ASSESSMENT COMMENTS ON METALLURGICAL ANALYSIS AURORA, TX ALUMINUM
SAMPLE
Anonymous, PA, 2008
1.1 Introduction
In 1973, samples from a mass of aluminum were sent by John F.
Schluesser to several metallurgical labs for analysis. From the
photographs it appears to be an irregular chip-like mass approximately
3 cm x 2 cm by 1 cm. In the published documents, it is claimed to
have been received from Bill Case of Dallas, TX on June 19, 1973. Mr.
Case reportedly found it beneath 4 inches of soil in a field in Aurora
TX, lodged against a limestone rock face.
Figure 1. Photographs of aluminum sample obtained from B. Case, 1973. Numbers on top scale correspond to 0.1 inch. As this was an amateur investigation, there is no documentation of proof that the sample came from this location. Furthermore, as its provenance is associated with Mr. Schuessler and Mr. Case, both associated with studies of paranormal phenomena and hoaxes, it is highly questionable that this sample was found in the location stated. There is no information regarding the age of the sample. Nonetheless, the sample did exist in 1973, and was subjected to seemingly valid metallurgical analysis. It is on these results that we comment.
1.2 Analytical Results
Figure 2. Sketch of sample and its sectioning into multiple samples for analysis (Schuessler documentation 1973)
The sample was apparently sectioned and sent to several analysis labs. The results are tabulated below.
1.2.1 EDAX Analysis Robert J. Danmeller, Marion Russo, (organization not given) In the documentation, it states this organization was given sample #2, but from their sketches, however, it appears they may have been sent sample #1. Analysis was conducted using SEM imaging and EDAX composition analysis.Runs 1-4 were taken from the face of a surface exposed by the sectioning, and correspond to the interior of the sample. EDAX specra indicates strong Al peak with 2 secondary peaks labeled Fe. Run 5 was taken from an exterior surface region.
Material Peak Actual (keV) Run 1interior Run 2interior Run 3interior Run 4interior Run 5surface Reported(keV) Mg Ka1 1.254 -- -- -- -- -- Mg K-edge 1.303 -- -- -- -- -- Al Ka1 1.487 4000* 4000* 4000* 4000* 4000 1.45 (Al) Al K-edge 1.560 -- -- -- -- -- Si Ka1 1.740 -- -- -- -- 304 1.70 (Si) Si K-edge 1.840 -- -- -- -- -- S Ka1 2.308 -- -- -- -- -- Pb Ma1 2.346 -- -- -- -- 194 2.35 (Pb) Bi Ma1 2.423 -- -- -- -- -- S K-edge 2.470 -- -- -- -- -- Cl Ka1 2.622 -- -- -- -- 122 2.65 (Cl) K Ka1 3.314 -- -- -- -- 161 3.30 (K) K K-edge 3.608 -- -- -- -- -- Ca Ka1 3.692 -- -- -- -- 168 3.70 (Ca) Ti Ka1 4.511 -- -- -- -- 615 4.50 (Ti) Ti K-edge 4.965 -- -- -- -- 137 4.95 (Ti) Cr Ka1 5.415 -- -- -- -- -- Mn Ka1 5.899 -- -- -- -- -- Cr K-edge 5.989 -- -- -- -- -- Fe Ka1 6.404 100* 200* 1400* 100* 217 6.40 (Fe) Mn K-edge 6.538 -- -- -- -- -- Fe K-edge 7.111 -- 30* 200* -- 66 7.05 (Fe) Ni Ka1 7.478 -- -- -- -- -- Cu Ka1 8.048 -- -- -- -- -- Cu K-edge 8.980 -- -- -- -- -- Zn Ka1 8.639 -- -- -- -- -- Zn K-edge 9.661 -- -- -- -- -- Pb La1 10.55 -- -- -- -- 54 10.55 (Pb) Bi La1 10.84 -- -- -- -- -- Table 1. Peak intensities from EDAX analysis on metallurgical sample taken at 4 interior locations (Runs 1-4) and one location on the exterior surface (Run 5). Data in rightmost column are peak locations reported, along with the material they were indexed to. (*) indicates estimate from EDAX screen shots
Energy dispersive X-ray (EDAX) is useful for identifying the presence of elements in an alloy, but quantitative composition measurement requires careful calibration to known standards. Nonetheless, there is no observable Cu or Zn found anywhere in the sample. This suggests the sample is a pure Al-Fe alloy, with some surface contamination.
1.2.2 MDRL Laboratory Ronald A. Weiss, Sr. Group Engineer, McDonnell-Douglas Research Laboratory The analysis was conducted by J.E. Holliday using X-Ray fluorescence and soft X-Ray spectroscopy. It is stated they were given sample #1
Material XRay fluorescence Soft X-Ray spectroscopy Al 0.95 0.98 Fe 0.05 0.01-0.02
Table 2. Composition of metallurgical sample determined by x-ray analysis
In this analysis, Holliday reports the presence of cavities often associated with shrinking, and an overall microstructure consistent with solidification processing. He identifies small crystals of Fe-Al intermetallic compound. It is noted they are more numerous near the outer surface than in the interior. The percentage of Fe is higher in the XRF signal because it samples the enitre cut surface, while the soft X-ray spectroscopy samples only a 1mm x 3mm spot on the cut surface, initially located in the interior of the sample. The second phase inclusions are described as needle-like, but their sizes are not given.
1.2.3 Spectro-Chemical Research Laboratories 3300 West Lawrence Avenue, Chicago IL 60625, Bernard B. Hauser
This analysis by an independent lab appears to have been ordered by Art Bethke, (Motorola?). It is not clear if this sample is from the same where this sample was cut from. Bethke later reported the composition most closely matched the 2011 alloy. The standard composition range for this alloy is shown for comparison the Table below.
Material Sample Alloy 2011 Al balance balance Cu 5.68 5.0-6.0 Zn 0.02 0.30 max Fe 0.38 0.7 max Si 0.26 0.40 max Mn 0.02 (<0.05) Ni -- (<0.05) Mg 0.01 (<0.05) Ti trace (<0.05) Pb -- 0.20-0.6 Bi -- 0.20-0.6 Table 3. Measured composition of metallurgical sample, with commercial aluminum alloy 2011 shown for comparison.
These results indicate the presence a large amount of copper, along with other components that suggest this is likely a commercial alloy, in contrast to the other analyzed samples.
1.2.4 Antsas Technical Services - EDAX analysis Antsas Technical Services, Another analysis via EDAX was conducted in 1994, again showing 2 Fe peaks in addition to the primary Al, and an absence of other materials. It is unknown if this data is from the same material analyzed in 1973. The analysis indicates the sample is 99.5% Al, with 0.5% Fe.
2. DISCUSSION Aluminum alloys containing significant concentrations of Fe have been prepared and stuided in the laboratory at least since 1916[1]. Precipitates of the AlFe3 intermetallic compound were identified in these alloys as early as 1919[2]. By the mid 1970's there were several hundred papers in the literature concerning Al-Fe as an alloy, owing to its interest as in intermetallic forming system[3], high temperature structural applications, and a creep-resistant high temperature conductor[5]. Such alloys consist of an aluminum matrix into which are dispersed iron aluminide particulates, that form a creep resistant microstructure enabling it to maintain structural integrity at elevated temperature[5]. The class of structural intermetallics compounds that includes iron aluminides (Fe3Al, FeAl), along with related systems nickel aluminides (Ni3Al, NiAl) and titanium aluminides (Ti3Al, TiAl) posess many attractive properties for high temperature structural applications. The aluminum rich composition favors formation of protective Al2O3 in oxidizing environments, low density, high melting points, and high temperature strength[6], and it is predicted they are the most likely to replace superalloys in future applications. A key challenge is overcoming the brittleness of pure single phase intermetallics at low temperatures and developing improved fabrication techniques.
Given the low solubility of Fe in Al and their widely different melting temperatures, producing a bulk alloy of these materials is difficult. An overall composition of Al0.95Fe0.05 can be prepared via solidification from a high purity melt above 700C containing Al and Fe in these quantities, or via powder metallurgy whereby Fe and Al particles are milled together in a mechanical attrition process, then sintered to form a bulk compact. In the metallurgical analysis of 1973, it is mentioned that the sample has large grains with needle- like iron-rich strucutures. This is suggestive of a solidification process where Fe-rich liquid segregates ahead of dendritic or cellular/ columnar solidification and forms extended iron-rich strucutres and precipitates in the interdendritic/intercellular spaces. Powder metallurgical microstructures typically would consist of a more equiaxed microstructure with small Al grains interspersed with compact AlFe or Al3Fe intermetallic particulates.
Figure 3. Fe-Al Phase diagram. Sample composition is on the aluminum- rich end at Al0.95Fe0.05.
3. CONCLUSIONS Technical From the available metallurgical analysis documentation of 1973, it appears · The sample is an alumunum matrix composite with overall composition Al0.95Fe0.05, with extended or needle-like Fe-rich structures, likely an iron-aluminide intermetallic phase. · Given the composition and microstructure this sample must have been produced in a well-controlled metallurgical process, such as in a laboratory. · The capability to produce this material has existed since 1920, but this composition would not have been widely available until sometime after World War II. By 1973 it would have certainly been available to someone with R&D connections in the aluminum or aerospace industries.
Relation to location of discovery · The claim is that this metal sample was recovered from an 1897 'debris field' in Aurora TX, but there is absolutely no proof that this sample is truly from this location. The sample discovery was not properly documented and changed hands several times thus making it useless for further study. · Although Al-Fe alloys have been produced in research quantities throughout most of the 20th century, they are not available commercially, and therefore highly unlikely to have been deposited by normal human activity in a rural area such as the location alleged. · If the sample were truly collected from a debris field (for which there is no proof) it is almost certain that additional amounts of material would remain at the site. These fragments, likely in much smaller sizes, perhaps 1 mm or less, would probably lie within the top few cm of soil or embedded in rock faces. This alloy would also be likely to remain relatively stable underground for decades. · Although they may not be locatable by 'hobbyist' metal detectors it is likely that archaeological excavation with fine particle fragment collection techniques could discover additional samples of this alloy-- if it exists in a debris field of fine particulates. · If new samples could be found (with proper on-site scientific documentation), the crucial step would be to examine in detail the composition and microstructure to ascertain with more certainty how it might have been produced. Additional analysis to estimate the time this material was in contact with the soil would be needed.
4. REFERENCES 1. O. Bauer and O. Vogel, "Aluminium-zinc alloys", Internationale Zeitschrift fur Metallographie, v 8, n 3, p101-178, (1916). 2. P.D. Merica, R.G Waltenberg, J.R.Freeman, "Constitution and metallography of aluminium and its light alloys with copper and magnesium", Bulletin of the American Institute of Mining Engineers, n 151, p1031-1049, (1919). 3. S. Nasu, U.Gonser, P.H. Shingu, Y. Marakami, 57Fe Mossbauer spectra in splat quenched Al-0.5, 1, 3 and 5 at% Fe alloys, Journal of Physics F (Metal Physics), v 4, n 2, L24-28 (1974). 4. A. Olszowka-Myalska, J. Szala, J. Cwajna, Characterization of iron aluminides formed in situ in an aluminium matrix compositMaterials Characterization, v 56, n 4-5, p379-83 (2006). 5. R.W. Westerlund, "Effects of composition and fabrication practice on resistance to annealing and creep of aluminium conductor alloys", Metallurgical Transactions A (Physical Metallurgy and Materials Science), v 5, n 3, (1974). 6. J.R. Davis, Heat Resistant Materials, ASM Handbook, 1997.
1.1 Introduction
Figure 1. Photographs of aluminum sample obtained from B. Case, 1973. Numbers on top scale correspond to 0.1 inch. As this was an amateur investigation, there is no documentation of proof that the sample came from this location. Furthermore, as its provenance is associated with Mr. Schuessler and Mr. Case, both associated with studies of paranormal phenomena and hoaxes, it is highly questionable that this sample was found in the location stated. There is no information regarding the age of the sample. Nonetheless, the sample did exist in 1973, and was subjected to seemingly valid metallurgical analysis. It is on these results that we comment.
1.2 Analytical Results
Figure 2. Sketch of sample and its sectioning into multiple samples for analysis (Schuessler documentation 1973)
The sample was apparently sectioned and sent to several analysis labs. The results are tabulated below.
1.2.1 EDAX Analysis Robert J. Danmeller, Marion Russo, (organization not given) In the documentation, it states this organization was given sample #2, but from their sketches, however, it appears they may have been sent sample #1. Analysis was conducted using SEM imaging and EDAX composition analysis.Runs 1-4 were taken from the face of a surface exposed by the sectioning, and correspond to the interior of the sample. EDAX specra indicates strong Al peak with 2 secondary peaks labeled Fe. Run 5 was taken from an exterior surface region.
Material Peak Actual (keV) Run 1interior Run 2interior Run 3interior Run 4interior Run 5surface Reported(keV) Mg Ka1 1.254 -- -- -- -- -- Mg K-edge 1.303 -- -- -- -- -- Al Ka1 1.487 4000* 4000* 4000* 4000* 4000 1.45 (Al) Al K-edge 1.560 -- -- -- -- -- Si Ka1 1.740 -- -- -- -- 304 1.70 (Si) Si K-edge 1.840 -- -- -- -- -- S Ka1 2.308 -- -- -- -- -- Pb Ma1 2.346 -- -- -- -- 194 2.35 (Pb) Bi Ma1 2.423 -- -- -- -- -- S K-edge 2.470 -- -- -- -- -- Cl Ka1 2.622 -- -- -- -- 122 2.65 (Cl) K Ka1 3.314 -- -- -- -- 161 3.30 (K) K K-edge 3.608 -- -- -- -- -- Ca Ka1 3.692 -- -- -- -- 168 3.70 (Ca) Ti Ka1 4.511 -- -- -- -- 615 4.50 (Ti) Ti K-edge 4.965 -- -- -- -- 137 4.95 (Ti) Cr Ka1 5.415 -- -- -- -- -- Mn Ka1 5.899 -- -- -- -- -- Cr K-edge 5.989 -- -- -- -- -- Fe Ka1 6.404 100* 200* 1400* 100* 217 6.40 (Fe) Mn K-edge 6.538 -- -- -- -- -- Fe K-edge 7.111 -- 30* 200* -- 66 7.05 (Fe) Ni Ka1 7.478 -- -- -- -- -- Cu Ka1 8.048 -- -- -- -- -- Cu K-edge 8.980 -- -- -- -- -- Zn Ka1 8.639 -- -- -- -- -- Zn K-edge 9.661 -- -- -- -- -- Pb La1 10.55 -- -- -- -- 54 10.55 (Pb) Bi La1 10.84 -- -- -- -- -- Table 1. Peak intensities from EDAX analysis on metallurgical sample taken at 4 interior locations (Runs 1-4) and one location on the exterior surface (Run 5). Data in rightmost column are peak locations reported, along with the material they were indexed to. (*) indicates estimate from EDAX screen shots
Energy dispersive X-ray (EDAX) is useful for identifying the presence of elements in an alloy, but quantitative composition measurement requires careful calibration to known standards. Nonetheless, there is no observable Cu or Zn found anywhere in the sample. This suggests the sample is a pure Al-Fe alloy, with some surface contamination.
1.2.2 MDRL Laboratory Ronald A. Weiss, Sr. Group Engineer, McDonnell-Douglas Research Laboratory The analysis was conducted by J.E. Holliday using X-Ray fluorescence and soft X-Ray spectroscopy. It is stated they were given sample #1
Material XRay fluorescence Soft X-Ray spectroscopy Al 0.95 0.98 Fe 0.05 0.01-0.02
Table 2. Composition of metallurgical sample determined by x-ray analysis
In this analysis, Holliday reports the presence of cavities often associated with shrinking, and an overall microstructure consistent with solidification processing. He identifies small crystals of Fe-Al intermetallic compound. It is noted they are more numerous near the outer surface than in the interior. The percentage of Fe is higher in the XRF signal because it samples the enitre cut surface, while the soft X-ray spectroscopy samples only a 1mm x 3mm spot on the cut surface, initially located in the interior of the sample. The second phase inclusions are described as needle-like, but their sizes are not given.
1.2.3 Spectro-Chemical Research Laboratories 3300 West Lawrence Avenue, Chicago IL 60625, Bernard B. Hauser
This analysis by an independent lab appears to have been ordered by Art Bethke, (Motorola?). It is not clear if this sample is from the same where this sample was cut from. Bethke later reported the composition most closely matched the 2011 alloy. The standard composition range for this alloy is shown for comparison the Table below.
Material Sample Alloy 2011 Al balance balance Cu 5.68 5.0-6.0 Zn 0.02 0.30 max Fe 0.38 0.7 max Si 0.26 0.40 max Mn 0.02 (<0.05) Ni -- (<0.05) Mg 0.01 (<0.05) Ti trace (<0.05) Pb -- 0.20-0.6 Bi -- 0.20-0.6 Table 3. Measured composition of metallurgical sample, with commercial aluminum alloy 2011 shown for comparison.
These results indicate the presence a large amount of copper, along with other components that suggest this is likely a commercial alloy, in contrast to the other analyzed samples.
1.2.4 Antsas Technical Services - EDAX analysis Antsas Technical Services, Another analysis via EDAX was conducted in 1994, again showing 2 Fe peaks in addition to the primary Al, and an absence of other materials. It is unknown if this data is from the same material analyzed in 1973. The analysis indicates the sample is 99.5% Al, with 0.5% Fe.
2. DISCUSSION Aluminum alloys containing significant concentrations of Fe have been prepared and stuided in the laboratory at least since 1916[1]. Precipitates of the AlFe3 intermetallic compound were identified in these alloys as early as 1919[2]. By the mid 1970's there were several hundred papers in the literature concerning Al-Fe as an alloy, owing to its interest as in intermetallic forming system[3], high temperature structural applications, and a creep-resistant high temperature conductor[5]. Such alloys consist of an aluminum matrix into which are dispersed iron aluminide particulates, that form a creep resistant microstructure enabling it to maintain structural integrity at elevated temperature[5]. The class of structural intermetallics compounds that includes iron aluminides (Fe3Al, FeAl), along with related systems nickel aluminides (Ni3Al, NiAl) and titanium aluminides (Ti3Al, TiAl) posess many attractive properties for high temperature structural applications. The aluminum rich composition favors formation of protective Al2O3 in oxidizing environments, low density, high melting points, and high temperature strength[6], and it is predicted they are the most likely to replace superalloys in future applications. A key challenge is overcoming the brittleness of pure single phase intermetallics at low temperatures and developing improved fabrication techniques.
Given the low solubility of Fe in Al and their widely different melting temperatures, producing a bulk alloy of these materials is difficult. An overall composition of Al0.95Fe0.05 can be prepared via solidification from a high purity melt above 700C containing Al and Fe in these quantities, or via powder metallurgy whereby Fe and Al particles are milled together in a mechanical attrition process, then sintered to form a bulk compact. In the metallurgical analysis of 1973, it is mentioned that the sample has large grains with needle- like iron-rich strucutures. This is suggestive of a solidification process where Fe-rich liquid segregates ahead of dendritic or cellular/ columnar solidification and forms extended iron-rich strucutres and precipitates in the interdendritic/intercellular spaces. Powder metallurgical microstructures typically would consist of a more equiaxed microstructure with small Al grains interspersed with compact AlFe or Al3Fe intermetallic particulates.
Figure 3. Fe-Al Phase diagram. Sample composition is on the aluminum- rich end at Al0.95Fe0.05.
3. CONCLUSIONS Technical From the available metallurgical analysis documentation of 1973, it appears · The sample is an alumunum matrix composite with overall composition Al0.95Fe0.05, with extended or needle-like Fe-rich structures, likely an iron-aluminide intermetallic phase. · Given the composition and microstructure this sample must have been produced in a well-controlled metallurgical process, such as in a laboratory. · The capability to produce this material has existed since 1920, but this composition would not have been widely available until sometime after World War II. By 1973 it would have certainly been available to someone with R&D connections in the aluminum or aerospace industries.
Relation to location of discovery · The claim is that this metal sample was recovered from an 1897 'debris field' in Aurora TX, but there is absolutely no proof that this sample is truly from this location. The sample discovery was not properly documented and changed hands several times thus making it useless for further study. · Although Al-Fe alloys have been produced in research quantities throughout most of the 20th century, they are not available commercially, and therefore highly unlikely to have been deposited by normal human activity in a rural area such as the location alleged. · If the sample were truly collected from a debris field (for which there is no proof) it is almost certain that additional amounts of material would remain at the site. These fragments, likely in much smaller sizes, perhaps 1 mm or less, would probably lie within the top few cm of soil or embedded in rock faces. This alloy would also be likely to remain relatively stable underground for decades. · Although they may not be locatable by 'hobbyist' metal detectors it is likely that archaeological excavation with fine particle fragment collection techniques could discover additional samples of this alloy-- if it exists in a debris field of fine particulates. · If new samples could be found (with proper on-site scientific documentation), the crucial step would be to examine in detail the composition and microstructure to ascertain with more certainty how it might have been produced. Additional analysis to estimate the time this material was in contact with the soil would be needed.
4. REFERENCES 1. O. Bauer and O. Vogel, "Aluminium-zinc alloys", Internationale Zeitschrift fur Metallographie, v 8, n 3, p101-178, (1916). 2. P.D. Merica, R.G Waltenberg, J.R.Freeman, "Constitution and metallography of aluminium and its light alloys with copper and magnesium", Bulletin of the American Institute of Mining Engineers, n 151, p1031-1049, (1919). 3. S. Nasu, U.Gonser, P.H. Shingu, Y. Marakami, 57Fe Mossbauer spectra in splat quenched Al-0.5, 1, 3 and 5 at% Fe alloys, Journal of Physics F (Metal Physics), v 4, n 2, L24-28 (1974). 4. A. Olszowka-Myalska, J. Szala, J. Cwajna, Characterization of iron aluminides formed in situ in an aluminium matrix compositMaterials Characterization, v 56, n 4-5, p379-83 (2006). 5. R.W. Westerlund, "Effects of composition and fabrication practice on resistance to annealing and creep of aluminium conductor alloys", Metallurgical Transactions A (Physical Metallurgy and Materials Science), v 5, n 3, (1974). 6. J.R. Davis, Heat Resistant Materials, ASM Handbook, 1997.