RAPID COMMUNICATIONS IN MASS SPECTROMETRY, VOL.

11, 13091314 (1997)

Role of Secondary Ion Mass Spectrometric

Analysis in the Brazing of Precious Alloys
C. Piccirillo, M. Fabrizio, S. Daolio* and B. Facchin
Istituto di Polarografia ed Elettrochimica Preparativa, CNR, Corso Stati Uniti, 4, 35127 Padova, Italy

Secondary ion mass spectrometric characterization of Cd-free and Cd-containing brazing alloys for jewelry are
presented, analyzing the surface composition and elemental distribution along the thickness both for master
alloys and brazed joints. It was verified that the brazing process induced little modification in In-containing
alloys. On the other hand, Cd evaporation from the alloy was verified after heating, confirming its danger to
health under these conditions. The presence of intermetallic clusters was detected, indicating interactions
between brazing alloys and 18 carat gold. 1997 by John Wiley & Sons, Ltd.
Received 13 May 1997; Accepted 1 June 1997
Rapid. Commun. Mass Spectrom. 11, 13091314 (1997)
No. of Figures: 6 No. of Tables: 1 No. of Refs: 8

In a brazing process, two metallic objects (base metal)

are joined together using a low melting point metal
(filler metal) placed between them. Molten brazing
alloy spreads into the base metal by capillary flow so
that after freezing, the parts are anchored together.1
Suitable brazing alloys must meet the following
requirements: the liquidus temperature should be at
least 20 C lower than the solidus temperature of the
base metal (usability range); the molten alloys should
show good wetting and low viscosity; if there are to be
subsequent brazing processes, the brazing alloys have
to be thermally compatible. The brazed joints should
maintain their original mechanical properties and
resistance to corrosion. If brazing alloys for jewelry are
considered, it is very important, for the quality of the
final jewel, that the brazing process should keep a
constant gold content of joints and should not modify
the color (color matching).2
For ternary yellow gold alloys (Au, Cu and Ag), the
liquidus temperature changes remarkably with the ratio
Ag:Cu. For each carat fineness, Ag and Cu contents
have already been determined to obtain the lowest
melting point alloy. These compositions are the most
often used in jewelry for their workability. Therefore, in
considering brazing alloys, low melting point metals
have also been taken into account to achieve a further
decrease of temperature;3,4 in particular, Cd-containing
alloys (125%) have shown good wetting, fluidity and
color matching. However, because of its high vapor
pressure, this element can be very harmful (Cd reacts
with oxygen and the oxide formed causes diseases such
as pulmonary edema or osteoporosis).2 For this reason
Cd-free materials have been proposed, both for yellow
and white gold, in different carat fineness. Interesting
results were obtained with the use of Zn and Sn instead
of Cd; indium alloys, too, exhibit suitable features, even
if this metal is expensive in comparison with the
others.
As shown in these examples, it is evident that small
composition and processing differences influence the
Presented at the 15th Informal Meeting on Mass Spectrometry,
Smolenice, Slovak Republic, 1216 May 1997
*Correspondence to: S. Daolio
Contract/grant sponsor: Centro Ricerche FIAT
Contract/grant sponsor: Programma a sostegno della produzione e
del commercio dell Artigianato Orafo
CCC 09514198/97/121309-06 $17.50

Table 1. Chemical composition of analyzed brazing alloys

Sample

1
2
3

Master alloy (%)

75 Au, 9 Cu, 6.5 Zn, 6 Ag, 3.5 In

75 Au, 8 Cu, 5.5 Zn, 5 Ag, 4 Sn, 2.5 In
75 Au, 9 Cu, 6.5 Zn, 6 Ag, 3.5 Cd

quality of the final products, often determining their

commercial success or otherwise. From this perspective,
the physico-chemical characterization of alloys before
and after the brazing process, contributes by defining
the criteria for the choosing of brazing materials.
The secondary ion mass spectrometric (SIMS) technique has already been utilized to characterize metallic
samples of industrial origin, such as vanadium-, cobaltand tungsten-based alloys. Various researches have
been done on industrial alloys, analyzing the influence
of compositional changes and elemental distribution on
materials properties.5 On the other hand, there is very
poor literature concerning the characterization of noble
metal alloys used in jewelry. In the present paper, the
SIMS technique is proposed for studying precious
metal brazing alloys, in particular Cd- and In- or
(In + Sn)-containing ones, where the Sn addition has
been considered for lowering the cost of In-containing
alloys. As evidenced elsewhere,6 the potential of the
SIMS technique allows analysis of all the elements (at
trace level, too) at the surface and through the
thickness of the sample.
EXPERIMENTAL
Analyzed brazing alloys for 18 carat gold 3N (Au 75%,
Ag 12.5%, Cu 12.5%) were prepared replacing Cd by
In or (In + Sn) in the commercial base alloy BAg-27
(Cu 3436%, Ag 2426%, Zn 2428%, Cd 12.514.5%)
for use as reference material; to obtain final compositions as listed in Table 1 (sample 1: In-containing;
sample 2: (In + Sn)-containing; sample 3: Cd-containing alloy), 25% of alloy was mixed with 75% of Au.
Measurements were carried out both on the master
alloy and on brazed joints, in order to detect possible
structural modifications due to the brazing process. To
check composition homogeneity, spectra were recorded
on three different points for each sample.
1997 by John Wiley & Sons, Ltd.

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ROLE OF SECONDARY ION MASS SPECTROMETRICS ANALYSIS IN THE BRAZING OF PRECIOUS ALLOYS

SIMS investigations were carried out in a custombuilt instrument that has been described elsewhere.7 A
monochromatic (110 keV) O2 + ion beam (collimated
to 50 m) was generated in a mass-filtered duoplasmatron ion gun (model DP50B, VG Fisons, Manchester,
UK). The secondary ion optics were of the three-lens
design with a central stop interfaced with a Balzers
(Liechtenstein) model QMA 400 quadrupole mass
analyzer (mass range extended up to m/z 2048). A
secondary electron multiplier (90 off-axis) was used
for negative- and positive-ion detection in counting
mode. Lens potentials, quadrupole electronic control
units and the detection system were controlled via a

Balzers QMS 421 unit. The control of the instrument

and the collection of data were carried out by two
personal computers connected to a local area network.
Sputtering of the sample material was carried out at 3
keV O2 + primary ion energy.
RESULTS AND DISCUSSION
For all samples, mass spectra were recorded to determine surface composition. Figure 1 shows positive- and
negative-ion spectra of the master alloy, sample 1
before brazing. In the positive-ion spectrum (Fig. 1(a))
patterns corresponding to main alloy elements (Ag + ,

Figure 1. (a) Positive- and (b) negative-ion mass spectra of sample 1: master alloy.
Rapid Communications in Mass Spectrometry, Vol. 11, 13091314 (1997)

1997 by John Wiley & Sons, Ltd.

ROLE OF SECONDARY ION MASS SPECTROMETRICS ANALYSIS IN THE BRAZING OF PRECIOUS ALLOYS

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Figure 2. Positive-ion mass spectrum of sample 1: brazed joint.

Figure 3. Na + , K + , Cu + , Ag + and In + concentration depth profiles for sample 1:

(a) master alloy, (b) brazed joint.
1997 by John Wiley & Sons, Ltd.

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ROLE OF SECONDARY ION MASS SPECTROMETRICS ANALYSIS IN THE BRAZING OF PRECIOUS ALLOYS

Zn + , Cu + , In + ) can be seen; even though Au is the

major component, there is no peak for the Au + ion
because, in this matrix, the element has a low positiveion yield. Intense peaks corresponding to common
impurities Na + , Mg + , Al + , Si + , K + , Ca + can be
detected; in fact all these elements have a very high
positive-ion yield, so that their signals can be intense
even if these species are very diluted.
For higher m/z values, mixed clusters can be
observed (AgCu + , AgCuO + , AgCuCl + , CuIn + ,
CuInO + , AgIn + ): their presence indicates interactions
between alloy elements, as would be expected for
intermetallic compounds. In the negative-ion spectrum

(Fig. 1(b)) the most important signals correspond to Au

and its clusters (Au, AuO, AuO2, AuCuO,
AuCuOH, etc.) as well as peaks relative to In oxides.
Measurements were carried out on the brazed joint
of the same sample. Its positive-ion spectrum (Fig. 2),
when compared with the one of the master alloy (Fig.
1), shows two main differences. In fact after the brazing
process the intensity of signals corresponding to Ag +
and Cu + ions increases. This can be ascribed to the
18-carat gold distribution, because Ag and Cu are more
concentrated in it than in the brazing alloy. Conversely,
the In + peak decreases because it is spread along the
jointed wall during the heating process. Signals relative

Figure 4. (a) Positive- and (b) negative-ion mass spectra of sample 2: master alloy.
Rapid Communications in Mass Spectrometry, Vol. 11, 13091314 (1997)

1997 by John Wiley & Sons, Ltd.

ROLE OF SECONDARY ION MASS SPECTROMETRICS ANALYSIS IN THE BRAZING OF PRECIOUS ALLOYS

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Figure 5. Positive-ion mass spectrum of sample 2: brazed joint.

Figure 6. Na + , K + , Cu + , Ag + , In + and Sn + concentration depth profiles for

sample 1: (a) master alloy, (b) brazed joint.
1997 by John Wiley & Sons, Ltd.

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ROLE OF SECONDARY ION MASS SPECTROMETRICS ANALYSIS IN THE BRAZING OF PRECIOUS ALLOYS

to alkaline and alkaline earth metals increase after the

brazing process.
To determine the distribution of the elements in the
deeper layers, depth profiles were recorded, following
the behavior of some selected signals as a function of
sputtering time. Figure 3 shows depth profiles of Na + ,
K + , Cu + , Ag + and In + ions, both for the master alloy,
(a), and for the joint, (b). Differences in signal
intensities (already observed from mass spectra in Figs
1 and 2) can be seen. Signals corresponding to Na + and
K + are slightly increased in the master alloy; on the
contrary, for brazed joints, there is a rapid decrease
towards the bulk. This effect can be attributed to the
powders (salts and metal oxides) used as cleaning or
reducing agents during the brazing process.1 For the
same reasons similar behavior is also observed for
other ions such as Mg + or Ca + (not reported in Fig. 3).
It is interesting to see that only the outer layers of the
material are polluted by these additives.
In Fig. 4 positive (a) and negative (b) ion spectra are
reported for sample 2 before brazing. Most of the peaks
are the same as those already identified in the spectra
of sample 1; as expected, there are signals due to Sn and
its clusters as well, viz Sn + , SnO + , SnOH + , SnCl + ,
SnOx (x = 1, 2, 3). Figure 5 shows the positive-ion
spectrum of the same alloy after brazing. The behavior
is similar to that observed for sample 1. However, the
decrease of Sn + and In + peaks (i.e. of brazing alloy
elements) is less pronounced.
Figure 6 reports depth profiles of sample 2 (a) before
and (b) after the brazing process. Comparing master
alloys 1 and 2, the main difference is observed for alkali
metals, which slowly decrease from the surface to the
bulk in sample 2. Furthermore it can be seen that
profiles relative to components of brazing alloy 2 are
constant along the thickness considered, indicating a
homogeneous distribution.
As a reference material, BAg-27 alloy was studied,
carrying out the same measurements as those made on
the other samples (sample 3). The most intense signals,
different from alloys 1 and 2, correspond to alkali- and
alkali earth-metals; furthermore, organic fragments
such as CHn + (n = 0, 1, 2, 3), with m/z = 1215 u, can
be observed. As expected, peaks related to Cd + and its
clusters (Cu + , CuCd + , CuCdO + ) are present before
brazing. On the other hand, absence of all Cd-related
peaks is observed on spectra recorded of the final joint:
this is reasonable because, as already mentioned, Cd
vapor is produced during heating. The same behavior is
shown by peaks related to organic fragments, which are
burnt or volatilized at the high temperatures of the
brazing process.

Rapid Communications in Mass Spectrometry, Vol. 11, 13091314 (1997)

CONCLUSION
The brazing process represents a decisive and critical
step in jewelry manufacture but the alloys utilized are
often home-made to an empirical composition by the
gold craftsmen, affecting the final products. These
problems could be remedied by characterizing brazing
alloys with sensitive techniques in order to analyze the
components and their distribution both on the surface
and in the bulk of the master alloy and of the brazed
joint.
Preliminary data reported here were planned to
verify some previous results from energy dispersive
X-ray analyses8 concerning the behavior of low melting
point metals in these new alloys. The SIMS technique
was considered appropriate. Complete Cd evaporation
during heating was confirmed (sample 3) and the
presence of In in brazed joints (samples 1 and 2) on the
surface and throughout the thickness was verified. In
addition, organic and inorganic contaminants from the
treatment procedure were also detected, following their
penetration into the joints during the brazing process.
Although some cluster ions were not identified, the
results are considered to be satisfactory at this preparatory research stage. Therefore, as a perspective for the
future, it is expected that the SIMS technique will be
employed for studying high mass clusters and testing
the relation between element interactions and mechanical and visual properties of objects brazed with Cd-free
alloys.
ACKNOWLEDGEMENT
This research was supported by P. R. O. Art Programma a sostegno
della produzione e del commercio dellArtigianato Orafo of CNR
and MICA, Rome, Italy. Professor M. Magrini is acknowledged for
furnishing samples and for useful discussion. CP received a fellowship
from Centro Ricerche FIAT, Strada Torino 50, 10043, Orbassino
(TO), Italy.

REFERENCES
1.
2.
3.
4.
5.

M. M. Schwartz, Brazing, ASM International (1987).

G. Normandeau, Gold Technol. 18, 20 (1996).
D. Ott, Gold Technol. 19, 2 (1996).
D. M. Jacobson and S. P. S. Sangha, Gold Bull. 29, 3 (1996).
S. Daolio, C. Pagura, B. Facchin, S. Gelosi and C. Piccirillo, in 2nd
MS-Pharmaday, Massa 96, Siena, July 15 1996, Italy.
6. S. Daolio, J. Kristof, C. Piccirillo, B. Facchin and C. Pagura, Int. J.
Mass Spectrom. Ion Processes 152, 87 (1996).
7. C. Pagura, S. Daolio and B. Facchin, in Secondary Ion Mass
Spectrometry SIMS VIII, A. Benninghoven, K. T. F. Jansen, J.
Tumpner and H. W. Werner (Eds), Wiley, Chichester (1992), p.
239.
8. G. Magrini (private communication)

1997 by John Wiley & Sons, Ltd.