. 1.13.

Fig. 1 . 1 3 : Sb-Be graphite assembly : 1) graphite, 2) cadmium,

3) beryllium, 4) container with Sb source, 5) samples,

6) rod.

1 24
The Sb is surrounded by beryllium which incorporates channels for

the samples. The beryllium is surrounded by graphite serving as a

further moderator and as neutron reflector. The advantages were de-

scribed as follows.

a) Since the energy of the photoneutrons is only 24 keV fewer colli-

sions are needed for neutron thermalization than for the more ener-
252
getic Cf or Be(a.n) sources.

32
b) The thermal flux gradient at the sample location is small; this can-

not be achieved with hydrogenous moderators.

c) The absence of energetic neutrons reduces the number of interfering

reactions such as (n,p) and (n,a) reactions. On the other hand acti-

vation analysis by means of these reactions is impossible. A silicon

O Q O Q

determination by means of the reaction Si(n.p) Al is not feasi-

ble.
124
d) Since the '"Sb source can be withdrawn into its own shielded con-

tainer, samples can be loaded safely.

1.4. Neutron multipliers.

By surrounding a neutron source with a moderator and enriched

uranium a so called neutron multiplier is obtained. The assembly is

7 - 2 - 1
subcritical but neutron fluxes of up to 10 n.cm .s are possible.

Type R S - 1 multiplier was described Gambaryan (6) and is shown in Fig.

1.14.

Fig. 1 . 1 4 : Schematic drawing of the subcritical uranium assembly

55
RS-1 . (1) Active zone, containing granular UO (U en-
235.
riched to 36 I in U) mixed with polyethylene (660 g
235
U); (2) lead shield; (3) shield of paraffin loaded with

5 I boron carbide; (4) water shield.

33
 o *3 o O *5 C
It contains a Pu-Be source and 560 g U (36 per cent enriched

uranium dioxide granular, mixed with polyethylene). The power is 0.9

7 - 2 - 1
watt and the flux 1.3 x 10 n.cm .s . The advantages of the neutron

multiplier are high flux stability, simple operating conditions and the
possibility to irradiate a large number of samples simultaneously. The

neutron multiplier can be operated for a practically unlimited period.

34
2. PRINCIPLES OF ACTIVATION ANALYSIS

2.1. General equation.

Neutron activation analysis is usually carried out with thermal

neutrons through a (n , y)-reaction, i.e. neutron capture by the target

nuclide :

*M (n.r)A*>

If a target with N nuclei per cm is placed in a neutron beam <t>

-2 -1
(neutrons.cm .s ) then the number of interactions is given by :

.o-.N (cm~ 3 .s~ 1 ) (2.1)

From this one obtains the definition of the cross-section

number of interactions (cm .s )

o- (cm ) = ———————————————————————— (2.2)
«(cm .s ) N(cm )

2
Thus the cross-section is expressed as an area e.g. cm or more practi-
-24 2
cally in barn (1 b = 10 cm ).

If one considers a sample of N nuclei with a cross a. irradiated

in a constant flux <J> during an irradiation time t. according to the

irr
reaction :

a X
> N ————> N (stable)
1 (n,y)' "2 ' "3

where a is the reaction cross-section and X. the désintégration

constant (s ) then if N is considered constant, i.e. the burn-up is

negligible

35
 dN
dt" - N1

Integration between t=o and t. for N = o at t=o gives

«a N f l
N, = ____ 1 - e x p l - X2 t. r r ) (2.0

and

A = X„N„ = O.a.N. \ - exp(- > > t ) (2.5)

where A (in désintégration per second) is the activity of N after an

irradiation time t irr

More complex cases, e.g. several transformations, successive types

of decay, burn-up of N and (or) N should be dealt with by a more

general equation developed by Bateman-Rubinson (7).

If one considers

1 . the isotopic fraction ö of the irradiated element

2. N Avogadro's number, M the relative atomic mass of the element, w

A
the mass of the irradiated element

3. a waiting time t between the end of the irradiation and the coun-

ting of the induced activity

4 . the decay of N„ during the counting tim t

2 m
then the weight of the element to be determined is given by

A.M. _.
w = (2
o.a.NA.s'.e.D.c.e '6)

w NO
as N = ———— D = exp(-Xt.)
1 d
M (2.7)
1-exp(-xt )
S = 1-exp(-Kt ITT ) —— -
Xt
m

36
If gamma spectrometry is applied one has to take into account the peak

detection efficiency e of the detector at energy E and the absolute

intensity y of the gamma ray at energy E .

If one defines the specific activity as

0.N
A = —t?- Q.a.y.e (2.8)
sp M p

and N as the number of désintégrations measured equation (2.6) can be

P
written as

N
(2
S - . D . c'
t .A '91
m sp

Instead of using a single irradiation, waiting and counting times a

number of successive sequences can be performed in order to enhance the

signal to background ratio and improve the precision on the counting

statistics .

Givens et al. (8) derived an equation for the cumulative detector

response and optimisation timing parameters. For the n th cycle the

activity is given by

4 ,, -*T -2XT -(n-l)XT. .„ .„.

A = A.(1 + e + e + . . . e ) (2.10)
n 1

and the cumulative activity is

-XT,, n X T .
n n e ( 1 -e )
A = E A = —————- - —————— (2.11)
e i "XT -XT,2
i=1 (1-e ) (1-e )

where A, is the activity for conventional activation and

T = cycle time = t + t * t
irr w c
n - number of cycles

37
 For a given total experiment time t.= nT the maximum cumulative detec-

tor response occurs when t. = t with t = o. Although t = o is in

irr c w w
practice not feasible t should be as short as possible and the optimum
W

condition of equality of irradiation and measuring time does noet

change.

Actually the signal to background ratio should be maximized by

optimization of the number of cycles. The background will be due to a

number of isotopes present in the matrix and often in a specific case

to one isotope only. Numerical solution of equation (2.11) allows to

determine the number of cycles giving a maximum signal to background

ratio.

2.2. Activation in a Isotopic Neutron Source.

As already described isotopic neutron sources are usually sur-

rounded by a moderator to slow down the fast neutrons to thermal

velocities. Water, paraffine, beryllium and graphite can for instance

be used for this purpose.

In a thermal nuclear reactor the neutron flux is divided into

three components : the fast flux, the thermal flux and the epithermal

flux. The type of nuclear reaction and the cross-section are energy
27
dependent. In the case of Al for instance neutron capture can give
28 *
rize to the compound nucleus Al which can desintegrate in different

modes depending on the neutron energy, each type of désintégration

having its own cross-section :

27
A1 * n
27m
Al + n
28
27 A 1 28 * A1 + y
AI + n ——> Al
27
iAg + P

Na + a
26
A1 + 2n

38
2.2.1.

Fission neutrons have a continuous energy distribution with a

maximum higher than 10 MeV. They can be described by Watt's empirical

equation

n(E) = 0.7725 E 1 / 2 exp(- 0.775 E) (2.12)

The contribution of fast neutrons (above 1 MeV) to (n.y) reactions is

usually small and even negligible. They give however rize to threshold

reactions e.g. (n.n'l, (n.p), (n,«l, (n, 2n). Some of these are used

in activation analysis for instance for the determination of silicon by

op Op
Si(n,p) Al. Conversely they can cause interferences for instance
27 20
for the determination of aluminium by the Al(n.y) Al reaction where

the presence of silicon can give rize to positive errors.

The effective cross section in the fast neutron flux is defined as

rr <»' (
CD
)' (E)dE

—————
E)dE
(2.13)

J n

Values for a in an unperturbed fission spectrum can be found in refe-

rence ( 9 ) .

The reaction rate per nucleus is given by

,2.u,

where 4>T 3 S t is the equivalent fission flux.

The equations and cross sections mentioned above can obviously not be
252
applied for I.N.S.'s other than Cf. For Be(a,n) sources for instance

39
 the neutron energy is not continuous as in a reactor but quasi mono-

energetic around 4 MeV. This means that equation (2.14) and the cross

section values as such cannot be applied, but have to be determined

252
experimentally. Even for a Cf it is quite unlikely that the experi-

mental set-up will give rize to an unperturbed fission flux.

2.2.2. Thermal

Fission neutrons loose their energy through successive collisions

with the moderator until they are in thermal equilibrium. They are

called thermal neutron and follow a Maxwell-Boltzmann distribution.

The most probable neutron velocity at 20*C is 2200 m.s corresponding

to an energy of 0.025 eV. Different conventions can be applied to de-

scribe the reaction rate for ( n . Y ) reactions, as for instance developed

by Westcott and by Stoughton and Holperin. The most practical for acti-

vation analysis is probably the one proposed by Hjlgdahl valid if

a(v) - - (2.15)
v

This is the case for almost all nuclides of interest in activation

analysis .

The neutron flux and thus the reaction rate is divided into two

parts using a Cd-filter. Conventionally a Cd-cylinder is used (height-

diameter 2 / 1 ; wall thickness 1 mm) than a cut-off energy of E = 0.55

eV is accepted. Thus a sample irradiated under Cd is only activated by

epithermal neutrons and the conventional subcadmium flux $ is the sum

of the conventional maxwellian flux plus part of the epithermal flux up

to an energy of the cadmium cut-off.

40
2.2.3. Epithermal neutron flux.

Neutrons loosing energy by collisions with the moderator but which

have not reached thermal equilibrium are called epithermal neutrons.

In the ideal case the epithermal neutron flux per unit of energy

interval is inversely proportional with the neutron energy.

• (E) - (2. 16)

2.2.4. Reaction rate for (n,y) reactions.

By irradiating a nuclide in a neutron flux where two flux compo-

nents are present namely the conventional subcadmium flux <t> and the

conventional epithermal flux <I> the reaction rate will be given by

R = a * + I « (2.17)
os o e

As already stated equation (2.17) is derived from the H6gdahl conven-

tion and is only valid if equation (2.15) and (2.16) are valid.
1 97
If an nuclide for instance Au as an aluminium alloy is irradia-

ted with and without a cadmium filter the respectively reaction rates

will be given by

R,.
Cd = Io O e

= o <t> * I <t
s o e

If a and I are well known equation 2 . 1 7 can be solved for <t> and <!> .
o o s e
Considering eq. ( 2 . 1 7 ) eq. ( 2 . 9 ) can new be written as

(2.18)
t ' Nt . e . y . ( a < S > «• I * J S . D . C . e
m A o s o e p

41
 Values of a and I are tabulated for instance by De Corte et al.
o o
( 10).

2.3. Standardization.

If the neutron activation facility is kept unchanged i.e. source,

moderator, irradiation geometry etc. it is obvious that the flux will

also be constant and the induced activity will only be a function of

iradiation, measuring and decay time. Only the source strength as a

function of time will have to be taken into account. As the decay time

of the source is well known, it should be possible to standardize the

system only once. This can in principle be carried out according to

three methods

2 3 . 1 . Absolute method.

Equation (2.18) allows the determination of the neutron fluxes

from the irradiation of a suitable monitor with and without cadmium.

Hence equation (2.18) can be solved by an absolute measurement of the

induced activity if the désintégration scheme of the isotope of inter-

est is known and the detection efficiency of the detector is also well

known.

This method cannot be considered as practical as to many uncer-

tainties are introduced.

2.3.2. Relative method.

Each sample is irradiated together with a known amount of the ele-

ment (s) to be determined. If the neutron activation facility is kept

unchanged co-irradiation of sample and standards is not required as

42
neutron flux variations do not occur as can be the case with a nuclear

reactor. The standard (s) can either be the pure element or a compound

of known stoechiometry. They can be used separately or as a mixture.

If available, standard reference materials (SRM's) can also be used.

Obviously the result will be given by

N N
P P
w = w (2.19)
X S S. D . C . t € S. D . C . t e
m p X m p

Equation (2.19) only holds if the following conditions are fulfilled :

1. Sample and standard should be exposed to the same neutron flux. If a

flux gradient occurs vertical and (or) lateral as is usually the

case in an isotopic neutron source facility, a correction might be

necessary if standard and sample do not have the same geometrical

dimensions. If this is not the case a correction should be applied.

Obviously this correction has to be determined experimentally.

2. As the neutron flux in a I.N.S. is usually quite modest large

samples are often required to obtain a reasonably high induced

a c t i v i t y . Large samples (or standards) can give rize to neutron self

shielding which can be different in sample and standard. A correc-

tion is difficult to calculate especially for samples with an

irregular geometric shape. In general equations developed to correct

for neutron self shielding should be considered as approximations

and allow to estimate if the effect is important enough to be taken

into consideration. In fact the neutron flux can be modified in the

sample by selfshielding, but the presence of a sample and its

container can change the flux in the sample through flux depression

and neutron scatter. If appreciable amounts of an hydrogen or carbon

compound are present in sample or container the thermal to epither-

mal and fast flux ratio's can be modified.

As the size of an I.N.S. is usually quite small the irradiation

43
 sites are quite limited. For an annular source only one sample or

standard can be irradiated at a time. Although eq. 2.19 corrects for

a difference in irradiation, decay and measuring time between sample

and standard and for a difference in measuring geometry it is obvi-

ous that the greatest possible similarity between sample and stand-

ard should be aimed at.

2.3.3. Single comparator

I.N.S.'s are quite stable and have a constant neutron output (if

corrected for decay) if the facility is kept unchanged. Once the

specific activities of the elements of interest have been determined in

well established conditions samples can be irradiated without stand-

ards. As a precaution for unforeseen changes it is good practice to

monitor the neutron flux within a series of experiments to check if the

neutron flux is indeed unchanged.

2.3.4. k -standardization.

Instead of using the absolute nuclear data and thermal and epi-

thermal neutron fluxes one can use relative values :

9 N
A
A = —rr- (a « + I » J.y.e (2.20)
sp M os o e p

9 N
= —z-M oo 9e (f + Qo }.7.e p

where

(2.22)

and

44
 I
Q =— (2.23)
ao

Thus for a sample and a monitor one obtains

„. 8 M a y f + Q €
A sp - Asp ' —* ' — ' —* • —* • ____°
* • * _£ (2 24)
i'-'*>
M M
e M a y f + Q €
o o p

where the asterix refers to the monitor. Equation (2.24) can be writ-

ten as

A = A * . k .k,.k (2.25)
sp sp o 1 ?

0 M y a
k - _ _ _ _ _ £ (2.26)
o * ' * ' *
0 M y a
o

f * Q
k = ————y (2.27 )
f + û
o

(2.28)
€
P

Obviously eq. (2.24) can be solved if a single monitor is used, e.g. a

gold foil or a gold alloy (0,1 7. gold in aluminium) on condition that f

is known. This value can be determined once and for all if the flux

characteristics remain unchanged. This can be calculated from the Cd-

ratio of a suitable monitor e.g. a gold monitor or from a dual monitor

94 96
for instance the two isotopes of zirconium namely Zr and Zr.

General Conclusion.

1. If the general set-up of a neutron source is kept unchanged, the

neutron output and hence to neutron flux and its energy spectrum

will remain constant, except obviously for the decay of the source.

45
 2. The neutron energy spectrum of the source differs to a considerable
252
extend from a nuclear reactor spectrum, except in the case of Cf.

Indeed fission neutrons have a continuous energy spectrum, the average

energy being appr. 2 MeV and a most probable energy of appr. 0.8 MeV.

Sources of the l « , n ) type are monoenergetic at about 4 MeV, whereas

(y.n) sources produce neutrons at low energy e.g. 25 keV.

Hence the conventional neutron fluxes described for a nuclear

reactor, i.e. thermal- epithermal- and fast flux cannot be applied to

I.N.S's. In practice it is however useful to determine those fluxes by

means of generally accepted techniques.

2.4. Sources of error.

2.4.1. Flux gradients.

As the source size is often rather small important flux gradients

can be expected. These can be determined experimentally by placing a

wire centrally in the sample holder. Pieces of for instance 5 mm can

cut from the wire and are then measured. The lateral gradient at

different heights can be measured by irradiating circular foils which

are cut in sectors. The flux gradient should be measured for the

different types of flux e.g thermal, epithermal and fast if these are

applied. One should also keep in mind that the maximal fluxes do not

always coincide.

In general it is good practice to irradiate samples and (or)

standards of the same size in the same geometry to minimize this type

of errors.

46
2.4.2. Neutron shielding.

As the neutron fluxes are quite small it is advantageous to use

rather large samples to improve sensitivity and count-rate. Non negli-

gible neutron selfshielding effects can thus be important especially if

elements are present with large absorption cross sections. Corrections

are rather difficult to calculate and equations which correct for this

effect are not always reliable.

In fact the neutron flux can not only be modified by selfshielding

but also by the presence of the sample itself or by the use of a

cadmium box.

The total correction for the change in neutron flux as seen by the

sample is due to the product of three effects :

F = FA FD Fs (2.29)

F. = selfshielding ; F. = flux depression;

A D
F = flux scatter factor.

The selfshieding factor can be calculated approximately for foils,

cylinders and spheres

F = 1 - 0.5 d.E (0.9228 + log -1—) (2.30)

A , T 3 € Q

F. = 1 - 4 R.e ; Re « 1 (2.31 1
A, c 3 a a

F4 . = 1 - Re ; Re « 1 (2.32)
A, S a a

where d is the foil thickness, R the radius of an infinitely long

cylinder or the sphere diameter, E the macroscopic cross-section.

47
 2.4.3. Nuclear interference.

2.4.3.1. Threshold reactions.

As already stated in 2.2. the type of nuclear reaction induced

with neutrons depends on its energy. Fast neutrons can induce so called

threshold reaction. As a (n.p) reaction on element Z + 1 or a ( n , or I -

reaction on element Z + 2 can give the same isotope as a (n,y) reaction

on element Z positive errors can occur. This is for instance the case

for an aluminium determination in the presence of silicon, for a manga-

nese determination in the presence of iron or a sodium determination in

the presence of aluminium.

27
Al(n.y)28Al

„-, ,.,
Si(n,p) AI

55
Mn(n.y) 56 Mn

56,- , ,56
Fe(n,p) Mn U

23
Na(n,y) 24 Na

27
Al(n,a) 24 Na

Usually these effects are only important if the fast to thermal

flux ratio is high and if the concentration of the element giving rize

to the interference is a main component.

This type of intererence can be corrected for experimentally by

irradiating the pure element which gives rize to the interference.

2.4.3.2. Fission reactions.

If uranium (or other fissionable material) is present in the

sample, the fission products can give rize to important positive

48
errors, espescially for those elements giving rize to high fission

yields. For a given isotope i the activity of the fission product is

given by (for 1 g of uranium)

A (n.f) = J a(n,f) O.N S /Mu (2.33)

i l Ai
o(n.f) = fission cross section for natural uranium

M = atomic weight of uranium

S' = saturation factor with x. désintégration constant of

isotope i

J = fission yield of isotope i

The activity by (n.-y) reaction is given by

A (n,y) = o(n,r) e*N S./M (2.34)

JL A JL X

so that the ratio of the activities is given by

A (n.f) o(n.f).J .A
_i____ = ______1 x (2.35)
A (n.f) 233.e.o(n.r)

This ratio has the following values :

U1
Ce 0.54
U7
Nd 0.20
9
°Mo 0.85

Once this interference is determined experimentally an appropriate

correction can be applied.

49
 3. PROMPT GAMMA NEUTRON ACTIVATION ANALYSIS (PGNAA)

Capture of a neutron gives rize to prompt gamma rays from nuclear

- 12 -14
excited states. These have half-lives of only 10 to 10 seconds.

These gamma's have energy ranges from about 50 keV to about 10 MeV and

are usually quite complex. It is also obvious that nuclides which give

rize to stable isotopes by neutron capture can also be analyzed;

For PGNAA the measured activity under a photopeak of a gamma of energy

Ey is given by

N = NcTtfl .6 .g. t ( 3 . 1 )
P P
where

N = number of counts under the photopeak of energy E

N = number of nuclides giving rize to a prompt gamma of

energy E
2
a - neutron cross section (cm )
-2 -1
C> = neutron flux (cm ,s )

I = number of prompt gamma's of energy E emitted per neutron

capture

e = detection efficiency at energy E

P y
g = geometrical factor depending on the source-sample-detector

arrangement

t = total experiment time (seconds)

From ( 3 . 1 ) it is obvious that the weight of the analyzed element will

be given by

N .M
.g.t.N A
p A

Using an INS the method cannot be applied for trace analysis but only

for the determination of major and minor elements in bulk samples as

50
coal, ores, minerals and in process stream control. Typical elements

which can be analyzed are hydrogen, carbon, nitrogen, sulphur, sodium,

potassium, aluminium, silicon, calcium, titanium, iron arid chlorine.

An outlay for the onstream analysis of coal was described by Herzog et

al. (10) and is represented in Fig. 3.1.

Sourer drive

Sample Conta iner

Detector Sftie/tf/ng

Fig. 3.1 : Irradiation Facility for PGNAA.

252
Using a Cf-source of 2 mg on a sample corresponding to appr.

120 kg using a Ge detector with an efficiency of 22 7. an analysis is

possible for carbon, hydrogen, nitrogen and sulfur as well as for the

major ash components (silicon, aluminium, titanium, calcium, sodium,

potassium, iron and chlorine). The correlation with independent

chemical analyses was found to be highly satisfactory.

51
 4. THERMAL NEUTRON ABSORPTION ANALYSIS

4.1. Principle.

The neutron absorption of elements with a large neutron cross-sec-

tion as for instance cadmium and boron can be determined in matrices of

low neutron absorption. The attenuation of the neutron flux can be

determined either by direct measurement of the neutron flux for

instance with a BF -counter, or more practically by measurement of the

activity of a suitable monitor. The latter technique measures the

difference in activity induced in the monitor, by neutron irradiation,

with and without a layer of the sample under analysis.

In fact the flux perturbation can be divided into a flux

depression in the vicinity of the sample and a self- shielding effect in

the interior of the sample as shown schematically in Fig. 4 . 1 .

Fig. 4.1 : Schematic representation of flux perturbation factors :

<J> /* =flux depression factor, */» =self-shielding factor. <t>/1> -flux

perturbation factor.

The flux 9> at the surface of the sample is lower than the unperturbed

flux 9 0 . The resulting3 flux

1 -
depression ratio is
S O
» /« . The self-

shielding effect in the interior is due to a significant absorption of

the thermal neutrons by the sample As a result the mean flux 0> in the

sample is lower than * at the surface of the sample. The total effect

of flux depression and self-shielding is given by <&/« .

52
 If the unperturbed flux S>o and the attenuated flux c> are measured,

a quantitative relationship can be expected between the total perturba-

tion of the flux expressed as an absorbance log <J> /* and the amount of

absorbing material. De Norre et al. ( 1 1 ) examined the determination of

cadmium in zinc ores. From the composition of the zinc ores and from

the ratio o /M (absorption cross-section over atomic weight) one can

estimate the effect of neutron absorption of the ma^or and minor compo-

nents of the ore versus the Cd-concentration. This is illustrated in

Table 4.1 where the a 3 /M values are given

TABLE 4.1 : List of the elements, present in the zinc ores, together
with some important characteristics (see text)

Element Cone. range in Concentration a /A, Concentration

zinc ores , 1. in graphite blank. barn equivalent to
#9/9 0.005 7. Cd, 'I.

Cd 0.02 - 1 .45 21 .83

Zn 39 68 .5 0 .0168 6 .5
Fe 0 12 .9 0.2 0 .0457 2 .4
S 0 32 .5 0 .0162 6 .7
Cu 0.1 - 3 .0 0 .0593 1 .8
Cl 0 1 3 0 .931 0 . 12
In 0 0 .03 1 .690 0 .065
B - <0.01 70 . 21 0 .0016
Si 0 1 .6 0.3 0 .00570 19
Al 0 0 .6 0 .00864 12 .6
Ca 0 1 .8 0 01073 10 .2
Mg 0 0 .4 0.05 0 .00259 42
Mn 0.07 - 0 .4 0 .242 0 .5
Pb 0.3 - 20 0 00082 133
As 0 0. 7 0 05739 1 .9
Sn 0 2 .4 0 00531 20 .6

53
 as well as the concentration of the element in 1 giving an absorbance

equivalent to 0.005 7. cadmium.

4.2. Detection of the thermal flux.

Different techniques of monitoring have been applied. Spenke et

c q
al. ( 1 2 ) determined boron in steel using Fe as an internal monitor

whereas Selecki (13) used an indium foil between two layers of the

sample. De Norre et al. (I.e.) used a small cylindrical vanadium moni-

tor inserted into the cavity of the sample as shown in Fig. 4.2.

Fig. i<. 2 : Irradiation geometry applied in this work A = vanadium

detector; B - sample material.

4.3. Standardization.

To determine the imperturbed flux <3> a graphite cylinder contain-

o
ing the v a n a d i u m monitor is irradiated. The induced activity A in the

v a n a d i u m detector is proportional to * . To analyze for instance a

zinc ore a mixture of powdered ore and graphite (ratio appr. 1 : 2 ) is

pressed into a cylinder of the same dimension The activity induced in

the vanadium monitor A proportional to * and is reduced due to the

m
absorption of thermal neutrons by all the constituants of the sample :

54
 A
109
-T = E log (4.1)
m tot i

i = Cd, Zn, Fe. S ....

In practice a calibration is necessary for only for zinc, iron and

sulfur. This is obtained for each of these elements from cylinders con-

taining only these elements in graphite. Fig. 4.3a shows the absorb-

ance of the elements as a function of their masses.

They give rize to a linear absorbance and can be expressed as

A
109 - b.g. (4.2)
A
g
Thus the calibration line for cadmium can be expressed as

A A
0 , 0
log — = log _ * E b .1
g. (A.3)
1
m tot X Cd i

where b. = slope of the calibration line of element i

g. = amount in gram of element i

Fig. (4.3b) shows a calibration line for cadmium. The detection limit

for cadmium is appr. 0.005 7. whereas a relative precision of better

than 1 I can be achieved is cadmium is present at the 1 percent level.

4.4. Other applications.

It is obvious that the same method can be applied to the determi-

nation of other elements with high absorption cross sections. An obvi-

ous choice is boron, sometimes used for instance in special steels.

Other elements as In, Ag and Au can also be determined although they

give rize by neutron irradiation to radio-isotopes which can easely be

measured directly or after chemical separation.

55
 Ig A /A for lOrag Cd

0.020

10
gXgrams)

Fig. 4.3a : Calibration lines for zinc, iron, sulfur and the absorbance
for 10 mg cadmium.

Fig. ^.3b : Calibration line for the determination of cadmium in zinc

ores .

56
5. TRANSPORT SYSTEMS

As already mentioned in 1 . 1 . 8 and shown in Fig. 1 . 1 0 it is

desirable to install a pneumatic transport system to insure reproduc-

ible irradiation and decay times of the samples, espescially when

dealing with short lived isotopes as is often the case. A suitable size

of the pneumatic tubes can be 30 mm. diameter so that sample of 20 mm

diameter can be used in adequate containers made from polyethyleen or

nylon. Such a system can be controlled by timing units to regulate

irradion, decay and counting time, the presence of the samples at the

irradiation site being detected by means of a photocel. A blower and

electromagnetic valves provide the necessary air pressure to transport

the samples to irradiation site and back. The samples can be manually

unloaded and placed on the detector. A distance of ca. 15 m can easely

be covered within 3 seconds. A sample changer and a two way system can

be included to automate loading and unloading of the samples. Automa-

tion of the transfer system can of course also be achieved by means of

a microprocessor as for instance described by De Norre e.a. (14).

The complete system is controlled by a DEC L S I - 1 1 Microprocessor,

consisting of a central processor unit (CPU), random access memory (24K

bytes MOS) and standard serial and parallel I/O i n t e i f a r e s , connecting

the peripherals to the L S I - 1 1 data and adress bus A schematic repre

sentation of the system is shown in Fig. 5.1.

The pneumatic transport system and counting chain are connected to

the L S I - 1 1 bus by a standard DEC parallel interface (DRV-11). This

interface contains three 16-bit registers : DRCSR : control and status

register, DROUTBUF : o u t p u t register, D R I N B U F : input buffer register.

Each operation mode of the transport system and the counting chain

corresponds to a specific numerical content of the DRCSR and DROUTBUF.

57
 Central 12K x 16bit
50 Hz processor
Line clock memory
unit
i
LSI-1 1 bus

Standard Standard
Parallel DLV|] DLV11 serial
Interface I / Q 1[Uerface I/O interface Modified
DRV11 parallel
I/O interface
Pneumatic
transport
control

Transport syst.
position
detectors

Fig. 5.1 : Systematic representation of the automated analysis system.

The DRINBUF register is used for transfer of data from the binary

sealer to the microprocessor memory. The contents of these registers

can be changed d y n a m i c a l l y and conditionally under program control

Thus successive s t a g e s of the analysis sequence can be executed,

skipped or modified automatically by changing parameters in the program

before the start of the analysis run.

A comprehensive program is available to control the pneumatic

sample transfer, irradiation, decay and counting time. A second

program, specific for every analysis problem takes care of the data

reduction and interpretation to provide final analysis results in terms

of normalised and/or corrected count rates and eventually concentra-

tions. For data from the single channel analyser, normalisation, back-

ground subtraction, corrections for differences of the irradiation,

decay and counting periods can be carried out. For the data from the

MCA, peak areas are calculated adapted to the specific problem at hand.

The analyses results can be printed out or saved on disk.

58
6. MEASURING EQUIPMENT

6.1. General.

A large choice of radiation detectors is available today, although

in N . A . A . the most generally used ones are Nal(Tl) scintillation and

germanium semi conductor detectors as they have good detection effi-

ciencies for gamma radiation. Gas filled detectors as Geiger Muller or

proportional counters can of course also be used. They are mainly sen-

sitive to beta-radiation, with all the problems inherent to the meas-

urement of this type of radiation. Their use is rather exceptional and

will not be discussed.

6.2. Sodium iodide detectors.

In activation analysis with a I.N.S. the induced activities are

rather modest. due to the small fluxes usually available, even when

large samples (several grams) are used and minor or even ma^or

constituents are determined. If the spectra are not too complex it is

therefore preferable to use a Nol(Tl)-detector of rather large size 7,5

x 7,5 cm or even 12,5 x 12,5 cm. A well for instance of 30 mm diameter

and 40 mm deep is an additional advantage, as the detection efficiency

is increased as well as the reproducibility of the geometry. Such a

configuration has a detection efficiency of at least one order of

magnitude larger than even a "large" germanium detector and obviously

improves counting statistics and sensitivity of the analysis. The major

drawback of Nal(Tl) scintillators is due to its rather poor resolution

which typically is 8 Z for the 0.661 MeV line of Cs.

As is well known a Nal(Tl) scintillator detector is coupled to a

photomultiplier to which a highly stable high voltage has to be

59
 applied, so that adequate pulses are obtained which can be fed via a

preamplifier to a linear amplifier and a counting system. This can be a

single channel analyzer (S.C.A.) or a multichannel analyser (H.C.A.).

The latter has clearly to be preferred as it gives a complete survey of

the spectrum. In both cases a stable amplification has to be achieved

which is only possible at constant room temperature. Even then a

regular check of possible shifts is advisable. If the counting rate is

high, as might be the case for large samples giving rize to short-lived

species the dead time has to be taken into account. Each detected

pulse in the counting chain needs a finite time to be processed.

During this time called the dead time, a new incoming pulse cannot be

processed and is lost. These losses can be calculated from the equa-

tion :

A = A' - A ' A r (6.1)

A' - A
r -- -——— - (6.2)
A' A
A = A' - A' 2r' (6.3 I

where

A = registered counting rate

A' = real counting rate

T = dead time per registered pulse

T' = dead time per incoming pulse

The counting losses can be determined experimentally by following the

activity of a relatively short lived species with well known half-life.

1 ? fl
The decay curve of I (half life 25.00 mm) is for instance given in

Fig. 6.1.

60
 to
ü 100 150 200
Time (min)

Fig. 6.1 : Counting losses due to dead time in a single channel a n a -

1 28
lyzer (decay of I; T - 25.00 min).

One can see that at a count rate of 2.10 counts per minute the

count losses are smaller than 0.1 1 and allow to determine A' by

extrapolation of the straight part of the decay line.

Fig. 6.2 shows the values of T and r' obtained from equations

(6.2) and (6.4). It appears that neither T or T' are constant as a

function of count-rate and hence that A cannot be calculated from

equations (6.5) and (6.6).

(6.5)
1 - Ar

- /I -
(6.6)
2r'

61
 -o
nj
OJ

2 -

1.10 2.10 3.10 A.10 5.10

Counting Rate

Fig. 6.2 Dead time of a single channel analyzer per registered pulse

(r) or per occuring pulse (r'l

One can conclude t h a t for a certain counting chain and counting condi-

tions (e.g. integral or differential counting) one has to determine

experimentally the dead time and limit the count rate to an acceptable

level. If moreover standard and sample are similar the errors due to

dead time problems will to a large extend be cancelled.

In case of a Nal(Tl) detector used in conjunction with an M.C.A.

the latter will of course be the main source of dead time. This can be

split into three parts due to pulse selection, conversion time and

memory cycle time :

= a (6.7)

T - dead time for pulse registered in channel N

N
a = constant time interval for entering pulse

c - memory cycle time

62
 As a consequence the real measuring time is shorter than the clock

time and increases rapidly with increasing count rate. MCA s therefore

offer a choice between live-time and clock time, the former being

corrected for the dead time. This automatic dead time correction, by

increasing the measuring time is only possible if the counting time is

short in comparison to the half-life. One can correct for this effect

according to equations developed by Junod (15) for counting a pure

short lived nuclide the true activity (in counts per unit of time) is

given by

exp(XDT) A
A' : ———————————— . — (6.8)
1 - exp(-X.LT) DT

where

A' = true counting rate at t - o

A = observed counting rate

DT = total dead time of counting = r.A

LT = total life time

Equations for counting short lived species in the presence of long

lived ones have also been developed.

The complexity of these corrections can however be avoided through

adequate electronic circuits. Bartosek (16) developed a so called dead

time stabilizer which divides the total counting time into a large

number of intervals which are short in comparison to the half-life and

thus corrects exactly for the losses during the counting. Moreover

additional dead time is generated to keep the dead time constant during

the whole measuring time. In practice the ADC is started every 10 ms

and the additional dead time in each measuring interval is equal to the

chosen dead time. This can be chosen between 10 7. and 60 I in steps of

5 'I. . Obviously the chosen dead time should be slightly larger than the

real dead time at the beginning of the measurement

63
 6.3. Germanium semi-c o n d u ctor detectors.

Germanium semi-conductor detectors have the a d v a n t a g e of a much

higher resolution than Nal(Tl) detectors, typically better than 2 keV

for 1 . 3 3 MeV gamma of Co (FWHM). The detection efficiency is however

usually one order of magnitude lower. Lithium drifted germanium detec

tors are now replaced by so called hyperpure germanium detector. They

h a v e the a d v a n t a g e that they can be stored at room t e m p e r a t u r e but m u s t

also be operated at liquid nitrogen temperature. Germanium detectors

are available in different sizes, configurations and geometries. Large

sizes are usually of the coaxial type as shown in Fig. 6.3.

p-type 600 microns

HPGe
Radiation

GEM HPGe Crystal

n-type .0.3 microns

HPGe

Radiation

GAMMA-X Crystal

Fig. 6.3 : Configurations of Coaxial Germanium Crystals.

They are available as p-type or n-type. The latter has the advan-

tage of having a thin sensitive layer of only a few tenth of a micron,

so that low energy gamma's and X-rays are detected with high effi-

ciency. The former have usually an insensitive layer of about 500 am

and thus are insensitive to low energy radiation. This can be an

advantage as high intensity low energy radiation easily gives rize to

64
high count rates and detector overload. Well-types are also available

with well sizes of a diameter of up to 15 mm and a depth of 40 mm. The

advantage is of course an almost 4tf detection geometry but the disad-

vantage of greater probability of coincidences. The configuration can

be either horizontal or vertical. The former is to be preferred for

N . A . A . purposes. It has the advantage of insuring an easier reproduci-

bility of the geometry and allows the use of a Marinelli beaker if

large samples are to be counted (see Fig. 6.4).

Marinelli Beaker

Sample

Ge Detector

Dewar

Fig. 6.4 : Schematic Diagram Showing Arrangement of Marinelli Beaker.

6.4. Detector calibration.

It is important to establish experimentally a number a detector

parameters of both the Nal(Tl) scintillation detector and Ge-semi-

conductor detector e.g. resolution, detection efficiency and energy

calibration. Experimental catalogues of gamma spectra of large numbers

of nuclides are available e.g. Adams and Dams (17) Keath (18).

65
 6.4.1. Resolution and efficiency.

The resolution is usually defined as the full-width of a total

absorption peak, sometimes called the photopeak, at half of the maximum

count rate (FWHM). For Nal(Tl) detectors the resolution is usually

1 37
given in percent for the 0.661 MeV line of Cs :

Resolution CI.} = AE(F ? HM) x 100 (6.9)

This resolution is usually about 8 X. Detection efficiencies are avail-

able in compilations such as those from réf. (17) and (19).

For germanium detectors the resolution is usually given in keV at

60
FWHM for the 1332 keV line of Co. It is also usefull to determine

the full width at one tenth of the maximum (FWTM) as this gives an

indication of the gaussian symmetry of the peak. Resolutions of better

than 2 keV are achieved. Detection efficiencies are referred to

Nal(Tl) scintillators of 7.5 cm x 7.5 cm and vary according to the size

(and price) between a few and 30 '/.

The detection efficiency, is of course a function of energy. The

total efficiency e is correlated to the peak of total absorption by

e =
t "P7T (6-10)

where

P/T = peak to total ratio.

The P/T ratio as a function of gamma energy is given by

log (P/T) = a log E + b ( 6 1 1 )

where a and b are constants depending on the measurement conditions and

the detector. Eq . (6 . 11 ) does not take into account absorbing or scat-

66
tering materials surrounding the detector. In practice € is measured

by means of calibrated point sources with known absolute activity A

(désintégrations per second) and known absolute gamma intensities.

Usefull source are given in Table 6.1. together with the half-

lifes, gamma energies and intensities. Typical results for e as a

function of energy are shown in Fig. 6.5.

TABLE 6.1 : Calibration sources for gamma spectrometry.

Isotope T E (keV) y Isotope T E (keV) y

133 226
Ba 10.5* y 53. 15 .01950 Ra 1600 y 609.32 .4426
61.00 .3904 (continued) 665.45 .0-1492
356.01 .6240 768.36 .04736
806. 17 .01208
Oil

Am 458 y 59.5* .3530 839.03 .005577

C "T

Co 271 .8 d 122.06 .8554 934.05 .03054

136.48 . 1066 1120.28 .1469
1238. 11 .05710
IS? **
Eu 13.5 y 121.78 .2821 1280.96 .01385
244.7 « .07423 1385.31 .007923
295.94 .004231 1401.51 .01301
344 . 38 .2641 1509 19 .02080
367 76 .008401 1661 .28 .01076
411.3 * .02301 1729 60 .02833
444.0 * .03077 1764 .51 . 1509
564.5 « .006133 21 18 .54 01177
688.6 « .008493 2204 . 12 04957
778.90 . 1300 2293.36 .002988
867.38 .04161 2447 71 015U
964 .0 * .1448
137
1068 4 * . 1 184 Cs 30 2 y 661 60 8462
54
1112.0 * . 1355 Mn 312 2 d 834 81 9998
1212.94 01390
88
1298 7 « 01743 Y 106 6 d 898 04 .9340
1408.03 .2071 1836 13 9940
226 *** 60
fia 1600 y 186 02 .03408 Co 5 272 y 1173 21 9988
241 91 .07082 1332 49 .9998
274 53 .005178 Na 2 604 y 511 0 1 811
295. 17 .1810
351 90 3510 <£*!
487.08 004342 1274 51 9995

67
 i

10

-4
10
10 10 E (keV)

Fig. 6.5 : Experimental peak efficiency curve for point sources.

6.4.2. Energy calibration.

Gammaspectrometry is mainly applied with multichannel analysis and

the relation between the obtained poise height or corresponding channel

number versus gamma energy has to e established. The same sources used

for efficiency calibration can be used to calibrate this relation.

Theoretically this relation should be a linear one. However due to

imperfections in the pulse amplification and/or) the analogue digital

converter (ADO this relation is not always perfectly linear. It is

therefore better to carry out a polynomial bit and check the fitting at

regular time intervals (for instance before the start of a series of

24 1
measurements) by means of a source of low and high energy, e.g. Am

and Co. A typical polynomial fit is given by equation (6.12)

68
 2 3
E(keV) = a + a,k + a„k + a.k . .. . (6.12)
o l i. J

E = energy in keV

k = channel number

a proportionality constants
n
Typical values for a were found to be

a = - 1.4426;
o
a, = 0.50159

= - 0.13315. 10

0.408148.10"
-13
a = - 0.434911 .10

6.4.3. Evaluation of the gamma spectra.

Erdtmann and Petri (20) give a survey of the different steps in

the evaluation of gamma ray spectra as shown in Fig. 6.6.

Evaluation of Gamma-ray Spectra

Steps of the procedure Data required

Search for the peaks

i
Determination of peak situations Parameters ol energy calibration curve

i
Calculation of gamma-ray energies Gamma-ray energies found

i Parameters of efficiency calibration curve

Calculation of peak areas Measuring time

I
Calculation of gamma-ray emission rates Nudide data (Gamma-ray energies and abundances.
/ half-lives, production modes)
i
Identification of the radionuclides

I Decay time
Calculation of radionudide decay rates
^ Irradiation time
^-^' __ Neutron flux and cross sections or
^^^^ Results from reference samples
Calculation of amounts of elements V'

Fig. 6.6 : Steps for the evaluation of -y-ray spectra and the calcula-

tion of activation analyses.

69
 Commercial M.C.A.'s usually provide Programms for most of the steps

given in Fig. 6.6. In activation analysis with an I.N.S. the spectra

are not as complex as those encountered in reactor activation analysis

and a manual evaluation of the spectra is not too much time consuming.

The peak search can be omitted if the peaks are intense enough to be

identified visually. Calculations of the peak area is best carried out

by an integration procedure as explained from Fig. 6.7. (I.e.)

CD
C
C
«
o

ö
o
o

B,
W
^1 *-2 3 ~4
Channel number (c)
Fig. 6.7 : Calculation of peak area by integration The peak area is

F , B and B are used to calculate B , the background under

p 1 r p
the peak .

The net peak area F is the area between channels C„ and C_ above the
p 2 3
dashed line and is obtained by summing the counts in channels C + 1

up to C -1. The background is assumed to be linear and corresponds to

the trapezoid B below the dashed line. The height of the left and
P

7C
right borders of the trapezoid are calculated from the mean over sever-

al adjacent channels.

Thus :

B B
[W1
1 c [C2- V 1 C4-

where
'2 ;
C n and 8 =E n
C C
' 3

The standard deviation on the peak area F is given by

s
c2;'^, •« •
2
B.
1
B
r
rc 3 -c 2 -n
+
————————
(l r r 1) 1 \ 2 ————————
(t r r \2
^n 2
W VS- J

71
 7. SAMPLE PREPARATION

As already described earlier a annular source or an array of

sources is to be preferred to a single source, namely to enhance the

neutron flux and to reduce flux gradients The type of I N S arrange-

ment limits of course the sample size. This is obviously also the case

if a pneumatic transport system is installed. In any case it seems

desirable that all the dimensions are chosen in such a way that samples

of a diameter of appr 20 mm diameter can be irradiated and that

source, pneumatic tube and sample holder (rabbit) are of corresponding

sizes As always in neutron activation analysis it is good practice to

use a standard which closely approximates the sample In the case of

powdered samples this can be achieved by mixing carefully the different

components as their oxides or components of well known stoechiometry.

As flux gradients and neutron absorption phenomena can be important two

alternatives are possible to avoid systematic errors :

1. The powders are homogenized after irradiation

2. The powders are pressed into cylindrical pellets under addition of a

binding component. This can be a wax or graphite. A proportion of

about 2:1 sample and graphite or wax are sufficient to obtain

mechanically resistant pellets of a size of 20 mm in diameter and 10

2
mm height at a pressure of about 400 kg/cm . A manual or hydrolic

press can be used for the purpose. One has however to keep in mind

that it is important to obtain pellets of identical size as this

affects the irradiation as well as the measuring geometry.

Obviously the second alternative is the best one as it allows quite

large samples to be reproduced accurately. If a press is not available

the powder, with or without binding agent can be pressed into the

72
sample holder and spacer can be used to fill up the container

completely so that the sample cannot move during transport.

If the sample is not available as a powder e.g. a metal, it can be

machined precisely to the desired size.

73
 8. APPLICATIONS

General Remarks.

It is assumed that an annular neutron source is available yielding

fi —?
a neutron flux of approximately 10 n. cm .s and that samples can be

irradiated with a diameter of 20 mm. A different neutron fluxes and

(or) sample size will obviously increase resp. decrease the induced

activity. Measurement are carried out with a Nal(Tl) detector of 7.5 x

7.5 cm with a well of 3.3 cm deep and A.3 cm diameter. Other sizes of

detectors will of course influence the detection efficiency and count

rate. This type of detector can be coupled to a single channel or a

multichannel analyzer. As another alternative a germanium semi

conductor, preferably hyperpure. can be used, with an efficiency of

about 20 I and a resolution of 2 keV or better, coupled to a 4000

channel analyser.

As already stated earlier the rather modest flux of a I.N.S. does

only exceptionally allow the determination of trace elements. There-

fore the main applications are in the field of minor or major

components where good precision and accuracy can be obtained. To

insure a reproducible geometry during irradiation and counting,

powdered material, e.g. biological, ores, metals, etc. can be mixed

with powdered graphite or wax in a 1:1 or 1:2 proportion and pressed

into a cylindrical pellet.

6.1. Determination of silver in lead.

8 . 1 . 1 . Introduction.

Silver present in ores is often concentrated in lead by heating in

74
the presence of lead oxide and a reductant. This gives rize to metallic

lead in which the silver is concentrated. The determination is usually

carried out by cupellation, i.e. by heating in an air stream. The lead

is transformed into oxide and taken up by the cuppel, leaving a

metallic silver bead which can be weighed.

8.1.2. Nuclear data.

Irradiation of silver gives rise to three radioactive species as

shown in Table 8.1.

TABLE 8.1 : Nuclear Data of Silver.

Stable Abundance (n, r) oo Io T...

1/2
E (keV)
y
+

Isotope product (b) (b) abundance (l)

107 51.83 108 37.3 96.0 2.37m9 {0.

433.
50Z)

618. 9 (0. 26Z)

633. 0 (1 .76Z)

109 48.16 110 88 1400 24.6s 658 (4. 5Z)

110m 3.90 69.0 249. 8d

8 (94
657.
.5Z)

A number of other element present in lead e.g. copper, zinc, antimony

and tin do not interfere as their concentration is usually very low.

In practice an amount of 1000 ppm of Cu or Sb results in an apparent

silver content of only 5.2 and 2.3 ppm, whereas zinc and tin are

completely negligible at their normal level.

75
 8.1.3. Equipment.

Well type sodium iodide détecta 7.5 cm x 7.5 cm with Multichannel

analyser, well of 3.5 cm x 4.3 cm.

8 . I . A . Sample and standard preparation.

Cylindrical samples of 5 + 0.1 mm height and 20 + 0.1 mm diameter

are machined from available lead ingots. This corresponds to a weight

of 1 7 , 5 gram. Standards are prepared by smelting in a quartz crucible

high purity silver foil (99.9 Z) cut into fine bits with lead grains.

All smeltings are carried out in a hydrogen atmosphere to avoid the

formation of lead dioxide. After heating for 30 minutes under a

hydrogen stream on a bunsen burner at appr. 550 "C the liquid smelt is

poured in a graphite mould preheated a temperature just above the

smelting point of lead (327 *C). The graphite mould is immersed in

cold water to avoid silver concentration gradients. Standards

containing between 250 and 4000 ppm can be prepared in this way.

8.1.5. Irradiation and counting conditions.

The lead samples or standards are introduced in a suitable poly-

ethylene container and are irradiated during 60 s, and counted during

60 s after a decay of 10 s. The spectrum of Fig. 8.1 shows an intense

Pb-X-ray fluorescence peak and a photopeak at 658 keV. The sum of the

counts is taken as shown in Fig. 8 . 1 . For the given conditions a net

activity of about 5000 counts per minute and per 1000 ppm of silver is

obtained with a background of about 1000 counts per minute. For silver

concentration at the 1000 ppm level the precision is approximately 1 Ï.

16
 3000

0)
C Pb X-Ray
C
m 72 keV
.c
o

c
o
CJ
2000

110
Backscatter
1000

50 100 150 200

Channel number

Fig. 8.1 : Spectrum of Ag.

8.2. Determination of manganese in pyrolusite and ferromanganese.

8.2.1. Introduction.

Pyrolusite is an important ore containing 30 Ï to 50 Z manganese.

It is used as such in the iron and steel industry or is transformed

into ferromanganese with a manganese content of 75 I to 80 I. Manganese

determination in these materials require a high precision of a few

tenth of a percent. A titrimetric procedure is usually applied for the

purpose namely the pyrofosfate or bismuthate methods. Typical pyrolusi-

te and ferromanganese compositions are shown in Tables 8.2 and 8.3.

77
 TABLE 8.2 : Chemical composition of some pyrolusites.

N Mn Fe SiO A1 P Ca Mg S
2°3 2°5 ° °

(1) 48.46 5.36 2.88 5.86 0.237 0.00 0.45 0.009

(2) 5*. 20 9.71 5.93 0.235 0.119 3 . 6 1 0.42 0.021

(3) 51 .19 12. 1 4.80 0.37 0.13 2.90 0.40

(4) 37.68 16.5 1.75 0.2

TABLE 8.3 : Chemical composition of some ferromanganese.

Mn Fe C Si

(1) 78.48 13.38 6 . 8 7 0.279 0.155 0.008

(2) 77.83 1 3 . 4 57 . 0 0 0 . 1 4 8 0 . 1 4 1 0.021

(3) 75.84 1 6 . 1 0 6 . 8 8 0.229 0 . 2 1 60 . 0 3 4

8.2.2. Nuclear Data.

The relevant nuclear data of the major components of pyrolusite

and ferromanganese are given in Table 8.4.

78
TABLE 8.4 : Nuclear Data.

Stable Abundance (n.y) or o l T... E (keV) +

o o 1/2 y
Isotope (Z) (n.p) (b) (b) 2 abundance

product

55 56
Mn 100 Mn 13.3 14.0 2.5785h 846.8 (98.9Z)
27 28
AI 100 Al 0.226 0.16 2.240 m 1778.9 (100Z)

1810.7 (27.2Z)

2 1 1 3 . 1 (14.3Z)
49
Ca 0.0019 Ca 1 . 1 2 0.50 8.719 m 92.1 (0.8Z)
3 31
°Si 3.10 Si 0.107 0.710 2.622 h 1266.2 (0.07Z)
26 27
Mg 11.01 Mg 0.0372 0.024 9.458 m 170.7 (0.84Z)
51. 52.
99.75 4.79 2.63 3.75 m 1434.0 (100Z)
56 56
Fe 91 .7 Mn 0.0009
28 28
Si 92.21 Al 0.02

8.2.3. Interferences.

From the data of table 8.4 it is possible to calculate the induced

activities for instance in pyrolusite 2. The activation by epithermal

neutrons was neglected, considering the high thermal to epithermal flux

ratio, whereas a thermal and fast flux of 10 n.cm .s was assumed.

The results for a 1g sample are represented in Fig. 8.2.

It appears that the most important interference is due to 28.Al. at the

end of the irradiation. The interference due to Si is completely

negligible as the gamma intensity is only 0.07 Z. The other elements

Ca, Mg and P also induce negligible activities if gamma spectrometry is

applied with a Nal(Tl) detector. Some pyrolusites contain traces of

51
vanadium. Even at a 0.1 Z level the interference due to the V(n.y)

79
 10-
56,
Mn(from n,y)

10
to
4J
C

o
Ü

IQ-
U
Ü

28
Al

31
10 Si
48
Ça
56
Mn(from n,p)
27
Mg
-1
10

40 80 120 160
Irradiation cime (min)

Fig. 8.2 : Calculated activity in pyrolusite 0970/677 as a

function of irradiation time (A - t ).

thermal fast

52
V reaction is entirely negligible. Some pyrolusites show a small

natural radioactivity mainly due to the presence of members of the

? *\ ? ? T ft
Th or U series. This activity can reach an integral count rate

of about 250 counts per gram and per 1000 seconds. It introduces a

positive error of only 0.08 I. For the analysis parameters given

elements with large absorption cross-sections (e.g. B, Cd, rare earths)

present in some pyrolusites, for instance B in those from South African

origin, can cause additional neutron shadowing effects in large sam-

ples. If the sample size is limited to 3 g (see further sample size)

80
this effect is also negligible. The activity induced by the threshold

reaction Fe(n.p) Mn is also negligible as it is five orders of

cc cc
magnitude lower than the one induced by the Mn(n,r) Mn reaction even

when the Mn-Fe-ratio is 5 : 1 .

8.2.4. Neutron and gamma-ray attenuation effects.

Due to the large sample size (3 g for pyrolusite with 1.7 g wachs;

9.8 g ferromanganese and 0.96 g wachs) and the large thermal neutron

cross-section of manganese, considerable self-shadowing effects do

occur as well as gamma-ray attenuation. If samples with constant

amounts of pyrolusite or ferromanganese are irradiated and measured the

resulting count rate is in fact influenced by both the neutron and

gamma attenuation effects. Moreover flux attenuation can occur within

the individual particles. To avoid this effect the particle size

should be kept smaller than 40 tim.

If the measuring conditions are kept constant (see further 8.2.5)

as well as sample size and sample density one can establish a net

neutron attenuation effect as shown in Fig. 8.3. The specific

activities are obtained from samples with known manganese content. One

can conclude that the calibration lines are linear for a manganese

content between 1 g and 2,5 g.

8.2.5. Measuring and irradiation conditions.

As already mentioned above a well type Nal(Tl) detector is used

coupled to a single channel or multichannel analyser. If the former is

used the base line can be set to include the back scatter peak, whereas

the upper limit should include the 2 1 1 3 keV line. If a MCA is used

channel summation should be applied to include the same energy region.

81
 165 _ x 10-3

o
0)
01

O
o
o
y=-(10847+340)x +(174509+590)
160

155
y=-(11033+280)x +(174202+530) .

150 O ferromanganese

• pyrolusite

J_ _L
1.0 2.0
Gram Mn

Fig. 8.3 Net-neutronattenuation curves for pyrolusite and

ferromanganese.

fl
If a source of 10 n.s is available the following sequence can

be applied :

Irradiation time : 200 s

Decay time : 800 s

Measuring time : 800 s

82
 6
This results in a total count of appr. 10 for samples with the

following compositions :

3 g pyrolusite + 1.7 g wachs

9 g ferromanganese + 1 g wachs

After mixing carefully they are pressed into pellets of 20 mm diameter

2
and 7 mm height at a pressure of *00 kg/cm . If other sizes are used

the calibration curves will obviously be different.

8.2.6. Calculations.

From a calibration line as shown in Fig. 8.3 the manganese content

can be calculated by successive approximation :

Mn , x A A
""... --TT—-rr:
st,1 st. 1

Mn = weight manganese in sample, first approximation

Mn = weight manganese in standard

A = number of counts in sample

S

A = number of counts in standard

S = specific activity of standard

S ^ ,. has to be corrected for the neutron attenuation difference

st, 1
between Mn st,
^ 1. and Mn st

S . , = S . . + (Mn . - Mn .) x R (8.2)
st, 2 s t . 1 s t , 1 st

where R is the slope of the self-shielding calibration line of Fig.

8.3. Usually the second approximation is within 0.1 Z of the third with
8 -1
a source strength of 10 n.s and the experimental conditions given. A

precision of better than 0.1 1 can be achieved for a triplicate

analysis.

83
 8.3. Determination of silicium and aluminium in bauxite.

8.3.1. Introduction.

Bauxite is an important raw material for the aluminium industry

Hence a rapid and accurate analysis is of great importance in the

bauxite exploitation site as well as in the aluminium industry itself.

The most precise analytical method is still the gravimetric one but is

very time consuming. Instrumental methods as X-ray fluorescence,

atomic absorption, atomic emission a.o. are also time consuming and

often laborious sample preparation and (or) dissolution is required.

Through neutron activation analysis with an I.N.S. fast instrumental

analysis can be achieved within less than 15 minutes with a precision

of better than 1 1. .

8.3.2. Nuclear data.

07 po
Aluminium can be determined through the reaction Al(n,r) Al

with thermal neutrons, whereas silicium is determined via the reaction

p n p D
Si(n,p) Al with fast neutrons. This can be achieved through a

double irradiation technique for instance with and without a cadmium

filter. Typical compositions of bauxite are given in Table 8 1.

From the composition given in Table 8.5 it appears that a number of

correction may be required due to the presence of Fe, Mn, Ti, V and P.

Pertinent nuclear data are given in Table 8 2.

c r RC RC
The correction for Mn induced by the reactions Fe(n,p) Mn and

Mn(n y} vary between 0.1 to 1.0 I. depending of course on the Fe and

Mn contents and can be corrected for by a measurement after the decay

pp p/ cc
of Al. The presence of Na interferes however with the Mn

84
 Z 0 CT> O in co r^ 0,
1 CO fO m OO CN — O 0 0
X • . . • 1 1 1 I I 1
pa ^ r^ i— CN CN o 0 0 0 0
in *~ CNl

vO
in
r-
^o
•
O
*_. O
cr,
O
CNl
O
f~^ O
*—
T—
X 00 « 1 1 - 1 1 1 1 1 1 1
pa <r CN CN * 0 CN o O

vD
CN co oo o i— 0 CJ*
,— 0 CN oo cn o o
X <r . « « i t ' l l 1 1 1 1 1
pa <f m CO O p^ CN 0 0
CO CN CM

o CO OO
cr\ m OO CM <r 0
X CT* 1 1 1 1 1 1 1 1 1 1
pa CM o o «— <J- CN 0
^0 CO

o oo CN
^j-
o CN
X r- CO 0
pa CM . . • 1 1 1 1 1 1 1 1 1 1
v£> 0 <r ï^ o 0
CN CN
"*

CTi
in r^ r^ m i^ O m
X co vO -a- -a- CM <y vO o
pa CN • « • i i - l l 1 1 1 1 1
CN -r— vO CO CN CN O
"* ^~ CM

_ CN u-l O
^
CN vD
(^ v_
tn cr. CO CO O
X CN . » 1 1 • 1 1 1 1 1 1 1
pa CN 0 oo CN ^3- CN O O
CM
"* *~

^
0 CO 0 vD in vD
LO n r^ CO 0
X CT> • • * 1 1 - 1 1 1 1 1 1 1
^J- ro o-i CNl CN CN O
m CM

tn o m CN o %
X co CO i^^. ^j- MD CTi ^o O
0) pa — . • • • 1 1 - 1 1 1 1 1 1 1
CN \JT) «—
i
v£5 CN o O
m CN

CN
m -T r-^ m CN in ^J-
x — -<r 1— m r^ OO CNl O
4-1 pa — . . . . 1 1 - 1 1 1 1 1 1 1
O 01 0 i— m CN 0 0
-3- CNl
C
o
•H
U
• 1-1 O in CM 00 Oï oo co ro in — CN *— — *— <r
W on <! o 0 iTi
. co OJ — C 0 0 0 o o o o o
O
pa o-. • • . . • • • • • * > • • •
^o o^ m CN o O O O O O o o o o o
i-
"Z. M3 U"l
U"l CN
v v v
o
o
1 U)
co u)
1/1 !-i 0
OJ •— 1
oo f~\ G CO CO
O CsJ •H C O CN CM in in o o
W CN o o o CN O o O O O CM O O O CN O co
•J ,—i •i-4 C -H QJ .,-4 n U CM fN U CO M C « C N O
pa < w M iJ In H o N: cu > c_) pa s: z: K & <s>

85
 measurement so that a correction is n e c e s s a r y , e s t i m a t e d from the

approximate aluminium content.

T y p i c a l d e c a y c u r v e s are shown in Fig. 8.4.

28
10 - Al (2.24 rain) pos 1
28
Al (2.24 min) pos 2
27
Mg (9.45 min)
u 24
CD
CO
Na (15.02 h)
O
O

0
O
O

10

10

30 60 90 120 150
time (min)

Fig. 8.* : D e c a y c u r v e s of p u r e Al (99.99 Z) in p o s i t i o n 1(«)

and in position 2(A).

86
 These decay curves were obtained by irradiating at position 1 and

2 corresponding to a high and low fast to thermal neutron flux as shown

in Fig. 8.5.

12

• r-l
O.
0>
•e.

I
en
a
•e-

Û 2 4 6 8 0 2 4

Height from bottom of irradiation place

Fig. 8.5 : Ratio 0 j./*,.. , and 0.. ,/0 ... , as a

—-——— fast thermal thermal epithermal
•function of height from the bottom of irradiation

place.

The interference due to Ti is negligible for a Ti-concentration

31 28
of _+ 3 I in bauxite. The interference due to the reaction Pin,a) Al

is also negligible for fosfors concentrations below 0.2 I.

As shown in Table 8.6 vanadium can occur in concentrations of up

52
to 0.12 1. As the V activity is short lived (3.75 m) with a gamma-
oo
ray at H34 keV it can not be separated from Al. Only the knowledge

87
 TABLE 8.6 : Nuclear data for neutron activation of bauxite.

Reaction Isotopic Cross section Half-life ^-energy

abundance 1 (mb) (keV)

28
SKn,p)28Al 92.21 2.0 2.240 m 1778.9
29 29
Si(n,p) Al 4.7 0.6 6.52 m 1273.3
3
°Si(n, a > 2 7 M g 3.09 0. 1 9. 458 m 843.8; 1014.4
2?
Al(n.y) 28 Al 100 0.231.10' 2.240 m 1778.9
27
Al(n.p) 27 Mg 100 4.3 9.45 m 843.8; 1 0 1 4 . 4

AKn.a) Na 100 0.65 14.959 h 1368.6;2754 .0

56
Fe(n.p) 56 Mn 91 .7 0.9 2.5785h 846.8; 1810.7;

2113 1
56
Mn(n,r) 5 6 Mn 100 13 .3. 10 J 2.5785h 846. 8; 1 8 1 0 ;

2113 1
5
°Ti(n.y)51Ti 5.4 0.171 5.752 m 320. 1 ;928.6
51
V(n,r) 5 2 V 99.75 4.88.10' 3.75 m 1434 .0
31
P(n,«) 2 8 Al 100 1 .3 2.240 m 1778.9

of the approximate vanadium concentration allows for a correction. In

the given irradiation and counting conditions (see further) it amounts

for aluminium oxide to a positive error of appr. 1 I absolute for 0.1 '/

vanadium pentoxide and to a negative error on silica of appr. 0.6 I.

One should also note that certain bauxites contain a non negligible

amount of natural radioactivity due to the 4n (thorium 232) and 4 n + 4

series (uranium 238). In some cases this amounts to 1200 counts per

300 seconds and causes a positive error on alumina of 1.4 1. A measure

of the sample before activation allows obviously to correct for this

effect.

88
8.3.3. Sample preparation, irradiation and measurement.

Finely grinded bauxite (particle size below 40 am) is mixed with

wachs (ca. 4.5 g bauxite and 0.9 g wachs) and pressed into a pellet of
2
8.5 mm height and 20 mm diameter at a pressure of 400 kg/cm . The

pellet is measured in the same conditions as after irradiation to

determine the natural radioactivity. One pellet is first irradiated in

position 1 (optimal fast flux) and one in position 2 (optimal thermal

flux). If this is not feasible one irradiates in a cadmium box (wall

thickness 1 mm) instead of position 1. The irradiation time is 200 s

A 4

for a source strength of appr. 10 n.s . After a waiting time of 40s a

first measurement is made during 300 s. The detector is a well type

crystal as already described. Integral counting is applied with a

S.C.A. at a threshold lower than the backscatter peak. A second

counting of 300 s is taken after a 100 second decay i.e. after complete
no of
decay of Al and Mg. A possible scheme of analysis of a triplicate

sample is shown in Fig. 8.6.

The alumina and silica content can be calculated as follows :

A, . = a w . + b WA, (8.3)
1 , net si Al

A . = c w . + b w4, (8.4)
2, net si Al

where

(A - BG) - (A - BG) x k
(8.5)
,net w.b

(A - BG) - (A - BG) x k
A, . = —:————————-————— (8.6)
2,net w.

89
 transport of sample to detector 300 s measurement
(decay = 40 s) for Mn correction

200 s irradiation 300 s measurement

W
,-J
o.
D
D
D
D
D
, 28A1 . 27M D
decay of Ai and Mg D
D
D
,D

40 80 120 160 200 240

Time (min)

>•' i 8 •_ 8. b : Analysis scheme for simultaneous determination of Al.,0- and SiO„ in three bauxite ores
with 6 standardized pellets for each ore.
A ;A = total count of 1st measurement in position 1 resp. 2

A' ;A' = total count of 2nd measurement in position 1 resp. 2

BG = background including natural radioactivity

k = correction factor for decay of Mn between 1st and 2nd

measurement i.e.

, .0.693 x 108.

a.c = silica coefficients i.e. specific activity due to silica

after irradiation in position 1 resp. 2

b,d = alumina coefficients i.e. specific activity due to alumina

after irradiation in position 1 and 2

Sl
wO l = °9C weight per gram bauxite

w., = Al„0^ weight per gram bauxite

Al 2 3
w = bauxite weight in sample,

By solving equation (8.3) and (8.*) one obtains a first approxima-

tion of w.Si
and w4Al
, from the results of equations (8.5) and (8.6).
24 56
These results do not take into account the activity of Na in the Mn

measurement. It can be calculated as follows

(A - BG)-[(A - B G J - t A , x w..)] x k

W
b

(A - BG)-[(A - BG)-(A x w )] x k
A" = -J ———————— ?———————2-——— £ ————— (8.8)
2, net
W
b

where
24
A" and A" = Na activity during the second measurement in

irradiation position 1 and 2 as measured from dedecay curve from pure

Al 0 pellet irradiated and measured in the same conditions as a

sample .

91
 Values for the irradiation and measuring conditions given are as

follows :

a = 35.710 b = 49.479

c = 6.092 d = 41.994

A1^ = 110 A"2 = 25

24
It is apparent from this data that the Na correction is quite small

and can be neglected for many practical purposes.

It appears that with the method described above an absolute precision

of better than 0.5 I can be achieved for both alumina and silica.

8.4. Determination of silicium and aluminium in aluminium-silicium

alloys.

8.4.1. Introduction.

The silicium content of silicium-aluminium alloys varies between

0.5 Z and 13 Z. The composition of typical alloys is given in Table

8.7.

TABLE 8.7 : Concentration (%) of elements present in Si-Al-alloys

Si Fe Cu Mn Mg Zn Ti Cr Ni V Ca

13.4 0.91 0. 10 0.57 0.75 0. 156 0.60 0.53 0.12

13.0 0.15 0.01 0.015 0.01 0.05 0.02
10.8 0.35 0.02 0.35 0.006 0.07 0.01
10.0 0.29 0.035 0.22 0.22 0.054 0.007 0.009 0.035
7.95 0.14 0.010 0.054 0.45 0,097 0.15
6.3 0.67 0. 11 0.65 0.80 0.125 0.10 0.07 0.045
4.65 0.42 0.30 0.39 0.44 0.032 0.025
0.975 0.23 0.005 0.31 0.80 0.091
0.99 0.62 4.91 1.25 1.64 0.096 0.094 0.094 0.10
0.50 0.54 0.040 0.038 0.033 0.079 0.048 0.036 0 040 0.046

92
As described further a single irradiation of the alloy under cadmium

cover allows a rapid determination of silicium with a precision better

than 0.1 Z absolute.

8.4.2. Principle.

From Table 8.3 it appears that by using an irradiation under

cadmium and a discriminator setting at 1400 keV interferences in the

29 29
silicium determination due to the reactions Si(n,p) Al,

Si(n.a) Mg and Al(n,p) Mg are eliminated whereas those due to

97 9 Z. Rfi RC *} L.
Al(n.a) Na and Fe(n.p) Mn are greatly reduced. The residual Na

activity can be taken into account, whereas the Mn-activity is

completely negligible, due to the small iron and manganese content of

the alloys.

8.4.3. Standardization and calculation.

The specific activities of aluminium and silicium are determined

by irradiating pure silicium and aluminium having the same dimensions

as the samples i.e. cylinders of 6 mm height and 20 mm diameter. As

already mentioned they are irradiated in a cadmium box with wall

thickness of 1 mm. For an irradiation at the site of maximal fast flux

of 200s and measured during 300s after a decay of 40s in the well-

type Nal(Tl) detector a specific activity of approx. 21.000 counts is

obtained per gram silicium and appr. 800 counts per gram aluminium
24
including about 90 counts Na.

The silicium content is now calculated by successive approxima-

tion :

93
 (8 9)
-
where

SA : specific activity of silicium in the sample, SA being the

28 24
first approximation, i.e. including the Al and Na acti-

vity

SA : specific activity of silicium in the standard.

The first apprimation for aluminium is given by

C 10 (8
A1.1 * ° - Si., '10)

By comparing the specific activity of the aluminium standard one

obtains a first approximation of the activity of the aluminium in the

sample :

SA = SA SA (8 11)
s,2 s.i - AI • -TOIT -
where

SA : specific activity of the pure aluminium standard

Al

The new value of SA can be introduced in equation (8.9) and the

j,t
sequence repeated until

ISA - SA )
——iiü————— S| "" 1 < 0.001 (8.12)
SA
s.n

This is the case for n = 4.

In the above procedure it is assumed that the sum of aluminium and

silicium is equal to 100 Ï. If this is not the case equation (8.10) is to

be replaced by

94
 C,_ = (100 - D) - C_. (8.13)
Al.n Si.n

where D is the sum of all the elements present except Al and Si.

The above procedure gives an accuracy of better than 0.2 Z

absolute compared to a chemical determination of Si. It is however

obvious that the relative precision will be dependend on the Si content

of the alloy. This is illustrated in Fig. 8.7.

c
o
c
o
c
o
• f-l
O •J
o> (0
S-i d
a. •H
>J
01
4-1
0)
n!
i—i
0)

Fig. 8.7 : Experimental precision on the silicium determination in

aluminium-silicium.

8.5. Determination of tin in cassiterite.

8.5.1. Introduction.

Cassiterite is by far the most important tin ore (SnO ) occuring

in granitic rocks or after erosion as a sandy ore. Typical compositions

are given in Table. 8.8.

The chemical standardization of tin in cassitirite is a rather

difficult problem. A gravimetric procedure can be used by precipitating

tin as SnO from a nitric acid solution. The coprecipitated impurities

are determined by difference after removing tin as SnI .

95
 ^
00 O CM ~3-00--— c M O u " ! * — O O ' —
Pd 4-1 r^- r^" ^D o o o c M o c o < r o - ^ - o o o
O 01 1 i . . . . . . . . . . .
PQ Prf iO O O o o o o o o o o o o o
v V V V V

CM O"! CO •—
r-» CM OO vO O O O •—
<ti -o- vO 0^ o o o o o
W 00 1 1 1 1 1 1 1 1 . . . .
vO ^D O o o o o o

CM fO vO r*^«
CM m o
W r-. ^ • ^ ^ • I l l l l l !
<}• ^— o o o o o o

\D »- en
^^ CO m in 0
W t-» 1 1 1 1 1 1 t ! 1 1 1 1
vO CM *— o

m oo r^ oo O CM co o~i
pa co CM O") O ^O •^ C^ CO
W r- . . . 1 1 1 1 1 1 1 1
vO CM CM T- o oo m o

^
OO vO
^
< 0 O O> o
W VÛ 1 1 1 1 1 1 1 1 1 1 1 1
xO vD O o

to
01 T— r^ 0s* ^-
V-i «U o 0 t- 0
o fjj vu • • 1 1 1 1 1 1 1 1 1 1 1 1
\O in o 0
HI r-^
4J V
• 1-1
i-i
0) t—
4J O C7> f"^ ro <r <r v-
•r-l < 0 cr. oo CM CM o m
00 fr") ^£> l 1 1 1 1 1 1 1 1 ...
(0 vD 00 CM *- 0 0 0
m ^O
o
i—i
03
Ü cn <f r- 1—
• i-< *^ o> CM OO ^
Ow W LO 1 1 1 1 1 1 1 1 1 1 1 1
o CO CM 0
U

0
en oo »- vO CO oo t-O *«^" r**^
pa cr. ^O ^O ro a- <r CM •—
U-l w m . . . i i i i i i i i
O **D -^- r-> T- O ^D •* O
m .—
G
O
•H
4J
^
n vD oo ON O •— CM
WJ M o~> \O ^O CM O <f vD O
O w m . . . 1 1 1 1 1 1 1 1
p1 \£3 o — c O CM CM O
jjï r~~-
O •v
o

,
00
• ^_l m in co
00 0) <U CM O O CM o
•U) 'Ö O CM CM CO O CM
W CO O C eu c • i-i n) ,u O -i-i •—* ft en -i-i 3 fi
C 0 en fa S ;/} f-H f-H ^ |2 C/5 <I^ C/> <C Pa O Pi
oa o
s
H

96
 The other alternative is a iodemetric procedure by oxidizing

Sn(II) to Sn(IV) with I or I0~

8.5.2. Nuclear data.

The nuclear data of some elements present in cassiterites were already

given previously. Table 8.9. includes only those not given previously and

present in cassiterites.

TABLE 8.9 : Nuclear data of Sn. Ta and W.

Isotope Occurence Isot.prod. I /o T y-energy (Z)

o o 1/24 / 0

122
Sn 4 . 6 3 123m Sn 5 . 4 0 40.08m 6 0 . 2 ( 8 4 Z ) ; 332 . 0 ( 9 7 Z )

12
Sn 5 . 7 9 125m Sn 60.1 9.525m 332.0(972)

181
Ta 99.988 182m Ta 3 3 . 3 1 5 . 8 m 17 1 . 6 U O Z ) ; K6. 8 UOZ ) ;
m.9(20Z) ;318.4(5Z)

186
M 28.6 187 W 13.7 23.9 h 1 34 . 2(9 . 5 ) ; 479 . 6 ( 2 3 . 4 )
685.7(29.2)

From the composition of cassiterites and from the nuclear data it

appears that activation analysis with a I.N.S. is possible if epi-

thermal activation is applied, combined with gamma spectrometry with a

Nal(Tl) detector for the reaction Sn(n,-y) Sn on the gamma at 332

keV. All the activated isotopes have no gamma's coinciding in energy

125m 182m
with the 332 keV line of Sn. except the 318.4 line of Ta.

However even at a concentration of 11. the interference is only 0.2 I.

91
 8.5.3. Sample preparation, irradiation and measurement.

16.5 g of cassiterite is mixed with 3.3 g wax and pressed into a

cylindrical pellet of 17.0 mm diameter and 26.0 mm height at a pressure

2
of + 400 kg/cm . The pellet is irradiated in a cadmium box (wall

thickness 1 mm) during 1000s at a place of optimum epithermal flux.

After a waiting time of 100 s, the sample is counted for 1200 s. After

a second waiting time of 2000 s, a second count is started in the

negative counting mode. The obtained spectrum is given in Fig. 8.8.

4 0 - 5 ._
It appears that the small peak of Sn half-life 40 mm) at 160.2 keV
1 9 f\m
i s well s e p a r a t e d from the Sn peak at 3 3 2 . 0 k e V , the net peak area

8000-

332.0 keV

:
a)
c
f.
u
6000
en
u
e.
o
u

4000

123mc '
Sn

160.2 keV 1
!

A /L
JU

2000

V^V^vV ^~ ———— ^ ———«J

r . 1
0 100 200 300

Channel Number

Fig. 8.8 : Net Nal(Tl) spectrum of a cassiterite sample.

98
being appr. 2.10 counts. This area is calculated according to the

Wasson method :

-k

A = E n. - (k+1/2) .u

It is i l l u s t r a t e d in F i g . 8 . 9 .

k=0

8000

u
g 6000
o

4000

2000

-60 -40 -20 20 60

Channel Number (k)

Fig. 8 . 9 : Peak s u r f a c e d e t e r m i n a t i o n a c c o r d i n g W a s s o n .

99
 8.5.4. Standardization.

It appears from Table 8. that the concentration of tin in cassitentes

varies between 50 1 and 76 Z, whereas a numer of other elements as Fe.

Mn, Ti, Nb and W also vary between considerable limits. It can be shown

by a Monte Carlo method of calculation that although the absorption of

the 332.0 keV gamma is quite high (+ 30 2) the difference for the

different compositions is below 0.15 I and can thus be neglected. Since

most cassiterites contain more than 90 T SnO , analytical grade SnO

can be used as a standard, by pressing pellets in the same way as de-

scribed for the samples. For standards with a tin content between 55 1

and 79 Z a linear calibration line is obtained. The error on a single

analysis can be estimated at about 0.5 I.

8.6. Determination of fluorine in fluorites and ores.

8.6.1. Introduction

Although the availability of specific fluoride electrodes has

greatly increased the reliability of fluorine determinations this

technique requires a dissolution of the sample and can give rize to

losses and systematic errors. Activation analysis is therefore an

interesting alternative as it is non destructive, rapid and precise.

8.6.2. Nuclear data.

19
Fluorine is a mono isotopic element as F and can give rize with

thermal, epithermal and fast neutron to a number of nuclear reactions

given in Table 8.10.

100
 19
TABLE 8.10: Nuclear data for neutron reactions with F and interfering

reactions.

Reaction Thermal Resonance Fast Threshold Half- Ma in

Cross Integral Cross (MeV) life •y-energies
section section (keV)
(b) (b) (mb)

19 -3
F(n.r)2°F 2.6.10-3 21 . 10 11.41s 1633.1
19
F(n.p, 19 0 1 .35 4.25 28.91s 1974;1375.6
19
F(n.2n) 18 F - 7.3x10~ 3 10.98 6.59.103s 511
19
F(n,«) 15 N 7.85 1.60 7.14s 6128-.71117
16
0(n.p» 1 6 N 0.019 1 0 . 2 7.14 6128:7117

4 Q 4 f% 4 Q

Methods based on the reaction F(n,2n) F are not specific as F is a

pure ß -emitter. Thus a chemical separation is required. Activation

20 19
with thermal neutrons in the presence of fast neutrons yields F, 0.

These isotopes cannot easily be measured instrumentally as the gamma's

are superimposed on the Compton radiation of the high energy ones. The
1Q 1R
reaction F(n,a) N has a reasonably high cross-section. a low
16
threshold and yields N, an isotope with short half-life and high

energy gamma radiation. If measured with a Nal(Tl) with threshold set

16
at 4 MeV the measurement is specific for N. The only interference can

be due to the presence of oxygen. The 0(n,p) N has however a very

high threshold energy at 10.2 MeV. Consequently the activity of N

induced by the latter by means of an (a.n)-source is lower by a factor

of approximately 200. If fluorine is present as a major or minor

element this correction is usually negligible.

101
 8.6.3. Irradiation, counting and calculation.

A powdered sample of fluorite of 14.5 g is mixed with 1.45 g of

wachs and pressed into a pellet of 2.00 cm diameter and 1.75 cm height.

It is irradiated for 20s at the site of maximal fast flux, transferred

into the well of the Nal(Tl) detector and measured during 20s in the

energy region of 4 MeV to 7.5 MeV. The number of counts collected is

approx. 5000 counts per gram of fluorine. Usually the CaF content is 7

to 92 I CaF and a correction for oxygen is not required. Teflon (with

a fluorine content of 61.29) can be used as a standard from a cylinder

of the same size as the samples. Fluorine can also be determined for

instance in zinc ores where the fluorine content varies approximately

between 0.1 1. and 1 7-.

A spectrum obtained from the teflon standard (A) and a zinc ore

containing 0.5 Ï fluorine is shown in Fig. 8.10.

The fluorine content is of course obtained from the ratio's of the

activities in sample and teflon standards.

Remarks :

1 . As the half life is quite short the samples are not removed from the

irradiation container. A blank correction can therefore be required

instead of a pure background.

2. For a low fluorine content and a high oxygen content the correction

for the 0(n,p) N reaction has to be applied. Therefore an oxalic

acid pellet can be irradiated to determine the exact correction.

Obviously the oxygen content has to be known or can be deduced from

the composition of the ore.

102
 16.

600 -

1-1
01
o.

c:
o
CJ

400 ~

200 -

200 300 400

Channel number

Fig. 8.10 : Nal(Tl) spectrum of a 16.5 g teflon sample (spectrum A) and a

14.5 g zinc ore sample (spectrum B); irradiation time 20 s;
cooling time 4 s; counting time 20 s. Spectrum B is scaled up
by a f a c t o r of t e n .

103
 8.7. Determination of manganese in plants.

8.7.1. Introduction.

Manganese is an essential element for plants, its function being

related to oxidation-reduction processes. It is also part of some

enzymes. Its content varies widely according to the species and

according to the soil on which they are grown. The order of magnitude

is usually between 10 and 5000 ppm. A number of SRM's of the National

Bureau of Standards, Washington DC, U.S.A. have been certified for

manganese as SRM/575 Pine Needles (675 jug/g Mn ) ; SRM/573 Tomato Leaves

(238 ng/g MnI ; SRM/572 Citrus Leaves 23 ng/g M n ) ; SRM/570 Spinach (165

Atg/g Mn). Certified Reference Materials are also available from the

Community Bureau of Reference (B.C.R.) : BCR No60 Aquatic Plant (1759

/ig/g M n ) ; BCR No 61 Aquatic Moss (3771 <ig/g; BCR No 62 Olive leaves

(57 /ig/g). These reference materials can of course be used to check the

accuracy of the method.

8.7.2. Nuclear data.

As already given in Table 8.4. manganese has a quite large thermal

neutron cross-section of 13.3 barn and a favourable half-life of 2.6 h.

56
It is a monoisotopic element as Mn-55. Mn is a -y-emitter with an

energy of 846.9 keV. Thus its nuclear properties are quite favourable

and good sensitivities can be expected. Plant materials contain

however large concentration of potassium and sodium and also trace

elements as bromine, zinc, copper, e t c . , so that a purely instrumental

method by gamma-spectrometry with a germanium semi-conductor cannot be

applied and a chemical separation is usually required. It is also

apparent that plant materials contain important amounts of iron. As

104
the abundance of Fe is 91.7 I it can give nze to a positive error

through the reaction Fe(n.p) Mn (cross section 0.9 mb.) with the

fast neutron flux. Even when a fast to thermal flux ratio equal to

unity is assumed and an iron to manganese ratio of 100. this error is

completely negligible.

8.7.3. Procedure.

Weigh 1g (or more if required) of dried and pulverised plant

material into an irradiation capsule and irradiate at the optimal

thermal flux site during 2 h. Transfer the irradiated material into a

250 ml beaker and add 20 ml of a mixture nitric acid (14 N) and

perchloric acid (70 Î) in a 1:10 proportion. Heat gently on a hot

plate. Add more nitric acid if required. Fume down to perchloric acid

fumes Leave to cool and dissolve in 25 ml 0.1 N perchloric acid.

Filter off any residue due to SiO or KC10 . Collect the filtrate into

a 250 ml separatory funnel. Add 10 ml of saturated hydrazine sulfate

solution to reduce the manganese to the bivalent state. After 5 mm.

add 20 ml of a 0.05 mol/liter potassium biphalate buffer and adjust to

pH=2 with 14N ammonia Extract the copper with 2 successive 20 ml

portions of 0 05 mol/liter oxine in chloroform. Thereafter adjust to

pH=8 with KN ammonia. Extract twice with 20 ml 0.05 mol/liter oxine

in chloroform Wash the organic phase twice with an aqueous solution

24
of pH = 8 to remove traces of Na contaminating the organic phase.

Transfer the organic phase into a counting vial and place on 3"x3"

N a l ( T l ) detector coupled to an M.C.A Determine the net activity under

the photopeak at 846 9 keV

The manganese content is calculated from the ratio of the

activities of a standard and the sample. As a standard a known amount

105
 of manganese (e.g. a manganese sulfate solution soaked into cellulose

pulp and dried) is irradiated in the same geometry and treated in the

same way as the sample.

8.8. Determination of cadmium in zinc ore by neutron absorption.

8.8.1. Introduction.

Cadmium occurs in most zinc ores and zinc concentrates in concen-

trations varying between 0.1 I and 1 1. as shown in Table 8 . 1 1 .

These ores and concentrates are an important source of cadmium.

The cadmium is usually determined by atomic absorption spectrometry

after dissolution of the zinc ore in sulfuric acid. Cadmium is usually

removed from these solutions by deposition on zinc powder, as the

former is more electro-positive Cadmium has a high absorption cross-

section for thermal neutrons (2440 barn) so that a direct determination

on the ore is possible by the neutron absorption technique.

8.8.2. Nuclear

As already described in f i> , a small metallic vanadium cylinder (6

mm height, 6 mm diameter) can be used as a measure of the neutron

absorption. The nuclear characteristics of vanadium are indeed quite

favourable : short half-life (3.755 mm), large thermal neutron

cross-section (4.79 barn) and large abundance of the V isotope

52
(99.750 1) so that the V is induced with good yields, even in a

modest flux.

106
TABLE 8 . 1 1 : Concentration (Z) o-f the most important elements in zinc

ores and concentrates.

Zn Zn Zn Zn Zn_ Zn
i 2 3 4 D D

Zn 54.21 59.64 51 .75 47.67 61.37 51.56

Cd 0.1 0.2 0.3 0.410.74 0.96

BCR BCR BCR

1 2 3

Zn 53-55 46-48 51-53

Fe 7 15 95
Cd 0.1 0.15 1-1 . 1
S 31 29 30
Cl 0.01 0.06 0.005
sio2 3 0.3 0.8
Al„0„ 1 0.05 0. 1
2 3
CaO 0.3 0.4 0.3
HgO 0.05 0.05 0.2
Mn 0.4 0.5 0.2
3°4
Pb 1 0.7 10
Cu 0.07 0.8 1 .5
As 0.05 0. 1 0.3
Co 0.015 - 0.005
BaO 0.05 - 0.001
Ag 0.007 0.012 0.015
Sn 0.001 0.001 0.001
Sb 0.005 0.005 0.01
Ni 0.001 0.001 0.001
Ge - - 0.02
F - 0.02 -

8.8.3. Sample and standard preparation.

The ore is mixed with wachs in a 1 over 2 proportion and pressed

into two pellets of 10 mm thickness and 20 mm diameter corresponding

107
 each to a weight of 6.25 g. The upper side of the press is shaped so

that a hole of 6 mm diameter and 3 mm deep is obtained. A pressure of

2
about 400 kg/cm is required. The two half samples are then fitted

with the vanadium detector.

Standards are prepared by mixing analytical grade ZnO, elemental

sulfur, carbonyl iron and cadmium oxide with wachs. This standards

(not including the wachs) contain 55 I Zn. 31 l S, 7 7. Fe and cadmium

from 0 I to 1.5 I.

8.8.* 2 rradlatlon and

measuring conditions.

The pellets containing the vanadium detector are irradiated at the

optimal thermal flux site during 200 s. The vanadium detector is

removed from the pellet and counted with the 3" x 3" Nal(Tl) well type

detector in the integral mode (i.e. from an energy on corresponding to

6 2-1
40 keV) during 400 s. At a thermal flux of appr. 10 n.cm .s the
52
V-activity corresponds to appr. 900.000 counts. The same vanadium

detector can be re-used after a delay of 15 minutes.

8.8.5. Interferences and calculation of the results.

As the neutron absorption technique is non-specific, other

"neutron poisons" will interfere. This could be the case especially

for boron as this element has a sensitivity which is 3.3. times higher

than cadmium. No boron could however be detected in zinc ores and

concentrates. Moreover one can calculate that 55 Ï Zn, 30 Z S and 7 Z

Fe give respectively rize to an absorption corresponding to 0.036 T .

0.022 I and 0.015 Z Cd. Any variation in concentration of these

elements as occurring in ores and concentrates can only cause a maximal

error of 0.01 Z cadmium.

108
 The results are calculated from the relation

log — = a + bx + ex (8.15)

where

52
A = net V activity in blanc standard
o
52
A = net V activity in sample

x = mg Cd in sample.

Typical values for a. b and c in eq. (8.15) obtained by least fitting

are shown in Fig. 8.11.

0.20 -

00
o

0.15 -

log i = -0.249x10~ 2 + 28.7x10~ 4 x - 85.87x10~ 6 x 2

A
0.10 -

0.05 -

80 120
mg Cd

Fig. 8.11 : Thermal neutron absorption as a function of cadmium content

109
 8.9. Determination of boron in steel by neutron absorption.

8.9.1. Introduction.

In steel containing 3 I silicon boron is sometimes added at the

100 ppm level to improve the magnetic properties. Boron is usually

determined by spectrophotometry after dissolution of the sample,

distillation of the boron as its trimethylester and addition of

curcumine to form a red complex. As boron has a large absorption

cross-section (765 barn) and a low atomic weight, the sensitivity is

3.3 larger than for cadmium. Moreover the density of steel being higher

by a factor of 7 a sensitivity of about 1 ppm B can be achieved.

8.9.2. Procedure and results.

The procedure is exactly the same as the one described in $ 8.8

except that the samples are machined to obtain cylinders of 20 mm

diameter and of 10 iron height, containing a hole in the center 3 mm

52
deep and 6 mm diameter. It appears that the net V activity yields a

linear relation as a function of the boron content as shown in Fig.

8.12.

The precision is 1.5 wg/g at the 100 ppm level.

110
Fig. 8.12 : Thermal neutron absorption as a function of Boron content.

Ill
 8.10. Other applications of INS

It is also evident that a I.N.S. can also be used to study the

chemical effects of neutron capture reactions, which is part of the so

called hot-atom chemistry. Szilard and Chalmers already discovered in

1934 that if ethyliodide is irradiated with neutrons, part of the

radioiodine is no longer present in the ethyliodide. This process of

chemical bond rupture due to recoil is therefore called the Szilard-

Chalmers process. It is perhaps usefull to mention briefly a number of

hot-atom applications where I.N.S. can applied either for research or

education. Reactions with organic halides can be studied, not only to

determine the free radiohalogens after neutron irradiation but also to

identify the numerous organic products formed. Of special interest can

80m 80
be the separation of isomenc states e.g. Br from Br. The role of

organic scavengers can also be studied in this context.

Irradiations of oxycompounds are also of great importance in hot-

atom chemistry, as for instance perchlorates, periodates, chlorates,

bromates, iodates, permanganates etc. They are not only interesting

from ,.ta hot-atom chemistry point of view, but also allow the prepara-

tions of radioactive isotopes of high specific activity. Thermal

annealing studies can of course also be studied. Finally self labelling

of organic compounds with tritium by the Li(n,a) H can also be

attempted.

Summarizing one can conclude that a I.N.S. is not only interesting

as a tool for neutron activation analysis but can also find numerous

applications in hot-atom chemistry. The latter should however be dealt

with in a separate monography.

J12
 REFERENCES

(1) Op de Beeck J. : Treatise on Analytical Chemistry. Second Ed..

part I, Vol. H. p. 739. John Wiley 8, Sons Inc., New York, N.Y.,
U.S.A. 1986.
(2) Geiger K.W. : Proc. of the I.A.E.A. Consultants' Meeting on
Neutron Source Properties edited by K. Okamoto, June 1980, pages
43 to 78.
Blinov M.V. : ibidem, pages 79 to 106.
(3) Proceedings on the Consultants' Meeting on Isotopic Neutron
Sources for Neutron Activation Analysis. I.A.E.A. Vienna, Austria,
21-24 May 1985; Edited by H. Vera Ruiz.
(4) Alaerts L., Op de Beeck J., Hoste J. : J.R.A.C., 15(1973)601.
(5) Alaerts L., Op de Beeck J., Hoste J. : A.C.A., 69(1974)1.
(6) Ganayev I.H. : Neutron multiplier type Co-1 for activation analy-
sis, Vses. Ob;]. Isotop, Atomizdat, Moscow 1970, p. 145.
(7) Rubinson W. : J. Chem. Phys.. 17(1949)542.
(8) Givens W . W . , Mills W.R., Caldwell R.L. : Nucl. Instrum. Methods.
80(1970)95.
(9) Handbook on Activation Data, I.A.E.A., Technical Reports Series
n' 273, May 1987.
(10) Herzog W., Wilde H . R . : Kraftwerkstechnik, 64(1984)348.
(11) De Norre L., Op de Beeck J., Hoste J. : J.R.A.C., 78(1983)137.
(12) Spenke H., Cless T., Karlik B. : Radiochemical Methods of Analy-
sis. Vol. I, I.A.E.A., Vienna 1965. p. 245.
(13) Selecki A., Nowakowski Z., : Radiochem. and Radioanal. Letters,
1 ( 1969)247.
(14) De Norre L., Op de Beeck J., Hoste J. : J. Radioanal. Chem.,
59(1980)453.
(15) Junod E. : Rapport CEA-R 2980, Paris 1966.
(16) Bartosek J., Adams F., Hoste J. : Nucl. Intr. and Meth., 103(1972)
43.
(17) Adams F. and Dams R. : Applied Gamma-Ray Spectrometry, Pergamon
Press. Oxford, G.B., 1970.
(18) Heath R. : Gamma-Ray Spectrum Catalogue, Ge(Li) and Si(Li) Spec-
trometry 3rd Ed. Report ANCR-1000-2, USAEC, Idaho Falls, Idaho,
U.S.A., 1974.
(19) Grosjean C.C., Bossaert W. : Table of Absolute Detection Effi-
ciencies, Univ. of Ghent, Belgium (1965).

113
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