Hacker News new | past | comments | ask | show | jobs | submit login
Additive manufacturing of an ultrastrong, deformable aluminum alloy (nature.com)
94 points by PaulHoule 48 days ago | hide | past | favorite | 59 comments



Commonplace aluminum alloy 7068 is also "ultrastrong" (~710-750MPa, more than the 700MPa in the paper,) and ductile.

WWII-vintage Japanese duralumin (Al-7075) is nearly as strong (~600MPa), and very ductile. It's also nearly 100 years old.

I guess the innovation here is that they're making this alloy with additive manufacturing techniques? It's not that noteworthy, IMO. It would be jaw-dropping if it were a 1000MPa alloy -- that's like the Holy Grail for aluminum -- but they're still far from that mark.


In the abstract:

"Light-weight, high-strength, aluminum (Al) alloys have widespread industrial applications. However, most commercially available high-strength Al alloys, like AA 7075, are not suitable for additive manufacturing due to their high susceptibility to solidification cracking."


Oh neato! I studied this in Grad school back in 2014!!

"the Innovation" is that high strength alloys like 2xxx and 7xxx are notorious for their "unweldable" nature.

So to report a fairly rigorous investigation of such a material being successfully processed via PBF is interesting.

There are essentially 3 ways to do it, different composition, grain refiner, or pulse shaping.

They seem to be targetting some combo of the first two.

The work is complete, but also very early..(limited macro mechanical work)

small scale mech props work can be very very different than practical size structures like a E8 coupon or fatigue test artifacts

The other issue is that creating new alloys is largely academic.. as the as qualification and supply chain constraints in most performance driven industries with any real market make it a non-starter

Not to say it's not interesting though, I'm excited to see where they take the work next!


>Additive manufacturing was performed by using a laser powder bed fusion (LPBF) instrument, SLM 125 HL metal 3D printer in Argon atmosphere with the oxygen level below 1000 PPM. Printing was conducted by utilizing a 400 W IPG fiber laser (λ = 1070 nm) with a laser power of 200–300 W

Sounds expensive.


Not as much as you’d expect probably - fiber lasers are pretty cheap now a days, and depending on accuracy needs, the 3D printer itself could be in the $1k range. And making an enclosure to allow argon flooding isn’t going to be much more either.


In materials science, are alloys as seemingly complex as "Al92Ti2Fe2Co2Ni2" commonplace?

How do we arrive at that kind of alloy? (If it was explained in the paper, I didn't understand it)


As mentioned in the paper, this is a typical "medium-entropy" alloy.

Pure metals are soft, because all their atoms have the same size, so the atom layers can slide over the others.

Mixing metals with different sizes increases the strength, because now the atom layers are no longer smooth, but they have bumps, which prevent sliding.

It can be shown that mixing many different kinds of atoms, taking from each about the same quantity, can provide very good mechanical properties, because the bumps in the atom layer will be frequent and they will have varied sizes and a random distribution, which will prevent any alignment between bumps, which could facilitate the sliding of the layers. Think about how to design an anti-sliding shoe sole. Random bumps of random size would give the best result.

The so-called "high entropy" alloys contain at least 5 different metals, with about the same quantity from each.

However the alloys that contain almost equal quantities of each component are very expensive. In order to make a cheap alloy, one must have one or at most two components in a much larger quantity than the others, so that the abundant components can be chosen from the few cheap metals, e.g. iron, manganese or aluminum, while the other components, which are added in small quantities, can be chosen from expensive metals, like nickel and cobalt.

For this reason, the better "high-entropy" alloys are normally replaced by the cheaper "medium-entropy" alloys, which use 5 metals, like the "high-entropy", but which are used in quite different quantities, with larger quantities from the cheaper metals, if possible.

The use of "high-entropy" alloys and "medium-entropy" alloys has begun only relatively recently. They are used to replace the cheaper classic alloys only when they offer a decisive advantage that can justify their higher cost.

This case is one such example. From the classic aluminum alloys, some of the weaker alloys, like AlSi or AlMgSi can be easily 3D printed, but they have low strength. The classic high-strength aluminum alloys cannot be 3D printed. Therefore this was a clear case when a newer kind of alloy must be tried, if high strength is desired. They have experimented with certain kinds of medium-entropy aluminum alloys, to keep the cost acceptable (and also in this case the high content of aluminum keeps the density low and the conductivity high, which are frequently the reasons for choosing an aluminum alloy), and the results were good.

Nevertheless, this alloy is likely to be several times more expensive than AlSi or AlMgSi, so it will be used only when its high strength is necessary.


This is not a medium entropy alloy, it's a standard alloy in terms of the ratio of components, which forms medium entropy intermetallic precipitates which gives the alloy it's properties. Intermetallic MEA is an odd term I'm not really familiar with and would want to look into more, but is a little suspicious. Furthermore, while MEAs (3-4 equal primary components) and HEAs (5+ equal components) do have good mechanical properties, I'd be wary of the atomic size argument, last time I've been involved in it, that argument has increasingly been questioned, as the atomic size of the elements in question are generally pretty similar.


I get the sense that stronger alloys are more "brittle" and harder to do things like welding, as they'll crack instead of yielding from all the thermal stresses. This is probably the same sort of thing with laser melting and 3D printing: solidification under high thermal gradients. It seems this material is not only high-strength but also ductile enough to gracefully handle the thermal stresses.


It's more complex than that. A lot of the material properties depend on both the cooling and the tempering in aluminum alloys.

The phase diagrams for these types of alloys look wild (you often want to achieve a certain material phase during cooling to "lock" in to get certain characteristics), and it can be difficult to ensure that the smaller metals participate during cooling. Also difficult to dissipate these slightly during tempering, typically to increase ductility.

This is probably why 3d printing hasn't been done in earnest, you can't design something within tight tolerances with unknown material properties.


3D printing of metals is being done in earnest, although the industry prefers the term Additive Manufacturing. Metal powder bed fusion is a stable, reliable process that is being successfully used commercially. It's generally confined to high-value applications that require extreme geometric complexity, but it can be invaluable in industries like aerospace, motorsport and medical. The range of viable materials is still somewhat limited, but covers a good range from titanium and aluminium alloys through to tool steels and heat-resistant super-alloys.

https://www.renishaw.com/en/metal-3d-printing--32084

https://www.trumpf.com/en_US/products/machines-systems/addit...

https://www.carpenteradditive.com/powderrange-metal-powders


So you need to control the solidification process to plot a course through the phase diagram, spending the right amount of time in each region, and ending up in a good place. And this alloy has a phase diagram that is compatible with a method of 3d printing.


I think this is also why welding aluminum alloys was such a pain before the introduction of friction stir welding, which doesn't melt the metal. FSW was invented surprisingly late, in the 1990s.


It is not uncommon to have an alloy with 10 elements. Usually it is 1 to 3 main elements and some minor additives, and that’s the case here.

Steels can be very complex as well.


If you just look at stainless steels, there are many alloys with 6+ elements, example below (904L is also know as Rolesor, used for steel Rolex watches)

SS 904L: Nickel, Chromium, Carbon, Copper, Molybdenum, Manganese, Silicon, Iron

Tool steel alloys (used for machine tools, hand tools, knives, etc) have iron, carbon, tungsten, chromium, vanadium and molybdenum.

Carbon steel is the most basic alloy steel, it consists of iron and carbon (and impurities).


If you notice these alloy elements add up to 100. This alloy can be thought of more as 92% Al with 2% each of the other elements. Its a metal-metal matrix composite, primarily pure aluminum with localized, tiny grains of what would be thought of as a traditional alloy (various aluminum-titanium, aluminum-iron, etc. alloys)


They're telling you the mole fraction of each element of the powder. It sums to 100.


I'm not familiar with that format, but it's not rare for alloys to have half a dozen or more alloying elements.


That notation is used sometimes in the literature on model alloys. This does not survive contact with engineering, where they tweak the formula to a hundredth of a percent.


Even with a precise formula that's only 20% of the work. With these superalloys the hard part is getting them to crystalize correctly so that all of the elements fit in the right spots in the matrix and stay there while it cools. A lot of them require seed crystals to form, which complicates the problem.

That’s why this laser sinterable superalloy is really interesting.


Oh yes, of course. I only referred to the notation. Additive manufacturing adds tons of issues on top of the basic problem of getting the alloy to crystallise in the right form (which we’ve had to deal with for millennia).

But the field is developing rapidly and we are already talking about complex concentrated superalloys. There are spectacular advances happening right now at every level of alloy development. The fact that additive manufacturing is far out of equilibrium is a problem for now, but this could become an advantage instead with the right alloys.


This is not a superalloy (i.e. turbine blade material), just a strong normal aluminum alloy that can be additively manufactured.


What features exactly are you asking about on that "like"?

The paper has links for other work with all kinds of similarity.


I rephrased it a little, I was wondering if other materials were as complex as that alloy appears to be, or if an alloy with that number of elements was used widely.

Apologies for the poorly phrased comment.


Cool, but is Selective Laser Sintering less energy intensive than traditional extrusion + machining, or die casting, etc?


Energy intensity rarely matters as much as utility and economic factors around tooling.

Aluminum is already incredibly energy intense to refine - 190-230 MJ/kg. [https://energyeducation.ca/encyclopedia/Aluminum#:~:text=The....]

This isn’t even making a dent.


If it’s not transparent and strong enough to build a whale tank then I’m not interested.


Mh, how recyclable is this alloy? Because with aluminum alloys that's the most important issue (beside the classic fatigue phenomenon).


> with aluminum alloys that's the most important issue

To you, maybe. Not to everyone. Different people have different priorities.

If there was one single most important issue, we could all agree to use the single best alloy and be done with it.


Metals, even abundant ones, are not infinite resources and recycle scrap metal tend to be much less energivore than mining new one, so aluminum per se it can be recycled ad infinitum, with just energy, like glass. They are VERY GOOD materials because of that. Oh, sure in practice it's not that easy because we almost never use pure aluminum, pure glass, but as long as the extra elements are very marginal and/or easy to separate there are not much issues. They can be called circular.

Steel so far it's not because to make new steel out of scrap metal we need coke, there are various experiments to recover steel only adding energy but so far nothing on scale so while recyclable formally (and VERY recycled) it's not circular.

Due to volumes and natural resource limits anything we can do ad infinitum is a godsend because we know if we are able to produce and recycle enough we will never be short of it. That's why it's definitively a general priority. We have started to understand that anything we do on scale we also must count how to dispose of it and how much resources we consume in the process, the era of abundance enough not to care is largely ended and the outcome is hard enough to learn the lesson.


Even if it's not easy to recycle this alloy, it will still be easy enough. It's far from "the most important issue".

And I give that answer while purposefully ignoring how much aluminum there is in the world.


You seems to be very sure, but... I'm not much.

Yes, aluminum is abundant, BUT we already have witnessed scarcity issues in the supply chain, mostly due to poor diversification combined with geopolitical issues, but anyway scarcity. Since smelting and scrapping aluminum it's roughly easy recyclability is important because it can be "domestic" easily, like the one of glass.

Try to see the big picture, not the detail, meaning the complexity of current state of things and the fragility such complexity imply in a world heating toward a III worlds war.


Aluminum is 8% of the Earth's continental crust by mass. We are not going to run out of it. Recycling it is for saving energy, not conserving aluminum.


I can’t see why it couldn’t be recycled? Though I think the most important issue would be its suitability to its intended use case. Recyclability would be somewhere down the list.


Because most alloys are damn hard to separate. Aluminum is very abundant on earth and we can recycle it to the infinity only with energy, so together with glass is a key element of a circular economy, unfortunately pure aluminum is next to useless, and alloys are hard to recover, that's why I ask. We can recover some of them, avional for instance, but many others are damn hard.


How are alloys a worse source of pure aluminium than natural deposits? Are natural deposits available where the aluminium is very pure once you squint hard enough to not see anything else in the mix that has sufficiently different properties to be easily shareable?


It's a matter of easiness of separations: in natural deposits you have to process much material to get a little quantity of mineral, but getting a pure enough mineral is still easy.

Separating alloys it's often much harder because alloy component tend to change phase together (so you can make them liquid, but you still have no way to separate when they are liquid) chemical bonds keeps them together. For some it's easy, let's say you add a substance that separate them, or heat separate them because they change from solid to liquid at different temperatures and so on, for many others it's complicated enough you recover little quantity of the original material spending too much in the process.


Thanks. So an ore with a high aluminium content that also has some amount of e.g. iron (I read that as an example in another comment?) would be worse than an ore with much less aluminium, but where everything else is "more different". Or where it actually does contain a multitude of metals that would be inconvenient in an alloy, but that happen to be bound to different "carriers" that are easy to separate before splitting the molecules. Interesting. Really makes one admire the geological processes that gave us those convenient ores.


This material is intended for specialized applications and probably fairly low volume as a result. Recyclability is probably not at the top of the priority list for features.


Everything is recyclable with enough energy.


I would guess not at all, from the composition.


This particular alloy is specifically designed to be melted and cooled as part of its manufacturing process. It seems like it would be the easiest to recycle: just melt it back down in a different 3d printer. Maybe grind it up first?


If you somehow accumulate for re-processing solely this alloy, then sure.

It's where it gets mixed up with other 'waste', that complicates things.


It's the same issue as plastics. But if the material becomes ubiquitous enough that it's worth building a special recycling stream, products would probably be built to facilitate recycling. Markings etc.


Why?

The vast majority of alloys can be recycled by just melting them down and separating the elements.


The difficulty is separating the components. At least nickel and aluminium, and also iron and aluminium forms lots of intermetallics, they really don’t want to separate. Aluminium is notorious for this.


But wouldn’t those intermetallics be extractable via pyro/hydrometallurgical processes or molten metal extraction, leaving mostly aluminum?

The ratio of Al to the other components is over 10:1 so as long as the intermetallics can be separated, they don’t even need to be recycled, just slagged off (then sent to a more specialized recycler)


That’s not possible for all of them (for reasons slightly different for each element so I am not going to write a wall of text; happy to provide more information if you want).

If we assume that it is possible, then for Al92Ti2Fe2Co2Ni2 the waste would be Fe2Al6 + Ti2Al6 + Co2Al9 + Ni2Al6, so 27 of your 92 Al would be tied up in the waste. It’s a rough estimate and there are some caveats (I did not bother looking at ternary or quaternary intermetallics, or the miscibility of the binary ones, for example).

A more realistic scenario would be to dilute that with pure Al to get some lower-grade Al alloy, rather than recycling it directly into pure Al or very specific, very complex alloy.


> (for reasons slightly different for each element so I am not going to write a wall of text; happy to provide more information if you want)

Yes, please :-)


Here’s an attempt :)

# caveats

This is just my feeling. I looked only at the binary phase diagrams, in reality there could be ternary or quaternary compounds. The article mentions that the alloy is an Al-rich matrix with the other elements in small crystals within it, with different structures and compositions. So the picture is quite complicated. To get a definitive answer, someone would need to do a proper study. I am not saying that it is impossible, just that it sounds very hard. That said, there could very well be other ways that escape me at the moment. I am happy to investigate further for a fee :)

# Fe-Al, looking at the phase diagram here [1]

There is a tiny temperature range (between around 650 and 660 °C) in which solid Al coexists with liquid Fe-Al. So in theory the mixture could be heated until it is all molten, then cooled slightly to precipitate Al, which could then be taken out, leaving Fe-enriched liquid. It seems feasible but impractical (temperature control would need to be absolutely spot on, and other elements would probably change the picture a bit).

# Ti-Al, phase diagram here [2]

There is a temperature range in which Al-rich liquid coexists with solid TiAl3. That solid could be removed, leaving a liquid that is mostly Al but still has significant Ti impurities.

# Co-Al, phase diagram here [3]

This one is similar to Ti-Al, except that Co is more soluble in liquid Al than Ti is, so there would be more Co impurities after taking out the Co2Al9 solid. The temperature range is also much narrower (650°C-700°C, eyeballing the diagram).

# Ni-Al, phase diagram here [4]

It’s worse than the others, because Ni is soluble even in solid Al. Also, melting is almost congruent, meaning that all the solid would melt at the same time, there is no coexistence of a liquid and a solid phase. This prevents from trapping the impurities in a solid to purify the liquid or the other way around. I don’t really see a way with this one.

# magnetism

Using magnetism was mentioned in the thread. I don’t think it would help. At high temperature, all these elements are paramagnetic. Some of them (Fe, Ni and Co) have a larger magnetic moment and would be more strongly attracted in a magnetic field than Al and Ti, but I don’t think it would be sufficient to really separate them (all of them are in minority compared to Al). And Al and Ti are not that different from a magnetic point of view and i don’t see them being separated by a magnetic field.

# oxidation

It is not inconceivable to inject oxygen to try to trap some elements in oxides that have typically much higher melting points than the metals, which would help with the narrow temperature ranges. These metals can form spinel compounds, at least TiFe2O4, NiFe2O4, and many more. One problem is that Al2O3 is also very stable (which is why it is very costly to get aluminium metal from aluminium ore. There are also aluminate compounds such as FeAl2O4. Figuring out which one is more stable and whether it could be feasible is quite a bit of work in itself.

[1] https://www.researchgate.net/profile/Qingyou-Han/publication...

[2] https://www.researchgate.net/publication/325471220/figure/fi...

[3] https://www.mdpi.com/materials/materials-13-03152/article_de...

[4] https://www.researchgate.net/profile/Matthew-Weeks-3/publica...


Thank you for taking the time to write this out! I learned a lot.

If you were tasked with recycling this metal, what order of operations do you think would work best to extract the most usable raw metals out?

Are there techniques to combine these phase diagrams to figure out multiple interactions? I’m guessing the minor components also have their own two phase regions that mess things up


Aluminum is used in steelmaking to "kill" (deoxygenate) molten steel. Aluminum oxide is used for some surfaces facing molten steel, as it doesn't dissolve.


Indeed. Aluminium sucks oxygen to form Al2O3 (sapphire), which is very hard, very stable, and melts at 2000°C.


Naively I would think iron could be separated magnetically. Or is molten iron not attracted to a magnet?


Molten iron is not ferromagnetic. Even solid iron ceases to be ferromagnetic above the Curie temperature of 770 C.


Probably can't directly separate the elements in the melt here but I'm not an expert on melt processing/purification of aluminum. Certainly possible with other methods but might not be economical.


We can have a look at phase diagrams for this. For example, for Fe-Al here: https://www.researchgate.net/profile/Qingyou-Han/publication... .

This shows that Al with some Fe is in 2 phases when it is solid (pure Al on one side and FeAl3 on the other). However, above 660.452°C, there is only one liquid and Al and Fe cannot be separated. There is a tiny temperature range where there is a combination of liquid Al and solid FeAl3, between 655°C and 660.452°C, so completely impractical from an industrial point of view.

That’s an example; it’s even worse with Al and Ni because even the solid is a mixture. I am less familiar with the Al-Co and Al-Ti phase diagrams, but looking at them Al-Co seems similar to Al-Ni and Al-Ti to Al-Fe. Multi-elements alloys would be a bit different but not too much: if everything is soluble in Al separately, then all of them at once are also soluble to some extent.

In short, it might be possible to extract pure Al for recycling, but it does not seem to be easy and there would still be a lot of Al bound to the other metals in the waste.


Ah, so that's why "irony aluminium" scrap (that is aluminium with iron in it, like an aluminium casting with steel bolts) has such a drastically lower value than pure aluminium scrap.


They could probably be separated by distillation, but the temperature would be quite high. Alternately, maybe some element could be found that would preferentially dissolve aluminum (magnesium?) and that then could be separated, again perhaps by distillation. Al/Mg mixtures can melt as much as ~200 C cooler than pure Al.




Guidelines | FAQ | Lists | API | Security | Legal | Apply to YC | Contact

Search: