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For silver, both the Ag K and Ag L signals, obtained inthe spectrum, allow the evaluation of

the depleted layer.


17
Whereas Ag L

radiation (energy 3.0 keV) originates domi-nantly from a depth of up to 2

m, the information depth ofthe Ag K

radiation (energy 22.2 keV) is up to

100

m in as i l v e r c o p p e r m a t r i x o w i n g t o i t s h i g h e r e n e r g y. B y c a l c u l a t - ing the ratiosofAg


L/AgK intensities it is possible to
obtaini n f o r m a t i o n o n t h e d e g r e e o f d e p l e t i o n . T h e v a l u e o f t h i s r a t i o can be used as an
indication of whether silver is enriched a t t h e s u r f a c e o f a c o i n o r n o t a n d i t c a n
b e a p p l i e d f o r estimating the error which occurs when EDXRF is used non-
d e s t r u c t i v e l y. B y c o m p a r i n g t h e s e r e s u l t s w i t h d a t a o b t a i n e d from non-corrodedand polished
silvercopper standards ofs i m i l a r c o m p o s i t i o n , i t c a n b e s e e n t h a t t h e A g L / A g K i n t e n -
sityratiosofthecoinsareupto

20%higher,whichindicates t h a t s i l v e r i s e n r i c h e d a t t h e s u r f a c e s o f t h e c o i n s ( s e e Ta b l e 1 ) .
Interactions of the photons due to absorption and scat- t e r i n g e f f e c t s r e s u l t i n a
d e c r e a s e i n t h e i n t e n s i t y o f t h e uorescence radiation. The thickness
D
o f a l a y e r, w h i c h emits 63.2% of the uorescent intensity of a bulk material o f i n n i t e
thickness, is given by Eqn (1).
18
This equationa p p l i e s t o t h e c h a r a c t e r i s t i c r a d i a t i o n a n d n e g l e c t s s e c o n d a r y or tertiary
excitation, which alter the value of
D
slightly.
D
D
1

sin

1
C

sin

where
D
D
thickness of layer, which emits 63.2% ofthe uorescent intensity (cm);

D
mass density (g cm

3
);

D
mass absorption coefcient of the specimen for the incident photons (cm
2
g

1
);

D
mass absorption coefcient of the specimen for the observed uorescent photons (cm
2
g

1
);

1
D
angle between the primary beam and the specimen surface (in our case 45

);

2
D
take-off angle between the uorescent beam and thespecimen surface (in our case 45

).A s c a n b e s e e n i n F i g u r e 5 , t h e m a i n p o r t i o n o f t h e u o r e s c e n c e
r a d i a t i o n o r i g i n a t e s f r o m t h e t o p l a y e r a n d the total intensity increases following a non-linear
function.I n s i l v e r c o p p e r a l l o y s t h e t h i c k n e s s o f l a y e r
D
, w h i c h emits 63.2% of the silver uorescent intensity, increases
withgrowingsilvercontent,whereasthecorrespondingthickness o f C u K

radiation decreases (Fig. 6). Owing to the lowerenergy of Cu K

radiation compared with Ag K

radiation,the Cu K

intensity is relatively more affected by absorptioneffects in the matrix.Figures 7 and 8 show the
inuence of the matrix com- position on the information depth. Whereas the information
depth of Ag K

radiation in a pure silver matrix is up to

110

m (99% intensity), in a nearly pure copper matrix itis only

65

m (99% intensity). For Cu K

, an informationdepth of

45

m can be calculated for pure copper, whichdecreases in correspondence with the matrix
composition(see Fig. 8).In order to determine the thickness of the depleted layerand the silver
concentration in the (non-corroded) core ofthe coins, SEM/EDX was applied to cross-
sections of a fewselected coins, which were in a bad state of preservation anyway.