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Table of contents
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Research conducted on wet 3D printing filaments by the
BCN3D Engineering team
Page 4
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Materials and conditions of the experiments
Page 5
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Test 1: Limit of printability
Page 5
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Test 2: Kinetics of absorption
Page 9
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Test 3: Mechanical properties and humidity
Page 13
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Investigation of the Detrimental
Effects of Humidity on Hygroscopic
Polymers and Filament Drying
Methods
Water is one of the most important constituents of the atmosphere, depending on geographical
factors and the weather, it can make up as much as 2% of the volume of the air that we breathe.
Most polymeric materials interact with water by absorbing it, regardless of its physical form. That is
why raw thermoplastic materials are normally subjected to a so-called dehydrating phase, when they
are processed at a high temperature before being used, to ensure that there is no water left in the
form of bubbles. These water bubbles would stay trapped in the polymer matrix and would generate
localized imperfections, which are detrimental to the aesthetical and mechanical properties of the
plastic object made out of them.
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Depending on the nature of the polymer and its behavior in a water-rich environment, it can be
characterized as hygroscopic or non-hygroscopic. Non-hygroscopic materials tend to absorb water
on their surface only, making it easier to remove by simple heating. On the other hand, hygroscopic
materials are able to absorb big quantities of humidity from the air and store it deep within their matrix.
Heating up a hygroscopic plastic helps to remove the water absorbed on the surface, but not the water
stored deep in their matrix. That is why hygroscopic polymers need to be looked after and stored more
carefully before being processed and to be kept in a dry and sealed environment.
The most common 3D printing filaments are formulated with hygroscopic materials, such as PA, TPU,
PVA, PET, or ABS.
The BCN3D Engineering team has been conducting research on the effects of humidity on 3D printing
filaments, with the aim of generating basic knowledge about how various materials absorb moisture,
how that affects their performance, and the best methods to keep them dry. Firstly, they examined
PA, PVA, and TPU filaments’ water absorption characteristics, and their ability to produce reliable
end results after being subdued to certain levels of relative humidity as they are the most hygroscopic
materials in our filament portfolio, therefore, the most sensitive to incorrect storage conditions.
A Psychrometric chart is the best way to visualize the relationship between Absolute
Humidity (AH), Relative Humidity (RH), and temperature (T): it consists of a multidimensional projection
of these three variables and can be of great help when understanding the phenomenon of drying of
solids with warm air.
Heating is indeed the easiest way to reduce the relative humidity of a volume of air. That’s the reason
why a stream of warm air is normally used to dry food and clothes.
As an example of how to use a psychrometric chart, the graph below represents a physical
transformation of typical atmospheric air (temperature of 25 ºC and RH of 50%). When that air is heated
to 45 ºC, its absolute humidity (expressed in the graph as Humidity Ratio) does not change: however,
the relative humidity of the system drops from 50% to 17% (The transformation is represented as
a horizontal pink line). When the relative humidity of a stream of air is reduced this way, its drying
capacity is greatly increased: this is the reason why a hot stream of air is the most common way to dry
hygroscopic solids, such as plastic pellets and filaments, wood, food, and plants.
Graph 1: Psychrometric chart for water in the air. The pink line represents the effect of heating on the
relative humidity of a stream of air. Source: http://www.flycarpet.net/en/PsyOnline
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Materials and conditions of the experiments
The BCN3D Engineering team created an environment in which they could control the humidity
and condition the filament spools, which is going to be referred to as the humidity chamber in this
document.
To measure the relative humidity inside the chamber, the team used two thermo-hygrometers,
an analog and a digital one. In order to be able to compare the data coming from the two different
instruments, they carried out a cross-calibration experiment, by plotting the RH measured by the two
thermo-hygrometers at different humidity conditions (Graph 2).
Graph 2: Analog hygrometer (AN) and digital hygrometer (DG) values of relative
humidity (RH) in different conditions. DG was arbitrarily taken as a reference.
It is clearly visible in Graph 2 that the analog instrument's curve flattens at values around 20%.
Therefore, it can be determined that its lower use range is limited to 20% RH. In the mid-range, the
two instruments gave comparable results. In the upper range of Graph 2, it looked like the analog
instrument had a strong positive deviation. However, the team would not take this into account, since
those data points were taken very far from the equilibrium as well as liquid water was just added to the
system, and the response time of each instrument could have affected the readings.
Each material reacts to humidity in a different way, with highly hygroscopic plastics capable of
absorbing up to 10% of their weight in water. This absorbed water is detrimental to the 3D printing
process, as it generates aesthetical and mechanical defects. For this reason, the BCN3D Engineering
team wished to determine the maximum amount of absorbed water that does not compromise the
printing process for the most hygroscopic materials available in the BCN3D filament portfolio. That is
why PA, PVA, and TPU filaments were chosen for the following experiment.
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A brand new spool of filament of each material was opened, dried overnight, and left for 4 consecutive
days at a given percentage of relative humidity and temperature in a closed environment. In order to
recreate the desired test conditions, a hermetical humidity chamber was used: this apparatus was
provided with a digital hygrometer and thermometer and a humidity controller, which would release or
absorb humidity, to keep the chamber and the contained spools exposed to constant levels of relative
humidity.
After spending 4 days in the chamber, the filaments were taken out and they were used to print a few
test prints to evaluate the damage caused by humidity.
Table 1: Various 3D printing materials’ weight change at different relative humidity rates
The results reported in Table 1, above, show the amount of water these 3D printing spools absorbed
in relation to the environment’s water content. When the spools were kept in a dry atmosphere (Entry
1, Table 1) no relevant increase in weight was recorded, however, when they were exposed to higher
humidity rates, the spools absorbed a proportionally higher amount of water.
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As the table shows, each material followed a unique absorption profile: PVA is the most hygroscopic
of the tested materials, and when kept at 70% RH for 4 days it absorbed the equivalent of 1.22% of its
original weight in water. Meanwhile, PA and TPU seemed to behave in a similar way when exposed
to low environmental humidity levels (Entries 1-4, Table 1, 10-40% RH), absorbing equal amounts
of water. However, while TPU’s absorption capacity flattened out above 40% RH, PA showed a more
hygroscopic behavior in a high humidity environment (Entry 5, Table 1).
On the following graph (Graph 4), you can see the plotted data points from Table 1, which shows
increased levels of relative humidity on the X-axis and the growth in the materials’ weight due to the
absorption of this humidity on the Y-axis.
Afterwards, the team started printing a few simple geometric shapes with these preconditioned
filaments to verify if the exposure to humidity compromised the printability of the materials. The test
prints consisted of a fine-walled cylinder and a cuboid shape, ideal for inspecting the presence of
bubbles, voids, and stringing.
Table 2: Outcome of the print tests after conditioning the spools at different humidities
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In the control experiment, when humidity was kept below 10%, all spools produced perfect prints, as
shown in the picture below, the printed samples show no imperfections (Photo 1 & Entry 1, Table 2).
Photo 1: From left to right, PVA, PA, and TPU, print test after 4 days at RH <10%.
At 12% humidity, while PA and PVA still printed as good as during the control experiment, TPU already
showed significant stringing, meaning that the viscosity of the melt was reduced by the presence of
water, acting as a plastifier (Photo 2 & Entry 2, Table 2).
Photo 2: Printability limits, from left to right, PVA at 40% RH, PA at 30% RH, and TPU at 12% RH.
PA started producing cloudy surfaces and showing stringing at 30% RH while PVA, even though it is
the most hygroscopic of the three tested materials, withstood high levels of humidity, maintaining its
printability at up to only 40% RH (Photo 2 & Entry 4, Table 2).
Photo 3: From left to right, PVA, PA, and TPU, test prints after 4 days at RH = 70%.
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Table 3: Printability limits for the tested filaments
PVA PA TPU
This experiment sheds light on important information about the behavior of PA, PVA, and TPU filaments
when stored in an environment with different levels of relative humidity. By measuring the amount
of water absorbed, the BCN3D Engineering team was able to identify PVA as the most hygroscopic
material, followed by PA and finally TPU. However, it turned out that TPU, which is the least
hygroscopic out of these three materials, is also the most sensitive to incorrect storage. In particular,
TPU was deemed not printable when exposed to RH of 12% for 4 days, corresponding to only 0.05%
water absorption by weight (Table 3). PA proved capable of absorbing higher amounts of water, which
makes it more hygroscopic than TPU. However, PA was less sensitive to humidity and could be printed
with good results after being conditioned for 4 days at 30% RH. The measured printability limit for PA is
0.10% water absorption by weight.
PVA stood out as the most hygroscopic filament in this study, being able to absorb up to 1.22% of water
when kept at 70% RH. When printing with PVA, satisfying results were obtained in most cases, with
only the spool conditioned at 70% RH drastically failing. We were able to determine the printability limit
of PVA as 0.47% water absorption by weight.
The second experiment that the BCN3D Engineering team conducted was meant to take into account
the effect of time on the rate of water absorption of different materials. They set the humidity rate
to 60% RH in the humidity chamber to simulate a quite common condition encountered in an office
or at home. The test consisted of measuring the weight gain over time of a set of dry spools of
filaments. The chamber was also equipped with an internal fan, to speed up the test and to ensure fully
homogeneous air conditions at all times.
The spools were pre-dried in a ventilated kitchen oven at 70°C overnight. The dried spools were then
placed inside the humidity chamber and their weight was measured about every hour during the first
day and every day for up to 6 days (Tables 4,5).
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Table 4: Kinetics data for PVA, PA, and TPU
Time (h) PLA (g) PLA % PAHT CF15 (g) PAHT CF15 %
Table 4 shows that PVA, the most hygroscopic material out of the five, is the fastest at absorbing
moisture and it is also the one that takes in the highest amount of water in the long run, reaching
almost 1% of mass gain after 6 days. PA and TPU are slower absorbers. TPU is slightly faster, but its
absorption curve flattens out earlier and reaches saturation after 50 hours. This phenomenon was also
evident from the results of Test 1. PLA also reached saturation quite early - around 75 hours - and no
increase in weight was registered after more days of conditioning.
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Table 5 shows that PAHT CF15, thanks to its composite nature, proved less hygroscopic than PA and
required a longer time to reach the same absorption level. This material, however, similarly to PA, has a
great water absorption capacity and did not reach saturation within the time of the experiment.
On the following graph (Graph 5) you can see the filaments’ increasing mass gain over time when
exposed to a fixed 60% relative humidity rate.
Graph 4: Filaments’ mass gain over time when exposed to a fixed 60% of
relative humidity rate
From the collected data, the Engineering team was able to calculate an approximate absorption rate of
0.05% mass gain per hour for PVA and 0.025% mass gain per hour for TPU, PA, PLA, and PAHT-CF.
Resistance to incorrect
High Poor Very poor High* Poor*
storage
Approximate absoption
0.05%/h 0.025%/h 0.025%/h 0.025%/h 0.025%/h
rate (%/hour)
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The Engineering team at BCN3D could also calculate a theoretical shelf life at 60% RH, in a well-
ventilated room, intersecting the data from Tests 1 and 2. From this calculation, the team could
determine that PVA needs 12 hours to reach the critical water content of 0.47%, which leads to
unsuccessful prints (Table 6). For PA, this time is reduced to 4 hours to reach the critical water content
of 0.10%. According to this calculation, TPU only needs 1.5 hours at 60% RH and it already fails the print
test (Table 6). These numbers are quite alarming and show how easily humidity and incorrect storage
can affect the outcome and consistency of the FFF 3D printing process.
They also examined the materials’ behavior when inside the Smart Cabinet, an environment designed
to be protected against humidity, as explained further down this document. The following graph shows
the environmental parameters of the Smart Cabinet in function, with the external relative humidity at
55%
Graph 5: The BCN3D Smart Cabinet maintains the internal humidity rate between 15-20%,
even with the external relative humidity at 55%
The BCN3D Smart Cabinet maintains the filaments in a low-humidity environment, greatly reducing
the chances of print failure due to excessive water content. As shown in Graph 5, even with an external
humidity of 55%, the Smart Cabinet ensures an internal humidity rate between 15-20%, to preserve
filaments’ printability, extend their shelf life, and to reduce aesthetic defects on the end results.
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Test 3: Mechanical properties and humidity
It has been made evident that printing with wet spools produces negative results. We have analyzed
the aesthetic effects of humidity on the printing process, but the defects shown are not just unpleasant
to the eye; each defect is a structural imperfection of the part and therefore a weakness. If the presence
of water generates bubbles and voids during the extrusion, interlayer adhesion will also be affected and
so, with each layer, we are introducing a great amount of imperfections which weaken the structure
that we are building.
Theoretically, it should be easy to quantify the influence of these local imperfections on the overall
strength of the printed part. For this reason, we set up a mechanical testing experiment where we
measured the tensile behaviour of a hygroscopic material, by printing after storing it at different
ambient conditions. For this study, PA was chosen as it is one of the most hygroscopic filaments used in
FFF 3D printing.
To measure the effects of humidity on the mechanical properties, we made sure to remove all moisture
from 4 new PA spools by leaving them in an oven (70 ºC) overnight. Then, each of them was treated
separately:
From each spool, a set of Type 1 tensile dogbones were printed at 100% infill, using a longitudinal linear
pattern to fill the shape. After printing, the dogbones were conditioned in a controlled environment
(50% RH, 25ºC) for 48 hours, to ensure the test was not affected by the humidity taken up after printing.
Tensile strength and Young’s modulus were measured as indicators of part strength and stiffness
respectively (Table 7).
The mechanical testing showed that the best mechanical values were obtained with a storage at low
humidity. PA 18% showed the highest tensile strength and Young’s modulus, meaning that the 3D
printed dogbone was capable of withstanding the highest load before breaking (Graph 6). Also, a higher
modulus of stiffness means that the printed part was capable of resisting deformation with a greater
force. The maximisation of these two values is a good protocol, to identify the best print condition,
as they are directly affected by interlayer adhesion and part density. Unexpectedly, PA dry showed a
lower strength and modulus than PA 18%: a possible interpretation for this is that the lack of water,
which acts as a plasticiser and lowers glass transition, affected the extrusion process and the adhesion
between the extruded filaments, resulting in a slightly weaker printed part.
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PA 35% behaved similarly to PA 18%, with good strength and modulus, if somewhat lower. When the
spool of PA was left unattended on a shelf for one week, apart from the worse surface finish and part
accuracy, we were able to detect a much worse mechanical behaviour, compared to the properly stored
filaments. PA Shelf is indeed 22% weaker and 57% less rigid than PA 18%.
This mechanical testing of 4 PA spools, stored under different humidity conditions shows the
tremendous effect of water on the mechanical behaviour of a part printed with PA. For this reason,
we encourage the storage of hygroscopic spools in a controlled environment characterised by a low
humidity, just as in our BCN3D Smart Cabinet. For an optimal duration of the spool, low humidity
storage, combined with an occasional spool recovery at 70 ºC is the ideal way to operate when working
with highly hygroscopic materials, such as PA, TPU and soluble supports like PVA and BVOH.
There are a couple of filament drying methods that are well-known in the 3D printing industry.
However, these methods have various disadvantages, which can end up even damaging the polymer.
Desiccants
The relative humidity rate cannot be controlled, and this method needs constant replacements and
maintenance.
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Other traditional filament drying methods
Constant heat baking filaments in order to dry them can mount up to high energy costs, as well, while it
only makes it possible to dry a few spools of filament at a time.
Adsorption dryers
Adsorption dryers are a common way to dry solids and polymers that have a tendency to absorb
moisture. The way they work is based on the affinity of the adsorbing agents to water; what they
effectively do is seizing water molecules from the air, greatly reducing atmospheric humidity. These
adsorbing agents are normally in the form of pellets or spheres, and are made of silica, alumina,
or special clays, which have the ability to absorb great amounts of water from the air, and can be
regenerated. The drying process consecutively increases the water’s evaporation rate from the
surrounding solid surfaces thus reducing their total water content. After absorbing a given amount of
water from the air, the adsorption material becomes saturated and its effectiveness quickly decays.
By isolating the absorption material from the heating chamber and increasing its temperature, we can
release all the absorbed humidity into the surrounding environment and regenerate the material.
The BCN3D Smart Cabinet also works based on this method, alternating between drying cycles
and regeneration cycles, thus maintaining a constant dry environment around the stored spools and
protecting them from sudden external changes.
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Vacuum process
Vacuum drying is based on the fact that vapor pressure and the boiling point of liquids are dependent
on environmental pressure. Water is no exception under this principle either, and, even if it can exist in
both vapor and liquid form under standard conditions (25 ºC and 1 bar), the relative proportion of the
two phases at the equilibrium can be controlled by either temperature or pressure. By reducing the
atmospheric pressure, it is possible to lower the boiling point of water. For example, if the pressure
would be reduced to one-tenth of the normal atmospheric pressure (from 1.0 to 0.1 atm) the boiling
point of water would change from 100 ºC to 33 ºC. This way it is possible to remove liquids from solids
without actually heating. For this reason, vacuum drying is considered a very mild and effective way
to reduce the water content of solids. It is also the method of choice for reaching very low humidity
contents, even for highly hygroscopic solids. However, a great disadvantage of vacuum drying is the
equipment cost and constant maintenance needed to ensure a safe and long-lasting operation.
Compared to all previously mentioned methods, the BCN3D Smart Cabinet has a low energy
consumption (12 W Avg / 100 W Max.) while it can keep the filament below the 40% relative humidity
rate, which is optimal for the majority of the 3D printing materials.
It can dry up to 8 small spools of filament (between 750g to 1 kilogram), or 4 big spools (up to 2,7
kilograms per spool), without heat, therefore maintaining the materials’ tensile strengths.
The BCND Smart Cabinet protects the filaments long-term and significantly reduces print failure due
to moisture. The silica gel inside, open to the dehumidifying environment, absorbs the moisture from
the air in the chamber. Once it becomes saturated, the gel is isolated from the materials and gets
heated up until it releases the moisture, purging it out of the system. After the purge, the silica gel has
been refreshed and ready to collect more moisture. This process effectively keeps the filament dry and
in optimal condition for its use.
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Besides offering material protection, the Smart Cabinet offers other benefits such as Uninterruptible
Power Supply (UPS), which protects equipment and work against power outages that could ruin hours
of printing.
Conclusion
The data collected during Test 1 was fundamental to understanding the hygroscopic behavior of
BCN3D filaments PA, PVA, and TPU. The test allowed to classify the three filaments based on their
hygroscopicity, with PVA as the most hygroscopic, followed by PA and TPU, progressively. Even if PVA
absorbed water the easiest, it proved to be the least affected by this phenomenon when it was time
to 3D print with it. On the other hand, TPU, which was classified as the least hygroscopic, could not
produce satisfying prints with water content as low as 0.10% by weight.
Based on the print test, we could establish a maximum humidity content for each material: this value
can be easily estimated by checking the weight of the spool after drying and before printing.
Based on the print test, we could establish a maximum humidity content for each material: this value
can be easily estimated by checking the weight of the spool after drying and before printing.
Test 2 showed how fast the different materials picked up the moisture from a 60% RH environment.
From this data, the BCN3D Engineering team could calculate how long it takes for each material to
become unusable and further drying is needed prior to printing.
The outcomes of this study showed how critical is the correct storage of the spools to the aesthetics
and mechanical integrity of the printed part. TPU should be looked after with special care as it is
proved to be the most sensitive material among the ones the team tested.
The results from Test 3’s PA spools stored under different humidity conditions proved water’s
significant detrimental effect on mechanical behaviour. The decrease of tensile strength and Young’s
modulus values reinforce the importance of keeping highly hygroscopic materials in low humidity
storage, with an occasional spool recovery at 70 ºC.
Interested in completing your 3D printing ecosystem with a Smart Cabinet? Reach out today!
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