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Timna Slag Identification

SEM Phase and Compositional Analysis of 4 Timna Slag Samples

Jessica Eileen Edwards 5/10/2011

An analysis of 4 lag samples taken from 4 separate pieces of slag found at the Timna valley mine site in Egypt using a Scanning Electron Microscope (SEM) to Identity phase composition in order to gain an understanding of the smelting technology used to create each sample and determine date of origin.

2 University of Liverpool ALGY 740 Prof. Matthew Ponting

Introduction

This analysis is a continuation and revision of my Timna Slag analysis done as a practical analysis project in for Prof. Matthew Ponting s Artifacts and analysis module from last semester. The goal of that project was to first identify the different phases of the slags, through reflective light microscopy, in order to identify what metal was smelted, the type of furnace it was smelted from (e.g. pit furnace or tap furnace) and the possible flux used. Three slag samples were used in the previous analysis; those same three slags were analyzed for the current analysis with the addition of a fourth sample to broaden the sampling pool. The method of the last analysis could only give so much information. Reflected light microscopy can only be a visual analysis, where the end results are based on comparisons and guesswork. This is not to say that the method doesn t have merit; it is just a more difficult method for those who do not have a background in mineralogy and crystalline structures, of which I do not. All of my conclusions were based on visual comparisons of mineral phases in slag micrographs found in other sources, like Bachmann s Identification of Slags from Archaeological Sites (1982). It wouldn t surprise you that information on slag composition and analysis are scarce, since the topic is currently not a popular one, but Bachmann s books, though old, is one of the best resources for anyone looking for examples of different types of slags and the phase compositions found in them. Because of my lack of knowledge in the area of mineralogy and crystalline structures this current analysis accomplished through the use of an SEM (Scanning Electron microscope). This equipment has a far greater range of magnification and has the ability to measure the amounts of compound found within the slag. Because of this, it can be confirmed if the findings from the last analysis were correct. This is one of the main goals of the current analysis, confirming the findings of the last analysis and changing what information needs to be corrected based on new findings. The second the goals is to identify slag sample 3, an interesting sample from the last analysis, that has unusual phases far different from what was seen in the other samples. This sample was the hardest to identify in the last analysis, in fact, no true identification of any kind could be determined from what could be seen using microscopy. All that could be determined was that it was copper slag, based copper Prills found in the slag, and that it was most likely tap slag do to the flow pattern of the mineral phases. Before going into the details of the analysis we should again revisit what exactly slag and the process of smelting is. Slag: Slag is a waste product, discarded vitrified material, from the process of metal smelting. It is produced from the unwanted non-metallic material, or gangue, from metal ores. Consisting mainly of (Si) minerals, the gangue portion of a metal ore melts at a lower furnace temperature than the desired metal. It is this characteristic that makes separating the metal from the gangue during smelting possible. Copper is heavier than the molten slag so it sinks to the bottom of the smelting furnace with the molten slag resting on top. In a tap furnace the molten slag is siphoned away from the copper and out of the furnace, this allows for a continuous smelting process without disruption. Slag holds important information concerning the process of smelting and how smelting technology has advanced over time. For example, a piece of slag can be analyzed to determine if it is from an early smelting furnace, tap furnace or from crucible smelting (smelting from a mold). Knowing this can give archaeologists a better understanding of the advancements in smelting technology at the Timna copper mines, how they advanced over time, what type of minerals the copper ores consisted of, what types of flux were used, the temperature at which the copper was smelted, and so on. A lot of information can be extracted

3 University of Liverpool ALGY 740 Prof. Matthew Ponting from a tiny piece of slag that can tell almost everything about the pyrotechnology that went into its creation. Photomicrography is just one analytical stepping stone towards gaining this information. (Bachmann, 1982. P. 9-14) (Hauptmann,2007. P. 20-21)(Nicholson and Shaw, 2000. P. 151-153)There are many more advanced analysis tools that can be used to assess the mineral and chemical content of slag, but sometimes the basics are a good place to begin. Photomicrography is the method of taking digital micrographic photos of a sample through a microscope and the method used in this analysis. While the information that photomicrography can give is limited it can help to give direction on what the next course of action should be towards further analysis. For example, for an analysis to find if a sample of slag came from a Sulfide ore or an Oxide ore, the method of photomicrography can be employed before a more extensive, and more expensive, method. If through a micrographic image, sulfide inclusions can be identified, then it can be determined that the slag is made from smelting sulfide ore, thus removing the need for a more extensive analysis method, such as inductively coupled plasma mass spectrometry (ICPMS). If sulfides cannot be identified, then the need for more discerning analytical techniques would be recommended, but it is better to be sure that such techniques are needed before deciding to pay for an expensive method of analysis. Smelting: The tools needed for smelting include: A hearth or furnace, crucibles, tongs, withies, blowpipes, bellows, and tuyres (Evely, 2000. P. 326). Different metals and minerals have different melting points. A hearth, or furnace, must be able to reach the temperature needed to properly melt both the metal and non metal parts of the ore in order for proper smelting to take place. For this to occur the hearth or furnace must be able to create a reducing environment; this means a low oxygen level environment (Evely, 2000. P. 325-328). Hearths would have been used in crucible smelting, where the ore would be melted inside a stone or ceramic crucible, allowing the metal to sink through the molten slag (the molten non metal substance of an ore) 1to the bottom of the crucible. This process would require multiple reheating to achieve any usable amount of metal. The slag, with the newly smelted metal, would be left to cool; then removed from the crucible. The metal that had pooled at the bottom of the crucible during the smelting would then be removed from the slag (Evely, 2000. P. 346-347). This form of smelting is not very efficient and would not have produced large quantities of copper. Furnace smelting produces a more stable firing atmosphere since it is an enclosed structure with better oxygen level control capabilities for an oxygen reducing atmosphere. Like with the crucible smelting the copper would be reduced from the ore then would pass through the molten slag to form an ingot on the bottom of the furnace. The first furnaces did not have tapping capability, so the slag would cool in the
1

Reduction in a nut shell: The formula for reduction in metallurgy is MeO+CO=Me+CO , where (MeO ) is the ore you are smelting, (CO) is the Carbon monoxide produced from the charcoal or wood fuel, (Me) is the reduced or smelted metal and (CO )is the Carbon Dioxide that comes from the Carbon Monoxide bonding with the oxygen in the ore (MeO). The process of reduction mainly comes from the process of (CO) becoming (CO ). (CO) is an unstable compound and all unstable compounds try to return to their most stable form. In reduction heating only the amount of oxygen needed for the combustion in the furnace is allowed. This low oxygen environment is what produces the carbon monoxide from the fuel. The (CO) seeks out more oxygen to stabilize and since the atmosphere does not contain enough oxygen for this, the (CO) takes the oxygen from the ore, turning itself into its more stable form of (CO), a gas that can be expelled from the furnace without hassle. Removing the oxygen from the ore helps the metal components to bond to each other during smelting and the non-metal components to break down faster during the smelt. (Matthew Ponting, Pyrotechnology Module lecture 24/03/2011)

4 University of Liverpool ALGY 740 Prof. Matthew Ponting furnace on top of the copper ingot. In a tap furnace the molten slag could be poured out of the furnace as the smelting process happened, meaning a continuous smelting process could take place. Smelting generally occurred in areas near the ore deposits where the molten metal would be made into ingots. (Evely, 2000. P. 341). In order to convey the findings of this current analysis properly a summary of findings for each of the sample analyzed in the last analysis should be given before explaining the new findings. This will be done in much the same fashion as in the last project, listing each sample and their findings separately. So we begin with Sample1: In the previous analysis sample I was assumed to be made of four mineral phases. A homogenous glassy phase, fayalite crystal phase, a magnetite phase and possibly a wstite phase. This was determined by analyzing the crystalline structures within the slag photomicrographs and comparing them to slag phases of other micrographs taken from Timna slags in Bachmann s book. I speculated from these comparisons that the long crystalline laths were fayalit, and the white dendrites were either magnetite, wstite or a mix of both, all within a glassy matrix of unidentified composition. (Bachmann,1982. P. 15) Information from Bachmann, and an interview with geologist Dr. Rick Burquist, gave me information to determine that slag sample 1 was most likely tap slag based on amount of crystalline formation was present in the slag. Taped slag would cool more quickly when exposed to the air causing smaller and fewer crystal formations. (Burquist, 2010.Interview). After looking at the bulk analysys of the large crystals ,I was pleased to find that after analyzing this sample in the SEM, many of my observations were correct. The large crystalline laths are indeed fayalite crystals due to their high (Fe) (around 42%) and (Si) ( around 36%) content with a small amount of (Mn) (around 20%) (plate 1). (Bachmann, 1982. P. 9-14) The smalls crystal bulk analysis showed them to be just magnetite crystals with no wstite ,based on their high (Si) content at around 42%, with (Fe) around 33% (plate 2). Interestingly, these crystals had a (Ca) content that measured around 12% (plate 2).It was also discovered that the glassy matrix these crystalline structures were incased in was fayalitic glass. Basically, it is the fayalite that was not able to crystallize due to rapid cooling. We know that it is fayalitic glass because of the Fe (around 23%) content mixed with the (Si) (around 45%)(plate 3).These crystals also had trace levels of (Ca), around 15%. Several bulk analyses were done of sample 1 to get an idea of the overall chemical composition of the slag as a whole (plate 3) and each separate phase (figure 9 and table 1). From the Bulk analysis of sample one as a whole, it was not surprising to find high (Si) and iron levels since fayalite and magnetite are present in the slag. The high iron levels helped confirm what I had speculated in my last analysis, that iron oxide flux used in the slag to lower its viscosity. The manganese is most likely comes from either the ore minerals or from what was used for the iron oxide flux. It is my belief that it comes from the ore based on findings from sample 4 which will be discussed later. The first bulk spotlight analysis of each phase gives a better look at each phase s chemical composition. Spots 1 and 4 have high levels of (Si) and (Fe), with (Si) being higher then (Fe), which is indicative of magnetite. 2, 5 and 6 also have high levels of (Si) and (Fe) with lower levels of magnetite (between 10% and 12%). The (Si) and (Fe) levels are opposite to 1 and 4, with the (Fe) being higher than (Si). This is to be expected from fayalite crystals. Spot 3 comes from the glassy matrix and shows (Si) to be the highest level then (Fe) and finally (Ca). It is possible that the (Ca) found within the slag comes from lime used to line the furnace walls since Oxide ores (ore used at Timna) does not generally have (Ca) in them. Number 7 was a a surprise, Its (Fe) content measured at 92.95% meaning it was reduced iron. This tells us about the temperature of the furnace when the slag was being formed. Iron smelts at

5 University of Liverpool ALGY 740 Prof. Matthew Ponting 1,100 C, so the furnace that produced this sample had to have reached at least that temp and have the correct reducing conditions in order to have reduced the ore enough to produce even a small amount of iron. (Ponting, 2011. Lecture) Spot 8 is a copper prill indicated from the High level of (Cu) (94.33%).(figure 8 & table 1) The levels of all the compounds within this sample match those from Beno Rothenberg s analysis, as being from the Middle Kingdom Period, in his book The ancient metallurgy of copper: archaeology, experiment, theory. (Rothenberg, 1990. ) (Figure 1) (Figure 1)

sample 1 Back Scatter image; (1) copper Prill (white), (2) magnetite (light gray), (3) fayalite crystals (medium gray), (4) fayalite glass (dark gray)

(Figure 2)

sample 1 image without Back Scatter; (1) copper Prill (white), (2) magnetite (light gray), (3) fayalite crystals (medium gray), (4) fayalite glass (dark gray)

(Figure 3)

Sample 1 Back Scatter Image; ) fayalite glass (dark gray), large fayalite crystals (medium gray), small angular magnetite crystals (light gray).

Sample 2: Sample 2, in the last analysis was found to be the same as sample one, with

(Figure 4)

6 University of Liverpool ALGY 740 Prof. Matthew Ponting the exception that there appeared to be more magnetite crystals and less fayalite crystals from what could be seen on the micrographs. The analysis of sample 2, through the SEM, shows that there are more dendrite magnetite crystals then in sample 1, just of a smaller size. But, there is more fayalite, unlike what was though in the previous analysis. The fayalite are also of a smaller size then those in sample1, they also appear better formed in this sample and are underneath the magnetite crystals. The bulk analysis of sample 2 shows high (Si) content and (Fe) content, but in this slag the (Fe) content is higher than the (Si) with the (Fe) content being around 61% and the (Si) content being around 28%. It is possible, that the reason why the fayalite crystals are better formed and more numerous in this slag, is due to the higher (Fe) content (Plate 5). The higher (Fe) content then the (Si) content provides more proof towards an iron flux being used during the smelting process. We also find varying (Ca) levels within this slag and its crystalline phases showing that it too was most likely formed in a furnace that was coated in lime. (plate 4) A bulk spotlight analysis was done on the individual crystalline phases within this sample. Spot 1 is a copper prill that showes a Cu content of 94.90%, very pure copper. Spots 2 and 3 could be reduced iron but due to its high (Fe) content, 2 being 91.56% and 3 being 94.10%, but because of the O levels, it is likely they are high (Fe) magnetite , (figure Sample 2 Back Scatter Image; (1) Large fayalite crystals (medium 10 & table 2). 4 and 5 are from fayalite gray), (2) small magnetite crystals (light gray), (3) fayalite glass crystals with (Fe) levels, 79.55% for spot 4 (dark gray), (4) air bubble (black) and 78.68% for spot 5. The (Si) levels for these two spots are much higher than 2 and 3, which is to be expected of fayalite since its formula is (Fe2SiO4) while magnetite is (Fe3O4). (Bachmann, 1982. P9-14) the last 2 spots, 6 and 7 are from the fayalitic glassy matrix and unsurprisingly the (Fe) content, though still high, is even lower than in the previous spots and the (Si) content higher (figure10 & table 2). Some corroded copper Prills were analysed from this sample, also using spotlight analysis. The inner part of the Prills and the substance surrounding them were the focus of the analysis to see what the substance was. All of the spots had some level of (Fe), Cu, (Si), and O but they all also have verying levels of Cl (Chlorine) and spots 6-13 had S (Sulfer). Both of these compounds are by-products from the corroding of the copper, the presence of the sulphur means that part of that substance is of copper sulphide. Copper sulphides are usually found in copper sulphide ores, but according to Prof. Matthew Ponting, sulphides can be found in slag from smelted oxide ores because they sometimes have minute amounts of sulphur in them(Table 3 & figure 11). (Ponting, 2011. Lecture) The evidence found in this slag sample suggests that it, like sample 1, is from the Middle Kingdom period, based on comparisons to Rothenberg s findings. (Rothenberg, 1990) This also means that my previous assumption for this sample also being tap slag is correct, since these types of furnaces were in use by this period. Sample 3: This was the sample that was unable to be identified in the last analysis. In the previous analysis it was speculated that the crystalline phase that dominated most of the slag was delafossite . It was believed that the slag came from a disrupted smelting process where the slag was did not reach a molten state, causing delafossite crystals to grow as the slag cooled. It

(Figure 5)

Tightly packed Knebelite laths (dark gray) surrounding a copper prill (light gray) with reduced lead (white areas around prill edges) Manganese Crystals encased in tightly packed Knebelite laths.

7 University of Liverpool ALGY 740 Prof. Matthew Ponting was also speculated that perhaps a different flux, other than iron oxide, possibly Manganese, was used. The theory about the laths being delafossite was proven wrong from the chemical analyses done on the slag. The spotlight analysis on different parts of the crystalline phase shows high levels of (Mn) (manganese) in the slag (figure 5). Between spots 1 and 4 the (Mn) levels go from as low as 35.20% to 45.76%, not much of a variation. The (Si) levels are of almost the same ratio to the (Mn), only slightly higher. Low levels of (Fe),(Ca) and (O) are also present along with minute traces of other elements left over from the ore. It is apparent that this is manganese rich slag, this is evident from the high levels of (Mn) the spot analys shows (figure 12 & table 4) and from the bulk analysis where the (MN) is listed at a level of 40.01% (plate 6). This means that the crystalline structure is Knebelite (figure 6), a mineral with the formula (Mn, Fe) SiO4. The fact that this slag is manganese rich means that it was created at the time the Egyptians at Timna switched to (Mn) as a fluxing agent. This would put the date of this slag in the Late New Kingdom period. (Rothenberg, 1990) It appears that the Egyptians made a good choice in changing to (Mn) as a flux since this slag has fewer copper prills embedded in its phases then the in samples 1 and 2, which used (Fe) as flux. The second bulk spotlight analysis shows the same thing, except a copper prill is evident for spot 1 and spots 2, 3 and 8 are shown to be( Pb) (lead). The lead being found in the slag means that conditions in the furnace were hot enough to reduce lead from the copper being smelted. (figure 13 & table 5) Sample 4: This slag sample was the one added to broaden the sampling pool for this analysis. It was meant to provide another copper slag sample that the other 3 samples could be compared to. Things did not work out that way, but this is not necessarily a bad thing. I first noticed something wasn t right when I was able to get my first look at sample 4 under a microscope. Not only did the crystalline phases appear drastically different but the metal found in the slag was not copper but Iron. This, as you can imagine, confounded me since no record of iron smelting at Timna has of yet been recorded. I was excited because I had helped discover something new but disappointed that I could not compare the sample to the other three like I had originally planned. Instead I can make at least 1 comparison regarding phase composition between copper and iron slags. To start off, the main phase of the slag consisted of white blobs; the best description for it I can give is that these blobs jumbled together resembled brain matter when looking at a cross section (figure 7). Not a pretty description, I know, but it s the best way I can describe it. These blobs were wstite crystals, what I had original speculated the Magnitite in Samples 1 and 2 could be during the previous analysis. Wstite , like Magnitite , is an iron oxide with the formula (FeO). From the bulk analyses done, the elements found in this slag are (Fe),(O),( Al),(Mg), (Si), (Ca),(P) and (S). If you recall, for sample 1 I stated that I believed the (Mn) came from the ore and not the flux. This is because the iron flux would have come from iron ore in the Timna valley, this would be the same ore most likely used to create this slag. As you can (Figure 7) see from my listing of elements no (Mn) is mentioned. This shows that the iron ore in the area does not have Mn , therefore it could not have contributed (Mn) to slag samples 1 and 2. The overall bulk analysis shows the (Fe) content at 79%, the Si at 7.37% and Ca at 8.87%. (plate 7) A spotlight analysis of the crystalline structures and glassy matrix show the same results, high (Fe) content with low (Si), along with

Wstite crystal formations (light gray) in glassy matrix(dark gray)

8 University of Liverpool ALGY 740 Prof. Matthew Ponting some high (Ca) readings in spots 3, 4, 5 and 6. (figure 14 & table 6). The spots with the high Ca are areas of the glassy matrix. Spots 1 and 2 have a much lower (Ca) and (Si) content, with a much higher (Fe), reaching into the 90% range (table 6). The (Ca) content can be explained by the Spotlight analysis mentioned below, but I the low (Si) content was unexpected so I searched for some literature on iron slags to find an explanation. Prof. Ponting provided me with a copy of Ramla Final Report on The excavations north of the White Mosque, which provided some helpful insight into iron smelting and slag composition. The article analyzed 2 iron slags that had similar phase compositions to mine; between the 2 the slags had high (Fe) content, suggesting an inefficient smelting process. Roman iron slags on average contain 40%-60% (Fe) and 20%-30% (Si), so the smelting process used for the two slags analyzed was either of an earlier method or the smelter was unskilled at controlling the furnace. (Gutfield, 2010. P. 293-294) from this information , and the fact that this sample was found at Timna where iron melting has not been recorded I have concluded that this iron slag was from an earlier iron smelting method , possibly by a small nomadic group passing through the Timna valley, based on the high (Fe) content and low (Si) content. A spotlight bulk analysis was done on the edge of the slag where their appeared to be remains of furnace wall in the slag. Spots 1, 2 and 6 had high Ca content, ranging between 76%-82%. There are also higher levels of Oxygen in these spots indicating that this area of slag is comprised of the lime from the furnace wall. Spots 3 and 5 are in the interaction zone where the glassy matrix of the slag and the lime furnace wall remnants mix together. This happens when the molten slag becomes hot enough to start melting the inside of the furnace wall. (figure 15 & table 7) Conclusion: From the analysis I have concluded that slag samples 1 and 2 are made up of 3 phases, fayalite, magnetite and a fayalitic glassy matrix. They both are also from a tap furnace that used iron oxide as a flux; most likely the flux came from iron ore available in the area. From the chemical composition analyses it was also determined that both samples came from the Middle Kingdom period of Egypt. It was also discovered that sample 1 had an iron prill, which meant that the furnaces at the time were advanced enough the reach temperatures of at least 1,100 if controlled correctly. Sample 2 had some corroded copper prills with copper sulphide surrounding them, finding sulphides in slag is not unusual but it normally only occurs in slag from smelting sulphide ore. Since Timna has oxide ore it is an unusual find but not impossible. Slag sample 3 was finally able to be identified as a Manganese rich slag with a Knebelite crystalline phase. The reason for so much (Mn) in the slag is due to a (Mn) rich ore being used as flux during the smelting process. Because this sample had a lower amount of copper, it would seem that (Mn) is a better fluxing agent then (Fe), this is Figure 8 probably why the Egyptians changed over to using it. Because sample 3 is slag from (Mn) fluxed smelting it is most was found to be from the Late New Kingdome period, when this type of flux was in greater use at Timan. Sample 4 was the biggest surprise with it being an iron slag. After researching iron smelting locations in the Middle East I could no reference to iron smelting ever taking place at Timna. This does not mean it didn t, but since no evidence has been found,

Sample 4: Iron Prill (White) surrounded by Wstite crystals (light gray) in glassy matrix

9 University of Liverpool ALGY 740 Prof. Matthew Ponting until this sample, it can be assumed that whatever iron Smelting operation was going on; it was on a small scale. This is also evident by the inefficiency of the iron extraction from the slag. It s possible the people smelting the iron were either using one of the earliest, less advanced, smelting techniques , or the (Fe) content of the iron ore at Timna was high enough that controlled smelting wasn t felt needed. I believe the latter and feel more comfortable dating this piece of slag around the beginning of the Iron Age (1200-1000 BC). This sample also had a high amount of Ca close to its edges. This was determined to be lime from the furnace wall that had begun to melt and mix with the slag. All of the samples had some levels of Ca in them, and just like with sample 4, this most likely came from lime furnace lining. Another reason I believe that the smelting technology used for this sample was an earlier primitive method, is because of the lack of iron prills found (figure 8) even though the (Fe) content was so high. This tells me that the reducing levels within the furnace may not have been controlled enough to reduce the iron from the ore into a metallic state. This is only speculation; I was unable to find the right type of information in order to determine if my theory was correct. While the microscope, and the micrographs I took with it, was helpful to my last analysis, it was only able to get me started. The one advantage I received from having to use the microscope is that I learned how to identify the mineral phases in the slag visually. If I had been able to have access to the SEM last semester to do my analysis, I would not have spent as much time trying to identify the crystalline structures from how they looked because I would have had the chemical composition information available. The analysis using the SEM is far superior to just using a microscope. I found that gaining information was easier and more information became available to me because after getting the chemical analysis for each slag I knew exactly what I needed to look for in the literature.

10 University of Liverpool ALGY 740 Prof. Matthew Ponting (Plate 1) Timna 1-Large Crystal Bulk Analysis

T ota l

(Plate 2) Timna 1-Small Crystal Bulk Analysis

T ota l

 

K a i Mn Fe O T otal

10 0.00

E le me t l i

Li K K K K K K K K K

e 1 1 1 1 1 1 1 1 1

k eV 1.487 1.740 2.013 3.313 3.691 4.510 5.898 6.403 0.523

K Ratio 0.0145 0.1390 0.0071 0.0052 0.0818 0.0077 0.0225 0.1969 0.0000

W t% 2.43 19 .58 1.06 0.58 8.84 0.89 2.65 23 .17 40 .81 100.00

At % 2.20 17.05 0.84 0.36 5.39 0.45 1.18 10.14 62.38 100.00

Com pou l2O3 i O2 2O5 K2O aO iO 2 M nO F e2O 3

E leme t Mg i a Mn Fe O T otal

Li K K K K K K

e 1 1 1 1 1 1

k eV 1.254 1.740 3.691 5.898 6.403 0.523

K Ratio 0.0105 0.1455 0.0049 0.1352 0.2564 0.0000

W t% 1.40 16 .82 0.44 15 .15 29 .05 37 .15 100.00

At % 1.52 15.82 0.29 7.28 13.74 61.35 100.00

Com pou M gO iO2 aO M nO F e2O 3

Cmp W t% 2 .32 35.98 0 .61 19.56 41.53 10 0.00

C hiSq u are 3.29 48.55 1.23 13.88 13.88 75.41 17.70

Cmp W t% 4 .59 41.88 2 .43 0 .70 12.37 1 .49 3 .42 33.12

C hiSq u are 70.94 70.94 70.94 18.96 18.96 2.34 6.90 6.90 73.40 30.0

 

11 University of Liverpool ALGY 740 Prof. Matthew Ponting (Plate 3) Timna 1-Small Crystal Bulk Analysis

Al i

t l

(Plate 4) Timna 1-Overall Bulk Analysis

T o ta l

100.00

1 0 0 .0 0

T o ta l

l K a Ti Mn Fe Te O

V TU

l i

K K K K K K K K K L K

1 1 1 1 1 1 1 1 1 1 1

1.487 1.740 2.013 2.622 3.313 3.691 4.510 5.898 6.403 3.769 0.523

0.0077 0.1054 0.0031 0.0020 0.0046 0.0224 0.0028 0.0553 0.2981 0.0121 0.0000

1. 37 15 .44 0. 45 0. 25 0. 50 2. 32 0. 30 6. 21 33 .96 1. 57 37 .62

1.34 14. 53 0.39 0.19 0.34 1.53 0.16 2.99 16. 07 0.32 62. 14

l2O 3 iO 2 2O 5 l K 2O aO T iO 2 M nO F e2O 3 T eO 3

2 .59 33. 04 1 .04 0 .25 0 .60 3 .25 0 .50 8 .02 48. 56 2 .16
1 0 0 .0 0

48. 60 48. 60 48. 60 1.18 3.20 3.20 3.20 13. 41 13. 41 3.20 39. 12
18.9

RQ

S S S S S S S S S S S Q

E le m e t

Li e

k eV

K R a ti o

W t%

At%

C o m po u

Cmp

W t%

C hi Sq u a re

H II II

!G

H II II

H II I I

e b O t l

Q S

@ F ED C B

a i

a i

e2O3 bO

.79 45.01 3. 3 0.78 14.87 1.94 4.05 22.92 2.01

66

E le e t Al i

i e A1 A1 A1 A1 A1 A1 A1 A1 A1 A1

e 1. 1.740 .013 3.313 3. 9 1 4.510 5.898 6.403 2.343 0.523

ti . 1 57 0.1530 0.0105 0.0057 0.0965 0.0097 0.0261 0.1351 0.0118 0.0000

t .53 1.04 1.59 0. 4 10.63 1.16 3.13 16.03 1.86 41.37 .

t . 7 18.10 1. 4 0.40 6.41 0.59 1.38 6.94 0.22 62.47 .

i re 53. 3 53.83 53.83 53.83 53.83 3.47 5.26 5.26 53.83 38.79 34. 6

4 ' 10 ) %

3 " ( &%

@ 8E F 8D 7 C 8 B 8 87 2 @ 8 79 7 8 7 ( ' ! &  ! %

7 # 7 $

7 # 7 "



7 54 3  

2 D 2 2 2 2 2 2 2 2 

  V U T V

2 @ 9

!G

12 University of Liverpool ALGY 740 Prof. Matthew Ponting (Table 1)

Ta 1 2 4

l . 0. 0 .24 .4 0.72 0.7 1. 2 0. 4

44.1 27.2 4 .07 2 .0 2. 27.1 2.0 1.27

K 0. 7 0.02 0. 0. 0.0 0.11 0.0 0.0

Ca . 0. 7 1 .0 1. 0 0. 0 0. 0.24 0.21

M 4. 1 11.17 4. 2. 10. 7 11.4 2. 1 0.4

e 1. 4 0.24 24. .1 0. 7 .1 2. .14

C .1 0.24 0. 0.4 0. 1 0.40 0.14 4.

0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

13 University of Liverpool ALGY 740 Prof. Matthew Ponting (Plate 5) Timna 2-Overall Bulk Analysis

T ota l

10 0.00

(Plate 6) Timna 3-Overall Bulk Analysis

E le men t Mg Al Si Cl K Ca Ti Mn Fe O T otal

Lin e KA1 KA1 KA1 KA1 KA1 KA1 KA1 KA1 KA1 KA1

k eV 1.254 1.487 1.740 2.622 3.313 3.691 4.510 5.898 6.403 0.523

KRatio 0.0026 0.0071 0.1532 0.0027 0.0046 0.0355 0.0058 0.2641 0.0263 0.0000

Wt% 0.53 1.18 21 .20 0.34 0.51 3.73 0.63 30 .99 3.02 37 .89 100.00

At % 0.55 1.11 19.18 0.24 0.33 2.36 0.33 14.33 1.37 60.18 100.00

Com pou nd M gO Al2O3 SiO2 Cl K2O Ca O T iO 2 M nO F e2O 3 T ota l

Cmp d Wt% 0 .88 2 .23 45.36 0 .34 0 .61 5 .22 1 .05 40.01 4 .32 10 0.00

C hiSq u ared 80.00 80.00 80.00 1.31 7.83 7.83 2.75 16.48 16.48 29.20 31.06

d c

E le me t l i K a Mn Fe u O T otal

Li K K K K K K K K

e 1 1 1 1 1 1 1 1

k eV 1.487 1.740 3.313 3.691 5.898 6.403 8.046 0.523

K Ratio 0.0029 0.0878 0.0050 0.0357 0.0149 0.4242 0.0151 0.0000

W t% 0.55 13 .12 0.54 3.64 1.60 47 .27 1.83 31 .46 100.00

At % 0.59 13.49 0.40 2.62 0.84 24.44 0.83 56.79 100.00

Com pou l2O3 i O2 K2O aO M nO F eO uO

Cmp W t% 1 .04 28.06 0 .65 5 .09 2 .07 60.81 2 .29

C hiSq u are 44.39 44.39 6.97 6.97 17.31 17.31 1.05 35.62 1 .2

YX

` ` ` ` ` ` ` ` X

b b

14 University of Liverpool ALGY 740 Prof. Matthew Ponting (Table 2)

yy

uv vv

vx

xu

u y

u y

y yv

xy

uw

w w

xw v

x w

yu

vy

x v

u v x

1
y v

0. 4% .1 % .1 % 1 .04% 1 . 7% .7 % . %

0.14% 0. % 0. 1% 0.0 % 0. % 0.7 % 0.7 %

0. 0% 0.7 % 0. 0% .7 % . % .00% 1. 0%

4. 0% 0.00% 0.07% 0.1 % 0.0 % 0.4 % 0.4 %

0.00% 1.11% 0. % 1.0 % 0. 7% 1. % 1. 1%

si

qp

gf

Ta

Al 0.1 % 0.4 % 0. 4% 0. % 0.40% 1.1 % 0. 4%

a 0.1 % 0. % 0.44% 1.0 % 1. 7% 17.0 % 17. %

e . % 1. % 4.10% 7 . % 7 . 1% 44. % 44.1 %

15 University of Liverpool ALGY 740 Prof. Matthew Ponting (Table 3)

Tag 1 2 3 4 5 6 7 8 9 10 11 12 13

Si 0.45 0.69 0.49 0.55 24.39 Si 0.55 29.08 29.28 0.51 21.24 4.40 29.58 0.43

l 27.53 16.78 26.71 18.59 1.27 l 17.12 0.13 0.09 0.12 0.19 6.58 0.10 27.74

Fe 1.13 1.71 0.85 1.24 71.76 S 0.18 3.84 14.35 0.12 4.57 0.24 6.71 0.13

u 70.88 80.35 71.94 78.87 2.58 Fe 2.40 65.63 51.62 3.83 72.29 53.85 62.02 0.99

O 0.01 0.47 0.00 0.75 0.00 u 79.53 0.19 3.05 95.39 0.73 33.57 0.37 70.71

O 0.00 1.05 1.55 0.00 0.84 0.96 1.15 0.00

16 University of Liverpool ALGY 740 Prof. Matthew Ponting (T b e 4) F gure 12


(T b e 5) F gure 13

T g 1

4 6 7

Spotlight Copper Prill: Sample

l nm l lj l l l n l k lm

l mo l n lk l l ln m loo nm l

l l l lk l n ln l lok j m

l n lkm l nk ln ljn k lm k ln ln

l lk o n l ko l m k lm l o l n l j

lon lnm l ln j l l j l l

l l n lj k lm k l nk lmj l l

l l ln l k l l l l

ln l k jk l l j kk ln l m l kn n lm

l k lmn l j l k l lm lmn lkj

A 0. 0. 1.4 0.66 7. 6 0. 4 10. 0. 4

S 1.4 . . 40 40.7 .7 40.70 . 7 1.6

K 0.07 0.00 0.00 0.00 . 00 0.0 4.17 0.00

0.16 0.00 0. . 6 .0 .0 . 40 0.07

T 0.16 0.46 0. 6 0.07 .6 0.00 7. 0.

0. 7 . 01 11. 1 47.6 6. 7 4 . 0 6. 0.70

Fe 1.0 0.4 .6 . 6.0 . 0 6. 0. 1

u . 1.40 0.7 0. 4 0.0 0.00 0.07 6.17

b 0.44 . 6 .6 0.10 0.00 0.1 1. 7 . 70

Spotlight Analysis Corroded Prills: Sample

O 0.1 0. 1 . 11 4.01 4.16 4.0 4.76 0.

hg

0.0 0.11 0.11 0.06

.64 4. 4 . 7 .

4 .76 40. 46. . 0

T g

g 1.1 0. 7 1.04 0.0

A 0.7 .77 1.0 .1

S 40. 1.4 40.67 .4

K 0.14 1. 0.1 .01

T 0. 0 . 0 0.00 4.1

Fe . 7 11.67 .6 11. 1

O . .7 .6 4. 7

k n

17 University of Liverpool ALGY 740 Prof. Matthew Ponting (Plate 7) Timna 3-Overall Bulk Analysis

a Fe O

T o ta l

100.00

1 0 0 .0 0

(Table 6) i ure 14
{z

1 2 3 4 5 6

0.56% 0.62% 0.69% 0.54% 0.00% 0.06%

0.32% 0.36% 0.31% 0.58% 0.30% 0.25%

Bulk Spotlight: Sample 4

Ta

Al 0.94% 0.88% 9.73% 10.52% 1.26% 1.15%

i 0.55% 0.47% 21.87% 26.39% 2.79% 4.72%

a 0.48% 0.44% 25.15% 39.98% 16.81% 16.78%

t s s r w

Mg l i

K K K K K K K

1 1 1 1 1 1 1

1.254 1.487 1.740 2.307 3.691 6.403 0.523

0.0012 0.0105 0.0224 0.0017 0.0630 0.4937 0.0000

0.29 1.99 3.45 0.21 6.34 55 .26 32 .47

0.35 2.18 3.62 0.19 4.66 29.17 59.84

M gO l2O3 i O2 O3 aO F e2O 3
T o ta l

0 .47 3 .77 7 .37 0 .52 8 .87 79.00


1 0 0 .0 0

7.12 7.12 7.12 0.87 24.14 24.28 87.86


17.21

e 95.17% 95.18% 38.80% 18.69% 78.15% 75.98%

O 1.98% 2.05% 3.46% 3.29% 0.69% 1.06%

qp

v u

r r r r r r r p

E le m e t

Li e

k eV

K R a ti o

W t%

At%

C o m po u

Cmp

W t%

C h i S q u a re

t s s r

18 University of Liverpool ALGY 740 Prof. Matthew Ponting (Table 7)

Figure 15

Tag 1 2 3 4 5 6

Slag and Furnace lining interaction zone: Sample 4

~ ~ ~ ~ ~ ~

~ ~ ~ ~ ~ ~

~ ~ ~ ~ ~ ~

~ ~ ~ ~ ~ ~

~ ~ ~ ~ ~ ~

~ ~ ~ ~ ~ ~

~ ~ ~ ~ ~ ~

~ ~ ~ ~ ~ ~

Mg 2.69 1.35 0.00 0.51 0.12 0.59

Al 0.31 1.01 3.30 1.88 2.29 0.54

Si 0.80 1.52 14.98 1.69 13.56 0.84

P 2.46 1.80 0.96 0.28 0.96 2.82

S 1.67 0.95 0.59 0.45 0.35 0.94

a 81.76 76.20 15.91 1.59 23.69 82.18

Fe 6.60 4.68 63.39 91.64 56.59 3.26

3.70 12.49 0.88 1.96 2.44 8.83

19 University of Liverpool ALGY 740 Prof. Matthew Ponting Bibliography Bachmann, Hans-Gert, The Identification of Slags from Archaeological Sites. Occasional Publications No. 6, Institute of Archaeology, University of London, England (1982) pp. 1-38 Berquist, Rick C,. Geologist , Personal Interview. The Virginia Division of Geology and Mineral Resources. January, 16 2011. Evely, R.D.G., Minoan Crafts: Tools and Techniques. Studies in Mediterranean Archaeology, Vol XCII: 2, Jonsered (2000) pp. 323-434 Hauptmann, Andreas, The Archeometallurgy of Copper: Evidence from Faynan Jordan. In Herrman, B. and G. A. Wagner s Natrual Science in Archaeology. Springer, Heidelberg, Berlin (2007) pp. 18-30 http://www.springerlink.com.ezproxy.liv.ac.uk/content/978-3-540-722373/#section=304896&page=1&locus=82 Nicholson, Paul T., Ian Shaw, Ancient Egyptian Materials and Technology. Cambridge: Cambridge University Press; UK (2000) Ponting, Matthew. Iron Smelting . Lecture . Pytrotechnology: ALGY 737, University of Liverpool, Liverpool 24 April 2011. Rothenburg, Beno. The ancient metallurgy of copper: archaeology, experiment, theory. London: Institute for Archaeo-Metallurgical Studies, University of London (1990)