Strontium Aluminate Replaces

Alumina on Aluminum Melts at 500

ppm Sr and Provides Die
Soldering Resistance
By
Raymond J. Donahue, Mercury Marine and
Jonathan D. Almer, Argonne National Laboratory
Let’s Call This Our Oxidation Window
 The hard facts

• The calculated equilibra for the Al-M-O system

shows curves for BeO, LiAlO2, NaAlO2 &
MgAl2O4 in the oxidation window but curves for
Ca, Sr and Ba are off-scale to the right. This
means theoretically that the elements Ca, Sr and
Ba should not become oxidized at
concentrations less than 10,000 ppm, which is 1
weight percent, which does not agree with
industrial observations that Sr and Ca report to
the aluminum oxide phase when these elements
were present in the melt at concentrations
greater than 50 ppm.
We are going to look thru p[O2]vs %Sr
window to view the oxidation of Sr
• The window [10^-47 atm to 10^-52 atm] by [0.1 ppm to 10,000 ppm] exhibits
MgAl2O4 and NaAlO4 but not SrAl2O4.
• With MgAl2O4 and NaAlO4, we show that p[O2] can change by a factor of 10 or
more with a change in delta G of only 1% because the equilibrium constant K =
1/(ppm Mg)(p^2[O2] = exp[- delta G/RT] For SrAl2O4 no reference p[O4] vs
ppm dissolved strontium curve exists for comparison.
• For Sr [no reference curve for comparison], calculate K=a[SrAl2O4]/(ppm
Sr)(p^2[O4]), calculate Ln(K)=-delta G/RT, solve for p[O2] for 1 to 10,000 ppm
Sr  SrAl2O4 curve “almost” not in thermodynamic window
• Using real data that Sr in 50 to 500 ppm range oxidizes to SrAl2O4 at an
equilibrium p[O2] of 10^-48 atmospheres
• The realistic SrAl2O4 curve, as expected, is shifted to the left [nearly four
orders of magnitude] and downward [nearly two orders of magnitude] and can
now be seen through “our window” for the oxidation of Sr. These results
indicate that SrAl2O4 is more stable than alumina above 1 ppm Sr, and further
explains increased oxidation at 50 ppm, presents of die soldering at 300 ppm
and absence of die soldering above 500 ppm Sr.
 THE REFERENCE SYSTEM: Al-O
System:
2 Al (l) + 3/2 O2(v) = Al2O3 (s)
𝑎𝑎 𝐴𝐴𝐴𝐴2 𝑂𝑂3 −
3
𝐾𝐾 = 3
= 𝑝𝑝 2 𝑂𝑂2
𝑎𝑎 2 𝐴𝐴𝐴𝐴 × 𝑝𝑝 2
𝑂𝑂2
ln(𝐾𝐾) = − ∆𝐺𝐺𝐺⁄𝑅𝑅𝑅𝑅
3
− 𝑂𝑂2 −325,375
ln 𝑝𝑝 2 = = 163.752
(1.987)(1000)
3 3
− 𝑂𝑂2 − 𝑂𝑂2
ln 𝑝𝑝 2
𝑒𝑒 = 𝐾𝐾 = 𝑝𝑝 2 = 𝑒𝑒 163.752 = 1.308 × 1071
3 1
𝑝𝑝 2 𝑂𝑂2 = = 7.65 × 10 −72
1.308 × 1071
𝑝𝑝 𝑂𝑂2 = 3.88 × 10−48 𝑎𝑎𝑎𝑎𝑎𝑎
Al-M-O system (Curves for Ca, Sr and
Ba are off-scale to the right)Fig. 1
 When Mg is added to an Al melt,
formation of MgAl2O3 is possible.
With the value of ( ppm Mg ) (p2[O2] ),
values of p[𝑂𝑂2 ] are calculated
 Magnesium Aluminate, continues
reverse engineering calculations
1
• 𝐾𝐾 = 5.82×10−93 = 1.72 × 1092
• ln 𝐾𝐾 = − ∆𝐺𝐺𝐺 ⁄𝑅𝑅𝑅𝑅 = ln 1.72 + 92 ln 10 = 212.38
• 𝛥𝛥𝛥𝛥𝛥 = 212.38 1987 = −422,000 𝑐𝑐𝑐𝑐𝑐𝑐/𝑚𝑚𝑚𝑚𝑚𝑚
• The calculated value of 𝛥𝛥𝛥𝛥𝛥 =-422,000 cal/mole compares
favorably to the -425,622 cal/mole used above from various
references for 𝛥𝛥𝛥𝛥𝛥, which yields the ratio 425,622 / 422,000 =
1.008 which says - 425,622 is 0.8% more negative than - 422,000
or -422,000 is 0.8% less negative than -425,622.
• Thus, (ppm Mg)( p2[O2]) = 1 / (1.72 x 1092) = 0.5814 x 10-92 = 5.814 x
10-93
• With this value for (ppm Mg ) ( p2[O2] ), values of p[O2] are
calculated in Table 3 for six orders of magnitude of ppm Mg. As
expected, the reverse engineered, calculated data points in Table
3 are very close to the actual data points in Figure 1.
Table 3. Results of reverse engineering
by using the data points in Fig. 1
Magnesium Aluminate Sensitivity
Analysis
 Conclusions on Magnesium
Aluminunate
• It is appropriate to conclude the magnesium section of this article with the
obvious observation that a solid film will grow on the surface of molten
aluminum. Starting with the case of pure aluminum, the oxide film is initially
gamma alumina but this changes to alpha alumina, which allows a faster
oxidation rate that is not influenced by the alloying elements iron, copper, zinc
and manganese, but other alloying elements magnesium, sodium and
strontium may have a bigger influence. Above about 50 ppm magnesium, the
surface oxide is the mixed oxide MgO-Al2O3 know as spinel [i.e., magnesium
aluminate], according to John Campbell in his 1991 book Castings on page 11
[published by Butterworth-Heinemann Ltd.] When the magnesium approaches
about 2 wt%, the oxide film is magnesia, MgO. Campbell further points out,
that since the majority of aluminum alloys probably have a magnesium that
exceeds 50 ppm and is allowed by 0.1% max limits for Mg for many aluminum
casting alloys of the pink sheets of the Aluminum Association, a spinel film is
to be expected as the norm on aluminum casting alloys.
 When Na is added to an Al melt, the
formation of Na-Aluminate may form.
Continuing the calculations for sodium
aluminate
Calculated p[O2] 17X too high; original
data: (ppm Na)(p[O2])=4 x 10^-46
SENSITIVITY ANALYSIS FOR SODIUM
ALUMINATE
 Strontium Aluminate Section:
condition when Sr is added to Al-melt
 Strontium Aluminate Section:
condition when Sr is added to Al-melt
 Similar to Na Aluminate, the same
small increase is made in Sr Aluminate
 Calculations that put SrAl2O4 curve
touching the upper right hand corner.
Calculation result: strontium aluminate
almost touching right hand corner
 First Conclusion From Last Slide,
which is Figure 2

• strontium aluminate with activity of one

curve is quite consistent with the labeled
MgAl2O4 curve and labeled NaAlO2 curve,
as being higher and less stable, with the
slope of the MgAl2O2 curve, and not
representative of what is observed during
oxidation of these reactive elements in
industry.
 The realistic Strontium Aluminate
curve results with lower SrO activity
 Fig. 3: Isobaric equilibrium phase
diagram of the system of SrO - Al2O3
SrAl2O4 RESULTS RELATED TO
INDUSTRIAL OBSERVATIONS
Discussion of SrAl204 results related
to industrial observations
SrAl2O4 RESULTS RELATED TO
INDUSTRIAL OBSERVATIONS
Combining the statements of the last
three slides
Final Calculations
SECOND CONCULSION
THIRD CONCLUSION
 FOURTH CONCLUSION

Honer and Youling studied the effect of Ca and Sr additions to

an Al-12% Si melt. They showed , by more rapid oxidation, that
Sr and Ca reported to the aluminum oxide phase when these
elements were present in the melt at concentrations greater
than 50 ppm. Cochran and co-workers conducted a similar
oxidation study on Al-Mg melts and showed that sodium
additions of only 6 ppm had a significant effect on the
oxidation rate in these alloys. These results are not
inconsistent with the results drawn for strontium aluminate
with lower activity for SrO, because a more rapid oxidation
rate might be measured at 50 ppm before the growth of that
oxide at 500 ppm has a measurable effect on die soldering
resistance.
 THE FINAL, MOST IMPORTANT, AND
FIFTH CONCLUSION

• ALL OF THE THERMODYNAMIC

PREDICTIONS THAT STRONTIUM
ALUMINATE [SrAl2O4] REPLACES ALUMINA
[Al2O4] ON MOLTEN MERCALLOY ALLOYS
[of 367, 368, 368, B360, F380] THAT CONTAIN
0.05-0.08% Sr AND PROVIDE DIE
SOLDERING RESISTANCE HAS BEEN
CONFIRMED BY X-RAY DIFFRACTION
WORK THAT ARGONNE NATIONAL
LABORATORIES HAS JUST PERFORMED
ON THE OXIDE ON MOLTEN ALUMINUM.