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Thread: Toughness Of Lead-tin-antimony Alloys

  1. #41
    Boolit Master


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    Thanks Grumpy. It all makes pretty good sense to me, now that I've re-read it and you've responded to my questions. I agree with most everything you say, especially about people making their boolits too hard.

    I found what is probably the same article by Dennis Marshall in the Lyman Cast Bullet Handbook. It's about a 12 or 13 page article which goes into a lot of scientific analysis of lead and lead alloys. Talks about binary & ternary alloys, metallic solutions, etc. More light reading!

  2. #42
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    Reading this is very interesting and makes one do some thinking.I'm new to this and am trying to learn as much as I can.Planning on casting my own when I get my project rifle put together.Was planning on using the wheel weights I have stockpiled as a basis,but according to an nra contributing writer wheel weights are to "hard" for round ball and black powder cartridge bulletts

  3. #43
    Boolit Buddy yodar's Avatar
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    Do you equate ductility with ability to obdurate?

    Yodar

  4. #44
    Boolit Master
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    Quote Originally Posted by yodar View Post
    Do you equate ductility with ability to obdurate?

    Yodar
    Ductility is the extent to which a material can be deformed plastically without fracture. Thus it is extremely high for pure lead, and extremely low for most type-metals. It seems to me that this is closely related to, say, a plug's potential to be expanded permanently in diameter without cracking, by squeezing it axially. In other words, ductility should be a measure of the extent to which a bullet is capable of obturating without cracking. However it does not relate to the pressure required to make it obturate, although many shooters probably treat these two considerations as closely related. There are some more subtle factors that come into the picture too: for some materials ductility in tension and compression may be different.

  5. #45
    Boolit Master Marlin Junky's Avatar
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    Maybe someone has already addressed this point, but how do the larger diameter boolits respond to the toughness testing? Would you be willing to repeat the tests with .375 cal boolits? I'm sorry I didn't have time to carefully read everything, but what were your casting conditions?

    MJ

  6. #46
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    Quote Originally Posted by Marlin Junky View Post
    Maybe someone has already addressed this point, but how do the larger diameter boolits respond to the toughness testing? Would you be willing to repeat the tests with .375 cal boolits? I'm sorry I didn't have time to carefully read everything, but what were your casting conditions?

    MJ
    There are two issues with larger diameter bullets - one test-related, the other metallurgy-related. The test-related issue I've discussed above: the length to diameter ratio of the bullet is important. Short fat bullets are unsuitable for transverse fracture testing. In addition there is a scale issue: the actual impact energy measurement would increase with bullet diameter, so it would be necessary to repeat the entire series of experiments, on all alloys, for each calibre. Just as the Charpy and Izod tests use a single, arbitrary specimen size to represent an alloy, I have used 30 calibre and am continuing to do so in the follow-up experiments. I do not think repeating the entire series with a different calibre would add anything to the science content of the work, except in relation to the metallurgy-related issue.

    The metallurgy-related issue has been raised by several people in the discussion above and elsewhere on this board: since the quenching process removes heat only via the exterior of the bullet, the surface-to-volume ratio will influence how quickly the core of the bullet cools. Most likely large calibre bullets will show more variation in hardness from surface-to-core than will small calibre bullets. This is a subject that might be worth investigating, but not as part of a series of experiments aimed at researching toughness.

    I've set out most of the details of casting conditions in the report, and supplemented it to some extent in the discussion above. I haven't mentioned that I generally followed my standard approach to casting: start with a metal temperature of 750 F until the mould warms up and the bullets become frosty, then wind back to 650 F. I use a lower temperature than 650 F for most moulds, but this series of experiments uses 311466, which is a Loverin design. My experience has been that I need perhaps 50 F higher casting temperature for this (Lyman DC) mould than I do for two-groove 30 calibre designs such as 311291. Conversely, the little 311255 is so easy to cast I use an even lower temperature - typically less than 600 F. The bullets were dropped onto a towel and air cooled, then heat-treated at a later date.

  7. #47
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    Red face

    Quote Originally Posted by grumpy one View Post

    The metallurgy-related issue has been raised by several people in the discussion above and elsewhere on this board: since the quenching process removes heat only via the exterior of the bullet, the surface-to-volume ratio will influence how quickly the core of the bullet cools. Most likely large calibre bullets will show more variation in hardness from surface-to-core than will small calibre bullets. This is a subject that might be worth investigating, but not as part of a series of experiments aimed at researching toughness.
    Very good thread here, as I slowly return to shooting cast boolits--from ~1968.

    As a professional metallurgical engineer (now retired), please allow me to attempt to clarify some of the basics. We all know what hardness and ductility are, but "toughness" is a bit er, tougher to understand. It simple means, metallurgically, the property of a metal's ability to absorb energy until it fractures.

    Metals deform both elastically (rubber band, will return to original length) and plastically (will not return). Nearly all of the energy absorbed in "tough" metals is in the plastic region. Ductility is a large part of this, but strength/hardness is also important. Pure gold is about as ductile as you can get, but its low strength prevents it from being a "tough" metal.

    The ductility part of toughness is also affected by "rate-of-plastic deformation" (strain rate). Faster strain rates always (nearly-?) reduce duct., and thereby also reduce toughness, sometimes to a very large degree. A metal which appears to be tough at moderate strain rates can fracture in brittle mode at high rates.

    For steel alloys, the explosion-bulge test was developed because of this phenom. Any "Charpy"speed related testing should of course be verified at expected bullet striking speeds, where the target material/deceleration rate gets very involved--as expected.

    Lucky for me I only shoot targets!

    Here's a rather technical link to some of the various hardening mechanisms of lead alloys for battery grids that explains age-hardening and softening. Anyone ever try to cast lead w/calcium?

    http://209.85.173.132/search?q=cache...=us&lr=lang_en
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  8. #48
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    Thank you for that information, and for the link to the article. I have been using the term 'precipitation hardening' indiscriminately to describe a combination of Guinier-Preston zones formed during aging, and what the article calls 'precipitation hardening as discrete second-phase particles are formed'. That is, I have not discriminated between stretching the internal lattice in the lead as a solute solidifies, and precipitating separate crystals into the lead matrix. Unfortunately, I don't know at what antimony percentage the latter becomes applicable. Do you have any information on this? I notice that the solubility limit for antimony in lead at room temperature is 0.44%, which may therefore be the point at which true precipitation hardening begins and incremental formation of Guiner-Preston zones ends. It appears the distinction is not trivial, because the article says Guinier-Preston zone hardening age-softens, while true precipitation hardening does so to a lesser degree. Frances Weaver published quite a number of photomicrographs, all of which show major amounts of precipitate grains in the appropriate matrix, but she only tested ternary alloys and all had at least 6% Sb and at least 2% Sn. The toughest alloys have considerably less than 6% Sb, and it would be useful to compare the best 'toughness zone' with the best 'resistance to age-softening' zone. Age-softening is a topic of perrenial interest on this board.

    My current speculation is that true precipitation hardening begins at 0.44% antimony, and incremental Guinier-Preston hardening ceases at that same point. If true, this may mean that age-softening in the alloys most likely to be heat-treated - say those with at least 2% antimony - may be predominantly a true precipitation hardening zone. This would explain the fairly slow age softening which is usually reported (i.e. most of the incremental hardness due to quenching is retained for more than a year). However this is speculation - I'd like to get it onto a tested-and-verified basis if possible.

  9. #49
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    I think the real problem with bullet hardness and strength is that the recrystallation temps. of lead and tin are so low--below room temp. for the pure metals. Mixtures of metals (alloys) have higher recry. temps.; sometimes much higher. If that were not true, bullets would end up being very soft indeed.

    Recrystallation will remove hardness/strength increases from cold-work (not a factor for cast bullets), but will do the same for GP/precip. hardening as well. The whole phenomena of GP and precip. hardening is quite complicated--the more you look into it, the more involved it becomes.

    Here's a link that explains things a bit.

    http://209.85.173.132/search?q=cache...=us&lr=lang_en
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  10. #50
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    grumpy (and milanodan, if you want to jump in),

    You said earlier that alloys with higher tin than antimony have inconsistent hardness. Does this preclude these types of alloys as useful cast boolit alloys?

    Again, going back to look at some things I need a softer alloy for, such as buckshot, black powder boolits, and low-velocity-load hollow-points, I'm looking at an alloy of approximately 96% lead, 2.5% tin, and 1% antimony. (25lbs pure lead, 15lbs WW, and 1lb tin).

    I believe this will be a fairly soft alloy, if I do not heat-treat it (which I won't for these applications), but specifically, I'm wondering if the very low concentrations of tin and antimony will make inconsistent hardness very pronounced. (I'm going for a softer alloy that still won't cause leading.)

    Also, I note that some of our differences may be based on what we're using our respective alloys for: you seem to be more for rifles and I for pistols. When it comes to rifle applications, I agree completely with your point of view that we can and should work for an alloy that is specific for the application. (4-4 sounds good, too, because it will be high enough in tin to flow well into intricate rifle boolit designs, like Loverins!)

    For pistol shooters though, we're looking for an alloy that we can make a bunch of bullets with that will work in broad application, be accurate and not lead. In other words, we want one to three alloys that "do-it-all" for us. I currently use WW with a bit of tin added to get me to around 94-3-3 for more than 90% of my loads. But, I've identified a need for a softer alloy, as described above, and a harder one for rifle boolits and pistol bullets that I want maximum penetration from.
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  11. #51
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    First, I haven't ever found out where Dennis Marshall obtained his information leading him to say that soft spots will form if you have more tin than antimony. He says that the problem is due to 'cellular precipitation'. This is also known as discontinuous precipitation and seems to be a mysterious phenomenon that lead-tin alloys, among others, are subject to. At this point I don't know what effect antimony has on it. Here is a tantalizing rather and informative snippet on it:
    http://garfield.library.upenn.edu/cl...MC82200001.pdf
    So, the short answer is that we are dealing with a rather technical metallurgical issue here.

    Second, when you need a soft alloy you may find you can use lead-tin rather than lead-tin-antimony, and end up with better ductility as well as avoiding age hardening or softening. I have the impression you should limit your tin to no more than 5% though, not only for cost reasons but also possibly because of the dreaded cellular precipitation. However I am by no means across this precipitation issue; mainly I am taking Dennis Marshall's advice that you should not allow tin to exceed antimony. If you accept that as a restriction, you should be basing your very soft-ductile alloy on lead and tin alone.

    Regarding your third point we are not currently on the same page. Because I am taking Dennis Marshall at face value, my approach to producing softer, more ductile alloys is as follows. At the extreme of softness, you take pure lead and add just enough tin to produce an extra 2 to 3 BHN numbers of hardness at most. When you reach 5% tin if you want it slightly harder you change tack and switch to the 1/1 alloy: 1% tin and 1% antimony. From there on you just keep tin and antimony equal. Once you start adding antimony the alloy becomes heat treatable, so you can choose from a range of hardnesses. By the time you get to 2/2 alloy, you are well into the rifle range of hardnesses; I think it would require a pretty exotic handgun to require the maximum level of hardness available with heat treated 2/2 (25 BHN).

    I have to offer a caution with regard to 4/4 alloy: subsequent experiments suggest that the 'optimum' alloy with regard to toughness has less than 4% of both tin and antimony. I have completed the experiments to find the optimum antimony percentage, but I do not know what that percentage is, because I can't get my samples analyzed for free yet. A possibility of getting this information exists, and I am waiting for it to come to fruition. Of course I'll post the results when I get them. Essentially, in the experiments reported in this thread I made a technical error due to not knowing the answers before I started. I did not maintain a constant tin-to-antimony ratio in the low-tin alloys I compared, and of course one of my findings was that the tin-to-antimony ratio has a greater effect on toughness than does the amount of antimony itself. So, I subsequently ran another series with the tin-to-antimony ratio held approximately constant, and found that a lower percentage of antimony than 4% is actually optimum. I am not resiling from the view that 4/4 is a most excellent alloy; it is just that a slightly lower percentage is likely to be even better. 4/4 is also a caster's dream, while the lower percentages are not quite so outstanding in this regard. My subjective impression is that 4/4 is easier to cast than pure linotype.

    Concerning your fourth point, 3/3 alloy can be heat treated to about 24 BHN, which seems to me sufficient for all but rather exotic rifle loads. It also has better ductility than 4/4 of course. If 24 BHN does not give you enough penetration, it sounds like it's time to use a different cartridge rather than a harder bullet. Hence my simple answer for the moment is that your 3/3 alloy seems to be very close to the optimum for toughness and should be an excellent choice for your all-purpose rifle alloy, with different heat treatments to suit different applications. Where you need a softer alloy than air cooled 3/3 - in other words less than about 14 BHN - you should consider 2/2 or 1/1.

  12. #52
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    Most of the metallurgical aspects of lead alloys are new to me, since I am primarily a steel metallurgical engineer. Here's a link to a good source of info. Interesting how the Romans used lead for water pipes--I took some photos of lead pipes at Pompei (Italian spelling, with only one i on the end), and they are rectangular, not round.

    Also interesting how the toxicity of lead was apparently known (somewhat) way back then. Didn't seem to help the Romans, or my beloved Beethoven either.

    http://books.google.com/books?id=TtG...result#PPP1,M1
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  13. #53
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    Thanks to you both.

    grumpy - if you don't mind, let me paraphrase back to you, just for accuracy's sake.

    It sounds to me like you think the 94-3-3 alloy that I use for my "all-around" alloy is plenty hard enough for any rifle or hard-penetrator pistol use, as long as I heat treat it, to get the maximum hardness out of it. By extension, I think you're saying to forget formulating any alloy with higher concentrations of tin-antimony, unless I want to take one last step up to 4-4 for castability-sake. (Again, this is presuming I heat-treat the bullets to get maximum hardness.)

    So, this leads me to a couple other questions:

    1. If I heat treat via water-dropping direct from the mould, does that get me into sufficient hardness range with this 94-3-3 alloy for rifles? (I know that there are many techniques to heat-treating and that the simple expedient of water-dropping direct from the mould, while accomplishing some heat-treating, is not optimum in garnering all the hardness one can get from an alloy.) Maybe as a corallary, you could suggest what BHN or velocity, a water-dropped 3-3 alloy could be/get to?

    2. In your experience, would the 3-3 alloy be soft enough for obturation when air-cooled for most 1100fps-1400fps pistol loads (9mm, 357, 44), yet hard enough to resist leading? (I'm just looking for an opinion here. I know that this question can seem leading and there are a ton of variables. I'm just looking at this theoretically, let's say.)


    And, just so you know why I don't seem to be following your advice on the soft alloy - I have access to tons (literally) of WW alloy, but very little pure tin and lead, so I try to incorporate WWs as much as I can to preserve my smaller supplies of the other raw materials. Hence, why I'm using at least some WWs in my "soft" alloy. I guess by air-cooling these, I can keep this alloy relatively soft for my applications.

    I'm amazed at how hard you've found you can get alloys like 1-1 and 2-2! Heat treating, done right, can sure change things.
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  14. #54
    Boolit Master on Heavens Range
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    The most important thing you can do to radically increase accuracy (on the aggregate) is to let the boolits age, quenched or not. I have been shooting coppered boolits lately that were made in 2001 with no changes in the load since. Using the BR gun (222 ackley), minute changes can be seen between boolit lots, even when shooting trash as targets at various ranges. That gun now has 2500 plus rounds through it and the accuracy is holding up for the same purpose over time which is surprising to me. This load is at least 40K CUP, and I have continually seen the "freebore" lengthen significantly. The real surprise is that the 225646 has been seated exactly the same since time began. Correction: cases are constantly neck checked/turned to give a 0.0008 clearance. Must use cases that are absolutely the same for the record "group", with weight variation of no more than 1/10 of a grain. ... felix
    Last edited by felix; 02-22-2009 at 11:47 AM.
    felix

  15. #55
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    3/3 alloy is easily hard enough for any rifle application I am likely to get involved in, but that is a pretty narrow range of a wide subject. There are people on this board who prefer up to 32 BHN for target shooting. I don't know their reasons, and am certainly not going to claim to know whether they are right or wrong. For your purposes though - hunting, and shooting targets to tune up your hunting rifles and loads - I feel confident that 24-25 BHN is easily hard enough. Nearly always, you'll actually prefer substantially softer bullets than that. For serious technical questions like how to get outstanding results by building an outstanding rifle and outstanding ammunition, listen carefully to Felix. He knows whereof he speaks.

    Regarding question 1, water dropping probably won't get you quite to maximum hardness but it will get you most of the way there. However I don't do it for a different reason. Unless you get a perfect free-drop of the bullets from the mould into the water every single time, you get highly variable hardness from water dropping. I've tried it, but I typically get hang-ups in the mould more often than not. I found water dropping an alloy that was 14 BHN air-cooled, gave me everything from 14 BHN to 25 BHN in a single casting batch.

    Concerning question 2, air cooled 3/3 alloy is about 14 BHN. That might obturate with a pretty stiff 357 load, but it seems to me to be too hard for target loads and probably is a bit hard for even mid-range loads. It also sounds to me to be too hard for just about any autoloading pistol short of an automag - though if you have a good enough barrel you might find it very successful. However you should get a proper answer for this question from a serious pistol shooter, on another thread.

    It doesn't require any black magic to get maximum hardness when heat-treating. For maximum hardness just hot-soak a small to moderate batch of bullets, stacked to facilitate water flow, for an hour at 240* Celsius, then get them from the oven to a bucket of tap-water very quickly - certainly within 1 second. With a low-tin 4% antimony alloy that gets me an average of 32.4 BHN after 14 days. Remember though that when you increase the tin, the heat treatment becomes less effective.

  16. #56
    Boolit Master Hanshi's Avatar
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    Cool

    I've always cast my own bullets out of wheel weight & similar alloy for the most part because commercial cast bullets are just too hard and lead forcing cones too much. They aren't as accurate as what I can cast, either. The exception I've found is in auto loading pistols where they perform fine for me. I now seldom cast bullets for cartridges and make do with what I can buy, anyway. I do cast lots of ball for muzzleloaders which I now shoot 98% of the time.

    Question: Is there any (easy/simple) way to remove hardening agent from lead alloys so they can be used more effectively in muzzleloaders? Just wonder if anyone has tried it.

  17. #57
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    I would like to thank all for their contribution to this fascinating thread.

    Dale53

  18. #58
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    Grumpy one you said this in one of your post here: Most likely large calibre bullets will show more variation in hardness from surface-to-core than will small calibre bullets. This is a subject that might be worth investigating, but not as part of a series of experiments aimed at researching toughness.

    Do you really think that being the larger caliber bullet having more surface area then the smaller caliber, thus making them more or less equal in releasing their heat through conductivity, therefore harden to the core equal also?

    Joe

  19. #59
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    Quote Originally Posted by StarMetal View Post
    Grumpy one you said this in one of your post here: Most likely large calibre bullets will show more variation in hardness from surface-to-core than will small calibre bullets. This is a subject that might be worth investigating, but not as part of a series of experiments aimed at researching toughness.

    Do you really think that being the larger caliber bullet having more surface area then the smaller caliber, thus making them more or less equal in releasing their heat through conductivity, therefore harden to the core equal also?

    Joe
    Joe, I think the cooling rate in the core of the casting will depend on four things:
    1. The heat transfer coefficient, which depends on the amount of coolant and shape of the quench bucket, and the chemical nature of the coolant which determines conductivity, surface wetting, and likelihood of localized boiling of the coolant (which really slows down the quench).
    2. The temperature of the coolant.
    3. The surface-to-volume ratio of the casting. High surface-to-volume ratio gives high rate of heat transfer in relation to how much mass of casting there is, so cooling happens faster. Thus a long pencil-shaped bullet with Loverin grooves all the way along will cool much faster than a round ball. Round ball is the slowest-cooling shape it is possible to have, because it has the lowest surface-to-volume ratio.
    4. The actual distance from the surface of the casting to the innermost point of the casting. The rate of heat transfer depends on the thermal conductivity of the metal (lead alloy), and the length of the conductivity path. So, the core of a 6" lead cannon ball will cool a lot slower than the core of a 30 caliber round ball.

    So, with the common quenching method we mostly use (bucket of tap water), the core of a 22 caliber Loverin will cool mighty quickly, and the core of a 50 caliber round ball will cool considerably more slowly. Of course none of this tells us what is the critical cooling rate to achieve any given degree of hardening.

  20. #60
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    Obturation is Not Wanted Or Needed

    Lee wants the pressure below where Obturation would happen. http://www.realguns.com/archives/118.htmCompare the pressure listed here for Obturation to take place.http://en.wikipedia.org/wiki/Obturate If a cast lead alloy bullet Obturates, it will deform and break down, leading the barrel. The structure of the bullet will be changed when jumping for the cylinder to the forcing come. Not so much change will take place in a auto fixed chamber firearm. Bullet's BHN x 1422 = Pounds per square inch.
    Quote:
    According to the chart, a very popular #2 alloy carries a 16 BHN, has a strength indictor of 22,703 PSI and should be limited to 20,000 PSI as maximum pressure. Wheel weight alloy with a BHN of 9 carries a strength of 12,748 PSI and a MAX pressure rating of 11,473 PSI.

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Abbreviations used in Reloading

BP Bronze Point IMR Improved Military Rifle PTD Pointed
BR Bench Rest M Magnum RN Round Nose
BT Boat Tail PL Power-Lokt SP Soft Point
C Compressed Charge PR Primer SPCL Soft Point "Core-Lokt"
HP Hollow Point PSPCL Pointed Soft Point "Core Lokt" C.O.L. Cartridge Overall Length
PSP Pointed Soft Point Spz Spitzer Point SBT Spitzer Boat Tail
LRN Lead Round Nose LWC Lead Wad Cutter LSWC Lead Semi Wad Cutter
GC Gas Check