Over the years poly(lactic acid) (PLA) – also known as polylactide – has become a popular thermoplastic for a variety of reasons. One of these reasons is that it’s easily produced from a renewable resource, i.e. lactic acid, with the resulting polymer even being compostable if you assume that your compost pile hits a steady 65°C or more, well above the polymer’s glass transition temperature (Tg).
That said, PLA by itself is a pretty crummy material, being exceedingly brittle and inferior to common alternatives like PET(G) in many metrics. Over the decades much research has gone into figuring out this material, its amorphous and crystalline states, as well as how to use plasticizers, copolymers, mechanical manipulation and PLLA/PDLA blends to produce more useful variants of PLA.
Today’s spools of thermoplastic filament that gets marketed as ‘PLA’ are the result of such engineering, though with plenty of remaining issues, as anyone who has struggled through a spool of brittle PLA filament can attest to. Although you can find plenty of tips online about how you should ‘just’ toss said spool into an filament dryer, oven or similar to bake it – with accusing fingers pointed at moisture intrusion, hydrolysis and kin – it helps to understand the fundamentals of how PLA works, and how it degrades.
Stereoisomer
Although we use the generic acronym of ‘PLA’, there are actually two chiral forms of poly(lactic acid). Generally the one that we most commonly find in our spools of consumer-grade PLA filament is poly(L-lactide) (PLLA), while its more rare chiral form is poly(D-lactide) (PDLA). These match their chiral lactic acid forms, being L-lactic acid and D-lactic acid.
If both PLLA and PDLA are combined into a single polymer chain you thus get another type of material with its own set of properties. Overall this PDLLA polymer is quite stable, preferring to stay amorphous while still resisting hydrolysis better than its other polymer forms.
While industrial production of D-lactic acid is possible, most production is in the form of cheaper L-lactic acid, with correspondingly FDM printer filament thus having a high chance of being PLLA. This, along with factors like the ratio of crystallinity versus amorphous areas determines the initial state of the material.
These two states, of crystalline versus amorphous are defined by the state of the polymers, with the crystallized state being the most stable form that is most resistant to degradation through hydrolysis, yet this state is also the most rigid and thus most brittle. This is of course just the beginning of all the fascinating materials science.
Polymer Types
While just the basic PLLA and PDLA polymers already provide a lot of fascinating materials science, there is a whole world of things you can do with these polymers. We already touched on blending PLLA and PDLA, whereby both types of polymers support each other. This same blending can be done with other types of polymers as well, to further modify the properties of PLA, with many of the essentials covered by Vincent DeStefano et al. in this 2020 paper.
In addition to blending polymers, we can also create copolymers, whereby PLA monomers are mixed with other monomers to create a new polymer type with certain desirable properties, like enhanced flexibility. This already gets us right in the territory of the countless additives for PLA to modify its plasticity, nucleation and other characteristics.
Of note are the different crystallinities of PLA, as also covered by DeStefano et al., starting with ɑ and ɑ’-crystallinity as the most common types, and a PLLA/PDLA blend being fully amorphic if it contains more than 10% of PDLA. Since most PLA blends tend to have less PDLA than this we generally classify PLA filament as semi-crystalline.
Plasticizing
Unsurprisingly, most of the additives and modifications to PLA focus on plasticizing it, which can be done through a number of methods in addition to modifying the amount of PDLA in the blend. A good overview of these methods can be found in this 2024 paper in Polymers by Elena E. Mastalygina et al..
Beyond PDLA/PLLA blends we can also blend in other polymers, including a range of flexible polyesters, though it’s essential to determine intermolecular compatibility. Common here are polycaprolactone (PCL), polybutylene adipate terephthalate (PBAT) and polybutylene succinate (PBSA), which like PLA are biodegradable polyesters.
Where things get interesting is with copolymers, which can also involve the aforementioned PCL, PBAT, etc., as well as polyethylene glycol (PEG), with a wide range of combinations possible. Some of these combinations are summarized in the graphic to the right from said paper by Mastalygina et al. using data from cited papers.
Although these methods, along with the more experimental structural modification approach, make the base PLA polymer more flexible, it’s also possible to introduce oligomeric and low-molecular-weight plasticizers which essentially wriggle into the PLA polymer matrix, thus increasing its mobility.
Another focus of such additives can be to act as nucleation agents for nano-crystallization, creating small spherulites that do not impact plasticity nearly as much as naturally forming large spherulites.
Plasticizer
The aforementioned paper covers a range of these plasticizers, such as PEG. Here a problem is that although PEG as a plasticizer additive does promote PLA ductility, PEG tends to migrate out of the polymer. Fortunately there is a dizzying amount of possible plasticizers here, ranging from lactic acid oligomers to epoxidized sunflower oil, as well as linseed, cottonseed, soybean, castor, and other oils.
In a 2025 paper in Polymers by D’Amico et al. the use of used sunflower oil (USOP) as PLA plasticizer is compared with the conventional plasticizer tributyrin (TB). Both show a very similar effect on the plasticity of the final product, though long-term stability of the plasticizer was not tested.
Of course, determining which plasticizer was used in any off-the-shelf spool of PLA filament is effectively impossible. A quick look at a number of commercial PLA filament options, ranging from Prusa to Bambu Lab, shows that their material safety data sheet (MSDS) lists the material only as ‘PLA with additives’.
In a way this makes even ‘regular’ PLA about as much of a mystery filament as so-called ‘PLA+’, with its arbitrary additives such as calcium carbonate.
Degradation
As for how that spool of filament degrades, we can thus draw a number of conclusions. The first is that hydrolysis is the primary degradation mechanism, gradually shortening the backbones of the polymer chains. Yet the other type is one that happens regardless of whether the PLA is fully dried and stored in a container of some sort. A good example of this can be found in e.g. a 2021 Polymers research paper by Tien-Wei Shyr et al. in which many variations of additive-free PLA samples were stored for multiple years.
One set of samples was put into zipper bags and stored in a vacuum-free desiccator, while the other set was stored in vacuum-sealed bags. Both sets were stored like this at room temperature for three years, after which their crystallization and hydrolysis levels were checked.
For the vacuum-sealed samples there was no significant degradation compared to the received samples, while the three-year old samples in the zipper bags had degraded significantly, suffering hydrolysis, nucleation and corresponding crystallization and thus brittleness.
Brittleness
When I recently did some FDM printing for a comparison article series with SLA resin printing, I had dug up a spool of white Sunlu PLA filament that I had left kicking around for probably around three years. This spool had seen itself stuck exposed to room conditions for at least a year when I noticed that after letting it sit fed into the extruder for a number of hours would result in it snapping.
Although I could still print with this filament if I didn’t let it sit too long, it was clear that not only was the PLA rather brittle at this point, it also had assumed a very strong preference for staying in the shape that it was in while on the spool.
What this suggests is thus two things: significant hydrolysis had weakened the filament, and increased crystallization had resulted in both rigidity and brittleness.
Unknown is whether something like a PEG plasticizer was used with this filament, with it having left the building somewhere in the past few years. If the plasticizer is no longer present that would obviously pose somewhat of a conundrum with any attempts to revive the filament.
Ultimately what one can do here is to heat the filament above its Tg for a number of hours, so at least 65 °C for the average PLA blend. This should restore the semi-crystalline state somewhat, although if enough damage has been wreaked by hydrolysis all bets are off. For this particular spool of PLA I did toss it into a Chitu Filapartner filament dryer as it allows you to set the temperature and time, but without a good way to measure the internal material temperature it may not have gotten hot enough.
Considering that this old spool of PLA was fully dried about a year prior in a Sunlu filament dryer using its PLA preset, followed by it being stuffed into a vacuum bag and into an ‘airtight’ container, it’s likely that most of the damage was indeed done by 1-2 years of exposure to room air.
I have saved a few samples of this old filament for later study, but in light of the research covered in this article it highlights just how hard the materials science is, even when it comes to a material as mundane as PLA. Ultimately the best you can do is keep it in that nice vacuum-sealed bag when not printing and pray to the 3D printer gods that you didn’t overlook something important and that maybe one day the filament manufacturers will bless us with details on what these ‘additives’ are.
This articles is written by : Fady Askharoun Samy Askharoun
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