Additive Manufacturing 89 (2024) 104265

Contents lists available at ScienceDirect

Additive Manufacturing
journal homepage: www.elsevier.com/locate/addma

The role of crystallization and annealing on the thermal conductivity of

material extrusion additively manufactured parts
Daniel J. Braconnier a , Ryan M. Dunn b , Eric D. Wetzel b , Randall M. Erb a, *
a
Department of Mechanical and Industrial Engineering, Northeastern University, 360 Huntington Avenue, Boston, MA 02115, USA
b
DEVCOM Army Research Laboratory, Aberdeen Proving Ground, MD, USA

A R T I C L E I N F O A B S T R A C T

Keywords: Despite the significant research being conducted on the mechanical reliability of additively manufactured parts,
Thermal Conductivity Fused Filament comparatively little focus has been paid to the property of thermal conductivity. Additively manufactured
Fabrication thermally conductive parts have the potential to benefit thermal management technologies that are currently a
Polymer Matrix Composites
bottleneck of many classes of advanced electronic devices. Creating parts with high thermal conductivities re­
Polymer Crystallinity
Thermal Management
mains a major challenge for the most prevalent form of material extrusion additive manufacturing, fused fila­
ment fabrication, which creates parts by extruding multiple layers of molten polymeric extrudate using an
automated gantry system. The low thermal conductivity of these parts stems from several types of interfaces and
voids inherent to the fused filament fabrication additive process, which create significant internal resistance to
the flow of heat through a part. To increase thermal conductivity, many researchers and companies have added
thermally conductive particles into the polymeric filaments. Still the achievable properties are largely con­
strained by the printing defects inherent to the printing process, especially when compared to injection molded
parts. In this work, we investigate the role of thermal post-processing to both anneal the printed part and to tune
the crystallization state of the polymer. We find that careful thermal post-processing of parts made with com­
mercial filaments can improve thermal conductivity values to 2.5 times the as-printed property values. Further,
we detail several correlations between processing conditions and thermal conductivity outcomes that will
improve the implementation of fused filament fabrication for addressing thermal management challenges in
industry.

1. Introduction
The energy density of everyday electronic devices is increasing,
creating thermal management challenges that limit processor speeds
and degrade battery performance. A way to increase the efficiency of
thermal management solutions is to leverage topological optimization to
generate new complex heatsink geometries using software [1–3]. Often,
these topologically optimized designs require additive manufacturing to
generate. Several additive manufacturing processes can be leveraged to
generate topologically complex thermal management devices including,
for example, powder bed fusion, vat photopolymerization, and material
extrusion. Of these, the material extrusion additive manufacturing
process commonly referred to as fused filament fabrication (FFF) is the
cheapest and most prevalent form of additive manufacturing in which
parts are created by laying traces of extruded thermoplastic on top of
each other guided by an automated gantry system. The thermal
conductivities of FFF parts are limited by the low thermal conductivity
of common thermoplastic polymers (~0.2 W/m⋅K).
To improve the thermal conductivity of FFF feedstock filaments,
many companies and researchers have considered loading the thermo­
plastic with thermally conductive fillers like copper or graphite particles
to create thermally conductive polymer composites (TCPCs) [4]. TCPCs
are both lightweight and amenable to economic, tailorable
manufacturing processes like injection molding and FFF printing. A key
advantage of these materials, compared with pure metal heat sinks, is
that they can be engineered with low or negligible electrical conduc­
tivity to reduce the likelihood of device-level electromagnetic interfer­
ence or electrical shorting. With injection molding, TCPCs can reliably
achieve thermal conductivity values of 6–8 W/m⋅K, sufficient for effi­
cient dissipation from low-power electronics [5–8]. However, thermal
conductivity drastically reduces when TCPCs are processed with FFF
printing [9,10]. The FFF process produces heterogeneous parts filled

* Corresponding author.
E-mail address: r.erb@northeastern.edu (R.M. Erb).

https://doi.org/10.1016/j.addma.2024.104265
Received 5 March 2024; Received in revised form 5 June 2024; Accepted 14 June 2024
Available online 17 June 2024
2214-8604/© 2024 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC license (http://creativecommons.org/licenses/by-
nc/4.0/).
D.J. Braconnier et al.
with a high population of inter/intra-layer interfaces and voids, leading
FFF parts to have significantly higher thermal resistance (and thus lower
thermal conductivity) than comparable injection molded parts. Seppela
et. al demonstrated some improvement could be achieved by optimizing
the weld formation during the print process by tuning FFF parameters
and closely monitoring temperature [11]. Current market-leading TCPC
parts printed via FFF have conductivity less than 4 W/m⋅K [1,12–14].
These lower values significantly limit the relevance and impact that FFF
can play in addressing thermal management challenges.
An underexplored route to improving TCPC parts printed via FFF has
been in the thermal post-processing of these parts to heal defects in the
as-printed structure, as well as growing crystallites that are more
conducive to heat flow. Such thermal post-processing has shown
promise recently to increase mechanical properties of FFF parts. Hart et.
al demonstrated that annealing FFF parts above the glass transition
temperature of the polymer matrix offers an adept way to heal inter-
layer defects and improve overall mechanical strength [15,16]. For
thermal conductivity, these inter-layer defects serve as a thermal resis­
tance to the transfer of heat. In addition, tuning the crystallization state
of the matrix polymer should serve to increase the efficiency of phononic
transport through the microstructure. Increased crystallization per­
centages have been shown to increase the number of ordered and low
resistance pathways for phononic transport, thus increasing the thermal
conductivity of polymers [17–20]. Exploring these concepts through
thermal post-processing may offer an avenue to improve the perfor­
mance of FFF parts in thermal management applications.
Here, we provide a systematic study into the role that thermal post-
processing plays in the resultant thermal conductivity of FFF parts. To
minimize variability in feedstock, we rely on two different off-the-shelf
FFF filaments that exhibit high thermal conductivity and low batch-to-
batch variation. First, we investigate the dependence that print quality
and print orientation have on the microstructure outcomes and resultant
thermally conductive properties of FFF parts. Second, with optimized
printing parameters, we investigate the function that annealing has on
healing inter/intra-layer defects, by bringing post-process temperature
conditions from room temperature all the way through melt tempera­
tures. Third, we turn our attention to the role that crystallization of the
polymeric matrix has on the thermal conductivity of the final part. We
then offer a holistic assessment on the role that thermal post-processing
Fig. 1. : Schematic showing the microstructure of a typical FFF part that is characterized with inter-layer and intra-layer defects that can create thermal resistance
and reduce the thermal conductivities of printed parts. These defects can be tailored through various processing pathways including a) unoptimized printing, b)
optimized printing, and c,d) annealing after optimized printing either below (c) or above (d) the polymeric melt temperature. The bar chart reports actual weak-axis
thermal conductivity values for a Graphite-PA6 part discussed in further detail within this paper. The “D” from the DAPS Lab logo was selected to demonstrate the
effect of various processing parameters to the final part geometry.
2
Additive Manufacturing 89 (2024) 104265
can play in enhancing the thermal conductivity of TCPC FFF parts.
Overall, higher thermal conductivities can be achieved with optimized
printing and annealing processes; however, clear thermal sagging of the
part can be observed if the annealing temperature surpasses the poly­
meric melt temperature (Fig. 1). We believe that a deeper understanding
of the processing, structure, and property relationships in FFF parts
comprised of TCPCs will enable this economic form of manufacturing to
address some of the pervasive thermal management challenges in
industry.
2. Materials and methods
2.1. Filament materials
Two different off-the-shelf thermally conductive FFF filament ma­
terials were chosen that exhibited high thermal conductivity and low
batch-to-batch variation: i) 2.85 mm Copper Filament (“Cu-PLA”, The
Virtual Foundry, Stoughton, WI), and ii) 2.85 mm Ice9 Rigid (“Graphite-
PA6", TCPoly, Atlanta, GA). Cu-PLA is a TCPC comprised of polylactic
acid (PLA) and ~50 vol% copper filler with no manufacturer-reported
thermal conductivity [21]. Of note, Cu-PLA is not marketed as a TCPC
but rather as a green body filament to achieve copper parts through
sintering. The copper phase is spherical particles with diameter of 75 ±
50 µm, as determined by scanning electron microscopy (Fig. 2a).
Meanwhile, Graphite-PA6 is a TCPC comprised of polyamide-6 (PA6)
and ~50 vol% of graphite filler with a reported thermal conductivity of
4 W/m⋅K in the strong axis and 1 W/m⋅K in the weak axis for printed
parts [22]. The anisotropy here is reported to be due to the predomi­
nance of inter-layer defects between printed layers. Of note,
graphite-filled thermoplastics have a lower electrical conductivity than
thermoplastics containing similar loadings of metal fillers. The graphite
phase in Graphite-PA6 appears to be 75 ± 25 µm aggregates of graphitic
flakes. The graphitic flakes are polydisperse with diameters ranging
from 5 to 25 µm with consistent aspect ratios of ~12 as determined by
scanning electron microscopy (Fig. 2b). Some additional characteriza­
tion in the as-received filaments is provided below and in Supplemen­
tary Information. These two commercial filaments exhibit more rigidity
and brittleness than standard polymeric filaments due to their high filler
content.
D.J. Braconnier et al.
Fig. 2. a) A PLA filament filled with 50 vol% copper particles and b) a PA6 filament filled with 50 vol% graphite particles were used to print thermally conductive
parts, such as the cubes shown here, using an off-the-shelf FFF 3D printer. Scanning electron micrographs of the cross-sections of fractured filaments were collected to
confirm filler morphology. Both filaments were used to produce parts.
2.2. Manufacturing and post-processing methods
For printing the TCPC filaments, a TAZ6 FFF machine (LulzBot,
Fargo, ND) was employed. No structural modifications to the TAZ6 were
required to print the commercial filaments. Micro Swiss (Ramsey, MN)
stainless-steel nozzles were implemented on the TAZ6. It was deter­
mined that a 1.2 mm nozzle allowed both commercial products a suffi­
ciently sized orifice to flow through. Smaller nozzle orifices (below
0.5 mm for Graphite-PA6 and below 0.8 mm for Cu-PLA) led to poor
filament flowability. Most print parameters were held constant across all
studies. The extruder temperature was set to 240 ℃. The bed tempera­
ture was set to 65 ℃. The print speed was fixed at 15 mm/s, with a layer
height of 250 µm. Prints were conducted with 2 outer shells and − 45/45
◦
infill raster (unless otherwise specified) at 100 % infill. Retraction was
left off; however, each of the TCPC filaments were capable of with­
standing print processes with retraction enabled. A thin polyvinyl
alcohol coating was required to achieve stable bed adhesion to complete
the prints successfully. All filaments were stored in sealed desiccant
filled chambers when not in use. Sample sets were printed at the same
time and all samples were removed from the build plate immediately
after completion to minimize any effects of residual build plate heat
transfer to the prints. Samples were stored in air tight containers. All G-
code to print each sample was generated using Simplify3D version 4.1.2
(Cincinnati, OH).
Annealing of samples was done by placing printed specimens into a
pre-heated DX302C drying oven (Yamato, Tokyo, Japan) at tempera­
tures of 100 ◦ C, 135 ◦ C, and 170 ◦ C for times ranging from 0 to 14 hours.
Samples were either removed from the hot oven and allowed to quickly
acclimate to room temperature at a cooling rate of approximately − 10
◦
C/second or were slowly cooled within the oven chamber at a rate of
− 1 ◦ C/minute.
For comparison, hot-rolling of filament material was conducted to
create samples that lacked printing interfaces. The feedstock filaments
were placed between two 3 mm silicone sheets on top of a hotplate set to
180 ◦ C for Cu-PLA and at 270 ◦ C for Graphite-PA6. The filaments were
allowed to melt. While on the hotplate, the composite melts were then
hot-rolled with an aluminum rolling pin. To ensure high levels of shear
alignment along the rolling direction, the composite melt was rolled thin
and then folded over onto itself, and re-rolled several times. Once
visually homogenous, the composite melt was rolled to a desired
3
Additive Manufacturing 89 (2024) 104265
thickness that ranged from 0.5 mm to 3.0 mm. The hot-rolled filament
sheets were removed from the hotplate and allowed to quickly acclimate
to room temperature at a cooling rate of approximately − 10 ◦ C/second.
Subsequently, 33 mm diameter disks were punched out of the composite
film for thermal characterization.
2.3. Thermal characterization
Thermal Gravimetric Analysis (TGA): TGA was performed with a
Discovery TGA (TA Instruments, New Castle, DE). Each ~ 10 mg sample
was ramped to 600 ℃ from ambient under an air environment. TGA was
used to confirm that both composites had ~ 50 vol% filler particles and
to determine the thermal degradation temperatures of both filaments
(Supplementary Information).
Differential scanning calorimetry (DSC): DSC was performed with a
Q2000 DSC (TA Instruments, New Castle, DE) using TA TZERO non-
hermetic pans with lids in an argon atmosphere at a samples size of ~
10 mg. DSC was performed to characterize as-received filament and
printed parts at all stages pre- and post-annealing. Specifically, the
crystallization changes were monitored in the filaments and printed
materials to understand relationships between property outcomes and
polymer conformations. A baseline protocol of the following steps was
used to assess the as-received commercial filaments (PLA/PA6): (1)
Ramp 10 ℃/min to 200/250 ℃, (2) Isotherm for 5 min, (3) Ramp − 20
℃/min to 22 ℃, (4) Ramp 10 ℃/min to 200 /250 ℃, (5) Ramp − 1
℃/min to 22 ℃, (6) Ramp 10 ℃/min to 200/250 ℃, (7) Ramp − 10
℃/min to 22 ℃. All other DSC runs were a ramp at 10 ℃/min to 200/
250 ℃ to assess the material’s characteristics after printing and
annealing steps. Percent crystallinity, Xc , was calculated based on Eq. 1
as follows:
ΔHm − ΔHcc
Xc = (1)
ΔHf ⋅w
Here, ΔHf is the enthalpy at 100 % crystallinity, ΔHcc is the enthalpy
of cold crystallization for the TCPC, ΔHm is the enthalpy for melting for
the TCPC, and w is weight fraction of polymer in the TCPC. ΔHm and Δ
Hcc were determined from the DSC characterization with the TA Uni­
versal Analysis software. The values used for ΔHf for PLA is 93 J/g and
for PA6 is 230 J/g [23,24]. The values used for w for filaments were
based on the TGA measurements and were 0.12 for Cu-PLA and 0.30 for
D.J. Braconnier et al.
Graphite-PA6.
Thermal interface measurement (TIM) testing: A TIM tester from
Analysis Tech (Burlington, MA, USA) was used to characterize the
thermal conductivity of FFF parts manufactured from the two com­
mercial TCPC filaments. Sample sets of 33 mm diameter disks of
different thicknesses were run to determine the thermal conductivity of
the samples. The bottom plate of the TIM tester was actively cooled to a
set point of 18 ℃. The target sample temperature was set to 50 ℃, which
was maintained by the tester actively tuning the elevated temperature of
the top plate. High viscosity silicone oil (Dow Corning 200®, 60,000 cSt,
CAS 63148–62–9, Sigma-Aldrich, Saint Louis, MO, USA) was used as an
interface fluid to ensure even and full contact with both TIM surfaces.
The contact pressure was set to 100 kPa. Each tested formulation con­
sisted of 3 or 4 different sample thicknesses ranging from 0.25 mm to
4.0 mm that were each measured 3 times such that the thermal con­
ductivity was determined from 9 to 12 individual tests, as shown in
Fig. 3. The TIM tester was used to determine both the weak axis and the
strong axis thermal conductivities of FFF parts (Fig. 3). For weak axis
measurements, simple 33 mm diameter disks could be printed according
to the process described in Section 2.2 , with the disk’s circular face
parallel to the build plate. For strong axis measurements, large cylinders
(extrusions of a 33 mm disk) oriented with the disk’s circular face
perpendicular to the build plate were printed then cut with a bandsaw
into three disks of increasing thicknesses. These cut disks were sanded
smooth prior to TIM testing.
2.4. Structural characterization
Scanning Electron Microscopy (SEM): SEM Micrographs were ob­
tained from a S-4800 SEM (Hitachi, Japan). All samples were sputter-
coated in 12 nm of platinum prior to imaging. Cross-sections of all
samples were embedded in EpoFix epoxy resin (Struers ApS, Denmark)
and polished prior to sputter coating. Micrographs of samples pre- and
post-annealing were collected at a probe current of 7 µA and an accel­
eration voltage of 12 kV to investigate the physical changes to the inter/
intra-layer interfaces within each printed part.
Fig. 3. Weak axis samples include all FFF interfacial defects within the TIM testing direction. Strong axis samples provide a set of continuous print beads along the
direction of TIM testing.
4
Additive Manufacturing 89 (2024) 104265
2.5. Heatsink testing
The application of both Cu-PLA and Graphite-PA6 as TCPC feedstock
for FFF processable heatsinks was tested using a custom benchtop
heatsink testing setup (see Fig. 4). The setup is a benchtop wind tunnel
that can flow laminar air across a heatsink that is affixed to the heating
side of a TEC1–12706 12 V 6 A Peltier plate (HiLetgo, China). K-type
thermocouples (Omega, Norwalk, CT, USA) are embedded between the
heatsink and the Peltier heating element to track local temperature. The
system was controlled by a Raspberry Pi 2B (“RPi”) connected to a
Robogaia Temperature Controller Relay, Waveshare 4-CH Current/
Voltage/Power Monitor HAT, Waveshare BME280 Environmental
Sensor, and Neem Tech Octo K-Type MAX31855 Thermocouple
Breakout Board. The Robogaia relay was programed to turn on and off
the HiLetgo TEC1–12706 40×40 mm Peltier plate heat source and the
Noctua NF-A12×25 5 V 120 mm fan. The Waveshare Monitor HAT was
used to record the input voltages and current. The thermocouple
breakout board was used to measure the temperature from the
embedded thermocouple pad between the bottom of the heatsink sam­
ple and the heat source. The environmental sensor was mounted to the
outside of the heatsink testing chamber and was used to measure
ambient temperature, humidity, and air pressure. The enclosure and
diffuser were printed via FFF out of 2.85 mm Natural PETG filament
(IC3D Inc., Hilliard, OH, USA). The diffuser was designed to take in the
forced air from the 120 mm fan and funnel the flow into a near laminar
flow prior to hitting the heatsink chamber. An aluminum mesh with
1 mm perforations was used to further ensure the directionality and
diffusion of the air flow from the fan. The temperature difference, ΔT,
between the embedded thermocouple pad and the ambient temperature
thermocouple was monitored over the course of a testing run.
To test a heatsink, the following protocol was followed: (i) the
heatsink was affixed to the Peltier heating element using PK-3 Thermal
Compound (Prolimatech Inc., Taiwan) and a mounting bracket; (ii) the
benchtop wind tunnel was closed and allowed to equilibrate at ambient
(~ 25 ℃) for 1 minute; (iii) the Peltier heating element was then fully
powered at 5 V until the temperature reached a steady-state; (iv) the fan
D.J. Braconnier et al. Additive Manufacturing 89 (2024) 104265

Fig. 4. a) A schematic of the heatsink tester used to measure the steady-state passive and active cooling performance values of the printed heatsinks. b) Schematic
depicting the strong axis and weak axis print orientations for the printed heatsinks. c) Example temperature output for a machined aluminum heat sink test. Passive
and active cooling values were determined when the slope the temperatures remained constant for 240 seconds.

was then turned on to apply active convection – and the temperature
decrease was monitored until the system again reached steady-state; (v)
finally, the heat source was powered off and the temperature was
monitored until the fan cooled the system back down to ambient.
Steady-state conditions were determined when the slope of temperature
across 240 seconds worth of data reached zero. Cu-PLA and Graphite-
PA6 heat sinks were printed in two orientations depicted in Fig. 4
including a strong-axis orientation (print beads parallel with the heat­
sink fins) and a weak-axis orientation (print beads perpendicular with
the heatsink fins). All heatsinks were tested in the as-printed state and
after being annealed. A test with an aluminum heatsink of the same
dimensions and surface topography was also run for comparison. The
chosen heatsink geometry had five straight fins that were 3 mm thick
separated by gaps of 5 mm, centered on a 3 mm thick substrate. The heat
sink filled a cubic build envelope that was 40 mm on each side. The final
weights of the heat sinks were 126.0 g (Cu-PLA), 40.2 g (Graphite-PA6),
and 72.4 g (machined aluminum).
3. Results
3.1. Initial characterization of commercial TCPCs
The DSC baseline procedure (Section 2.3 ) was performed on the as-
received Cu-PLA and Graphite-PA6 filaments to characterize the thermal
properties of the polymeric matrices. The glass transition (Tg ), crystal­
lization (Tc ), and melt (Tm ) temperatures as well as the percent crys­
tallinities (Xc ) for a − 20 ℃/min and − 1 ℃/min cooling rate are
reported below in Table 1 (n=3). Next, the filaments were printed with
printing conditions as described in Section 2.2 . These “as-printed” parts
were subjected to DSC testing in which a 10 ℃/min single ramp up was
run on the parts to characterize Tg , Tc , Tm , and Xc , as reported in Table 1.
For the Cu-PLA filament, minimal changes in the phase change tem­
peratures are observed before and after printing. On the other hand, the
Graphite-PA6 filament exhibits over a 10 ◦ C change in Tg and Tc after the
printing process.
In both Cu-PLA and Graphite-PA6 filaments, significant changes to
the percent crystallinity (Xc ) were observed depending on the processing
conditions. Cu-PLA subjected to a − 20 ℃/min “fast cool” from melt at
200 ℃ to 22 ℃ was found to have no crystallinity (Xc = 0.0 %). In
contrast, a − 1 ℃/min “slow cool” resulted in a significant crystallinity
increase to a Xc = 27.3 %. Further, when the Cu-PLA filament was
printed, the as-printed percent crystallinity was Xc = 5.6 %. For
Graphite-PA6, both a “fast cool” and a “slow cool” resulted in the sig­
nificant Xc values of 47.7 % and 54.6 %, respectively. The as-printed
Graphite-PA6 showed a decreased crystallinity of Xc = 34.4 %.
In addition, the degradation temperatures for Cu-PLA and Graphite-
PA6 were assessed using TGA (data supplied in Supplementary Infor­
mation). Degradation in Cu-PLA had an onset at 230 ℃ and peak at 260
℃. The Cu-PLA was found to extrude well at 240 ℃ during printing,
which raised the concerns of degradation occurring. However, no
degradation was observed during printing of Cu-PLA at these higher
extrusion temperatures likely because the printing nozzle creates an
oxygen deprived environment for the melted composite, and because the
time at elevated temperature is less than 1 minute. Degradation in
Graphite-PA6 had an onset at 420 ℃ and a peak at 450 ℃, well above
the print nozzle temperature.

Table 1
Thermal Phase Characteristics of Polymeric Components of Tested TCPCs.
Material Condition Tg (℃) Tc (℃) Tm (℃) Xc (%) after − 20 ℃/min Xc (%) after − 1 ℃/min Xc (%) after printing

Cu-PLA As-received 62 ± 2 112 ± 9 170 ± 1 0.0 27.3 -

As-printed 64 100 170 - - 5.6
Graphite-PA6 As-received 49 ± 0.5 169 ± 7 195 ± 0.8 47.7 54.6 -
As-printed 60 146 196 - - 34.4

5
D.J. Braconnier et al.
3.2. Effect of printing conditions on microstructure and resultant thermal
conductivity
Within the Simplify3D software, there are over 150 directly
controllable printing variables including extrusion temperature, bed
temperature, print speed, z-offset, flow rate (extrusion multiplier), print
orientation, nozzle diameter, infill patterns, outline overlap percentage,
fan speed, and many others. Such a variable space can obfuscate causal
dependencies [25,26]. Since the focus of this effort was to investigate
the role that thermal post-processing steps play in thermal conductivity,
a limited set of conditions were studied to determine their effect on the
resultant microstructure and thermal conductivity. Inter-layer and
intra-layer welding of extrudate, as well as print orientation, are ex­
pected to be key variables that influence the part’s resulting thermal
conductivity. Inter-layer and intra-layer interfaces are characterized by
the extent of wetted contact area, and the extent of molecular reptation
across that interface [16,27,28]. These interface characteristics can be
affected by time, temperature, and contact pressure, which are driven by
print parameters such as extrusion rate, layer height, nozzle tempera­
ture, time per layer, bed temperature, chamber temperature, and z-offset
parameter.
While tuning print conditions, an informative dependency was
observed between the part thermal conductivity and the z-offset
parameter. The z-offset parameter is the distance between the pro­
grammed z-axis origin and the physical z-axis origin as calibrated from
the true print bed position. The z-offset parameter can be leveraged to
produce different part densities within the first two layers of a print by
providing too little or too large of a layer envelope for the extrudate to
fill. A smaller z-offset can better weld extruded print beads while also
delivering higher shear that can cause micro-structure change to the
particle-filled filaments used in this work. A higher z-offset can lead to
weaker inter-layer and intra-layer welding in the first few layers. Given
the flow rate was held constant and the same amount of material was
extruded every time, a calculated print density percentage, φ, was
determined based on the designed volume of the printed part, Vd , rela­
tive to the actual volume of the printed part, Va , as changed by the z-
Fig. 5. a) Schematics and scanning electron micrographs of printed specimen cross-sections printed with different φ values. b) Plotting of the weak axis thermal
conductivity of samples with different φ values. c) Schematic of weak axis and strong axis TIM measurement. d) Measured thermal conductivity for weak axis and
strong axis samples for Cu-PLA and Graphite-PA6. Graphite-PA6 exhibits large anisotropy.
6
Additive Manufacturing 89 (2024) 104265
offset, Zoffset , according to:
Vd td Ad
φ= =( ) (2)
Va td + Zoffset Ad
Here, td is the designed thickness of the sample and Ad is the area of
each layer which remains the same between the Vd and Va .
The discovered linear relationships between thermal conductivity
and average print density percentage for Cu-PLA and Graphite-PA6
sample sets are shown below (Fig. 5a, b). Across both materials sets,
lower z-offsets delivered higher average print densities which are
correlated with higher thermal conductivities. Cu-PLA samples that
were printed with the z-offset that corresponded to a print density of
100 % exhibited occasional voids in the material (seen clearly in
Fig. 5a). Instead, Cu-PLA samples printed with a negative z-offset, which
provides a calculated print density of 121 % had a surface microstruc­
ture that lacked voids and an internal structure that was denser than the
near 100 % print density sample. Graphite-PA6 prints with a calculated
print density of 89 % had a lower thermal conductivity than parts with
100 % print density. However, this negative z-offset height is ultimately
a detriment to the print accuracy of a final part. As such, further results
in this study are all based on a z-offset that corresponds to calculated
print densities of 100 %.
Next, the effect of print orientation on thermal conductivity was
investigated. TIM disks described in Section 2.3 in both the weak-axis
orientation and the strong-axis orientation were printed (Fig. 5c). As
seen in Fig. 5d, the thermal conductivity of the Cu-PLA disks that were
printed with the weak-axis in the direction of TIM testing was 0.68 W/
m⋅K, while the strong axis was 0.89 W/m⋅K. The strong-axis therefore
exhibited a 31 % higher thermal conductivity than the weak axis. This
anisotropy was higher in Graphite-PA6 samples. TIM disks made from
Graphite-PA6 that had their strong axis along the thermal testing di­
rection exhibited a thermal conductivity of 2.51 W/m⋅K, while the
weak-axis samples tested at 0.56 W/m⋅K. Therefore, the strong axis
orientation was 348 % greater than the weak axis orientation.
D.J. Braconnier et al. Additive Manufacturing 89 (2024) 104265

3.3. Effect of annealing conditions on thermal conductivity
To uncover the effect that various annealing conditions have on the
thermal conductivity of printed parts, a design of experiments was
created that included several annealing temperatures and times for both
Cu-PLA and Graphite-PA6 printed parts. Anneal temperatures of 100 ℃,
135 ℃, and 170 ℃ were investigated with annealing times ranging from
0 to 14 hours. For consistency all sample sets were printed with a z-offset
that corresponded to a calculated part density of 100 % and in the weak
axis orientation. The weak axis orientation is used for easier printing and
faster iteration. Across all conditions tested, annealing at 135 ℃ for
6 hours produced the most compelling microstructural changes in both
Cu-PLA and Graphite-PA6. All annealing results are provided with dis­
cussion in Supplementary Information. For the case of 135 ℃, the
microstructure of Cu-PLA and Graphite-PA6 4-layer print samples pre-
and post-annealing were cross-sectioned and imaged with SEM as shown
in Fig. 6. Interfaces (circled in red) are shown to decrease in severity
with increased annealing time.
Cu-PLA samples annealed at 135 ℃ for 6 hours experienced an in­
crease in weak-axis thermal conductivity to a saturated value of 0.85 W/
m⋅K, which represents a 29 % increase from the as-printed weak axis
conductivity (0.66 W/m•K). Further annealing to 14 hours produced no
further measurable increase. A similar trend was observed for Graphite-
PA6 samples. The weak-axis thermal conductivity of Graphite-PA6
samples annealed at 135 ℃ for 6 hours increase from 0.58 W/m⋅K to
0.66 W/m⋅K, which represents a 14 % increase. For comparison, hot-
rolled samples were also produced (described in Section 2.3) to under­
stand thermal conductivities of samples without print interfaces. Both
material types have hot-rolled thermal conductivities well above the
measured values for printed specimens. Cu-PLA hot-rolled specimens
measured 42 % larger than printed and annealed Cu-PLA specimens.
Graphite-PA6 hot-rolled specimens measured 27 % higher than printed
and annealed Graphite-PA6 specimens. Although printed samples do not
match or exceed hot-rolled conductivity, annealing appears to improve
thermal conductivity from as-printed values toward hot-rolled values.
Further, annealing at the temperatures considered here did not lead to
measurable changes in geometry due to effects like thermal sagging.
3.4. Effect of crystallinity on thermal conductivity
Both the PLA and the PA6 matrices within each of the composites
herein are semi-crystalline. As represented in Fig. 7a, crystallites have
been shown to improve transfer of phonons relative to amorphous
polymers by increasing the order and the rigidity of atomic bonds
through a material. Crystallinity in the tested TCPCs can be tuned by
bringing the part temperature toward Tm and then either cooling slowly
to maximize the formation of crystallites or cooling fast to minimize
crystallite formation. Crystallinity was considered first for hot-rolled Cu-
PLA samples to isolate the variable of crystallinity from the effects of
printing and filler anisotropy. Fig. 7b shows the resulting thermal con­
ductivity of hot-rolled Cu-PLA samples (all at 50 vol% Cu isotropic filler)
with different levels of crystallinity (diamonds) plotted over Lewis-
Nielsen percolation models (L-N, solid lines) for each recorded crystal­
linity (Xc) value (see Supplementary Information for details). Lewis-
Nielsen models can show the role that percolation plays in thermal
conductivity relative to effective medium theory models (e.g. the
Maxwell model, dashed line) [29,30]. The crystallinity of each sample
set was determined with DSC according to Eq. 1. Plotting the PLA matrix
crystallinity in these hot-rolled samples against the composite thermal
conductivity, as shown in Fig. 7c, further highlights the positive corre­
lation that increasing crystallinity has on composite thermal conduc­
tivity. To determine if these correlations also exist in printed specimens
that have interlayer interfaces, weak axis Cu-PLA and Graphite-PA6
prints across all tested annealing conditions were characterized for
crystallinity and thermal conductivity and are plotted in Fig. 7d. There is
a positive correlation between crystallinity and thermal conductivity
across all weak-axis printed samples for both Cu-PLA and Graphite-PA6.
Considering this data for printed Cu-PLA, Lewis-Nielsen behavior was

Fig. 6. a) Schematic depicting how annealing at a temperature well above the Tg and below the Tm of the TCPC matrix can heal many inter-layer and intra-layer
interfaces. b) Scanning electron micrographs of printed specimen cross-sections to reveal existence of inter-layer interfaces (circled in red; dark regions that are
not circled are cavities from particles that were extracted during polishing). Inter-layer interfaces decrease in severity with increased annealing time at 135 ◦ C for
both Cu-PLA and Graphite-PA6. c) TIM measurements were conducted at 0 hr, 2 hr, and 6 hr marks during the annealing process. The thermal conductivity of both
Cu-PLA and Graphite-PA6 subjected to annealing was found to increase from as-printed values, but remain below hot-rolled values.

7
D.J. Braconnier et al. Additive Manufacturing 89 (2024) 104265

Fig. 7. a) Schematic comparing bonding schemes in regions of amorphous (less ordered bonds) and crystalline (ordered, stiffer bonds) TCPC matrix that affect the
efficiency of the phononic transfer of heat. b) Thermal conductivity of hot-rolled Cu-PLA post-processed with different cooling rates to achieve variations in crys­
tallinity (diamonds) plotted against Lewis-Nielsen percolation models (solid lines). c) Fixing the volume fraction of Cu particles at 50 vol%, the increasing thermal
conductivity of samples with higher crystallinity also follows the Lewis-Nielsen percolation model. d) Plotting the thermal conductivity and percent crystallinity of
weak axis samples subjected to several annealing conditions reveals a positive correlation despite the existence of interlayer interfaces, n=4. e) Comparison between
weak axis and strong axis prints for Cu-PLA and Graphite-PA6 samples which exhibit maximum crystallinity achieved through very slow cooling rates.

Fig. 8. Performance testing of FFF printed heat sinks under passive and active cooling. A machined aluminum heatsink is also tested as a comparison. The best
performing FFF printed heat sink made of strong axis Graphite-PA6 reached equilibrium temperatures less than 5 ℃ over the aluminum heat sink for the tested
heating load. The temperature reached without a heat sink is shown by the dotted line (n=3).

8
D.J. Braconnier et al.
not evident. Despite post-treatments that increase crystallinity in printed
Cu-PLA samples to nearly 50 %, weak axis conductivity remained below
1 W/m⋅K. When compared with the higher conductivities measured for
hot-rolled Cu-PLA, these results supported earlier observations that in­
terfaces and voids in printed samples strongly limit composite conduc­
tivity (seen in Fig. 6).
Next, the effect of part orientation coupled with high crystallinity
was investigated. Weak axis and strong axis parts were printed,
annealed, and subjected to a final slow cooling rate to produce
maximum crystallinity (Fig. 7e). Strong-axis Cu-PLA parts exhibited
0.87 W/m⋅K, while the most crystalline weak axis Cu-PLA parts ach­
ieved 0.85 W/m•K. This nominal change was a stark difference from the
effect observed in Graphite-PA6. Weak axis Graphite-PA6 samples with
maximum crystallinities of ~60 %, exhibited thermal conductivities of
0.68 W/m⋅K. Instead, strong-axis Graphite-PA6 samples that were
slowly cooled exhibited thermal conductivities of 6.36 W/m⋅K. This
strong axis value is 9.35 times (or +835 %) the weak axis value. This
value rivals common commercial thermal pastes used in thermal man­
agement devices [31]. Further, this measured value is well-above the
supplied commercial technical data sheet for these printed parts [32].
3.5. Performance testing of FFF printed heat sinks
To assess material performance in a relevant application test, 5-fin
heatsink geometries of both Cu-PLA and Graphite-PA6 were printed in
both strong axis and weak axis print orientations (shown schematically
in Fig. 4) with printed part results shown in two orientations in Fig. 8.
The heat sinks printed with both Cu-PLA and Graphite-PA6 exhibited
geometries of satisfactory accuracy relative to the designed geometry.
As is commonly observed, the FFF printed heat sinks showed striated
texturing from the print beads along the print direction. Each of the
weak axis and strong axis printed heatsinks were tested both in the as-
printed state and after thermal post-processing in which the heat sinks
were annealed and slow-cooled to maximize crystallinity, as explained
in the previous sections. Of note, no changes to part geometry, including
shrinkage or warpage, were observed during the annealing process,
which has been previously noted for injection molded parts [33]. In
addition, a test run with an extruded aluminum heatsink of the same
shape and dimensions was considered. The aluminum heatsink exhibi­
ted a surface waviness that approximated the striated texturing of the
FFF printed heat sinks.
All heatsink performances were measured with the procedure
detailed in Section 2.5 and are shown in Fig. 8. Across all tested heat
sinks, clear trends were observed between the measured intrinsic ther­
mal conductivity of the material and the maximum temperature rise
measured between the heating element and the heat sink. Temperature
rise is reported in degrees Kelvin above ambient. The machined
aluminum heat sink with an intrinsic thermal conductivity of 237 W/
m⋅K achieved the lowest temperature rise of ΔT = +48K with the
convective cooling fan turned off and ΔT = +28K with the convective
cooling fan turned on. CU-PLA heat sinks in strong and weak axis ori­
entations exhibited temperature rises of around ΔT = +59K with the
convective cooling fan turned off for all print orientations in as-printed
and post-processed configurations. These CU-PLA heat sinks achieved
reduced ΔT’s between +42K and + 44K, with the convective cooling
fan turned on. Graphite-PA6 heat sink performance tests appeared to
depend strongly on print orientation. In the weak axis orientation, both
as-printed and thermally post-processed Graphite-PA6 heat sinks
exhibited a ΔT ≈ +65K with the convective cooling fan turned off and
ΔT ≈ +52K with the convective cooling fan turned on. In comparison,
as-printed Graphite-PA6 heat sinks in the strong axis orientation
exhibited a ΔT ≈ +51K with the convective cooling fan turned off and
ΔT ≈ +34K with the convective cooling fan turned on. These temper­
ature rises were further reduced upon thermal post-processing of the
Graphite-PA6 heat sinks down to ΔT ≈ +50K and ΔT ≈ +31K with and
without the convective fan, respectively. These lower temperature rises
9
Additive Manufacturing 89 (2024) 104265
of thermally post-processed Graphite-PA6 heat sinks with strong axis
orientation were within 11 % of the measured temperature rise of the
machined aluminum heat sink.
4. Discussion
4.1. Effects of filler in FFF filaments
In this work, two commercial filament materials were investigated
that both contained ~50 vol% of particle filler. Previous work has
established that the volume percent of filler has a large effect on thermal
conductivity, with higher volume fractions of filler leading to higher
thermal conductivity. At lower volume fractions, thermal conductivity
with isotropic fillers such as the Cu particles in Cu-PLA increases with
volume fraction according to effective medium theory models (e.g. the
Maxwell model). These models do not incorporate percolation and are
not considered valid above ~30 vol% filler. Instead, the Lewis-Nielsen
model has been implemented to incorporate percolation as particles
approach close-packed configurations. The outcomes of these two
models are shown against the hot-rolled Cu-PLA sample conductivity in
Fig. 7b (assuming the copper particles have a conductivity of 400 W/
m⋅K and the PLA has an amorphous conductivity of 0.18 W/m⋅K and a
crystallite conductivity of 0.91 W/m⋅K). Comparing this effective me­
dium theory prediction to the measured hot-rolled Cu-PLA values sug­
gest that percolation is occurring in the Cu-PLA system and is better
described by a Nielsen model that incorporates a percolation condition
near the maximum packing fraction for the given particle geometry (see
Supplementary Information for detailed calculations and assumptions).
This suggests that the Cu-PLA system was formulated near the percola­
tion threshold. Of note, rheology responds in non-linear ways around the
percolation threshold, with particle jamming and interactions signifi­
cantly increasing molten filament viscosities. Such dependencies create
a relatively small design window to produce printable and highly filled
FFF filaments likely resulting in similar commercial offerings despite
disparate particle morphologies. The comparison of the Lewis-Nielsen
model was limited to the Cu-PLA system as the particle anisotropy of
the graphite flakes within the Graphite-PA6 introduces additional pa­
rameters within the Lewis-Nielsen model that require systematic vali­
dation not possible with a commercial material system. Likely, a
combination of phenomena (discussed below) is required to explain the
strong increase in thermal conductivity of the strong axis Graphite-PA6
system.
Similar particle loading in the two filaments was somewhat seren­
dipitous allowing for a more direct comparison of the role played by
particle morphology. As seen in Fig. 5d, a clear difference between the
two commercial filaments lies in the strongly anisotropic nature of the
graphitic flake based Graphite-PA6 system relative to the isotropic na­
ture of the Cu-PLA system containing spherical copper particles. Two-
dimensional fillers align along the print direction in the shear flows
characteristic of the extrusion in the FFF process both in the nozzle and
between the nozzle and the prior print layer [34,35]. In such a shear
flow, flakes will experience a fluidic velocity gradient across their sur­
face. By orienting the flake’s long axis perpendicular to this gradient
(and parallel to the flow direction), the hydrodynamic energy is mini­
mized [36]. Though the small velocity gradient that remains leads to
occasional particle tumbles known as Jeffrey orbits [37], the
time-averaged orientation of the flakes remains predominantly aligned
with the flow direction. Thus, the long axes of the graphitic flakes will be
mostly oriented along the print direction. This anisotropic orientation
during the printing process is compounded with the intrinsic anisotropy
of the graphitic flakes which showcase ~2000 W/m⋅K thermal con­
ductivity along the basal plane (along the long axis, [38]) and over two
orders of magnitude less conductivity through the basal plane. The
coupled orientation of the flakes with the high intrinsic conductivity of
the basal plane produces a high thermal conductivity in the strong axis
and a relatively modest thermal conductivity in the weak axis. Another
D.J. Braconnier et al.
contributing factor here is the role of interlayer interfaces (discussed
below). Meanwhile, in the Cu-PLA system, the spherical copper particles
are less likely to show orientability within shear flows. Further, the
copper particles themselves are generally polycrystalline showcasing an
intrinsic thermal conductivity that is isotropic. Despite the printing
process creating anisotropy in interlayer interfaces along the heat flow
direction, both the weak and strong axes of the Cu-PLA system measure
similarly.
4.2. Effects of inter-layer and intra-layer interfaces from FFF process
Poor printing conditions can result in significant porosity and
increased resistance, especially along inter-layer interfaces. These con­
ditions can be seen in the samples with low calculated print density
percentage (φ) in Fig. 5b and in comparing Figs. 1a and 1b. Optimizing
printing conditions can reduce the thermal resistance of these inter-layer
interfaces and increase thermal conductivity of printed parts even by
30–50 %. Even with tuned printing conditions, inter-layer and intra-
layer interfaces will remain. As shown in Fig. 1, the orientation of a
part during the FFF process changes the amount of inter-layer and/or
intra-layer interfaces which affects the thermal conductivity of the end
part. The role of inter-layer interfaces can be investigated by considering
the weak axis orientation (maximum inter-layer interfaces) compared to
the strong axis orientation (minimum inter-layer interfaces). For the Cu-
PLA, as seen in Fig. 5d, there was a surprisingly small effect with the
strong axis only exhibiting a 31 % increased thermal conductivity
relative to the weak axis. The role of inter-layer interfaces was obfus­
cated in the Graphite-PA6 system since the orientation of the graphitic
flakes was coupled to the thermal conductivity as described above.
The role of inter-layer interfaces can be further understood by
considering the hot-rolled and annealing results in Fig. 6 and Fig. 7. The
hot-rolled values represent the ceiling value of weak axis thermal con­
ductivity when no inter-layer interfaces exist. These values are well
above the achieved printed and annealed weak axis values suggesting
that inter-layer and intra-layer resistances exist across all printed spec­
imens even after annealing. Still, annealing below Tm led to a reduction
in voids (as evidenced in Fig. 6b) and increases the weak axis thermal
conductivity of a printed part by 29 % and 14 % for Cu-PLA and
Graphite-PA6, respectively. The added step of annealing parts is
straight-forward and requires simple ovens, making this a valuable step
for many implementations. Annealing above Tm, further reduces the
inter-layer and intra-layer interfacial resistances, but also results in
thermal sagging, as shown in Fig. 1d, resulting in major loss to geometric
accuracy. Stabilizing printed parts during annealing above Tm may be a
fruitful research direction that parallels prior studies focused on me­
chanical outcomes that implemented shells or dual-material filaments
[39–42].
4.3. Effects of crystallinity
Polycrystalline thermoplastic polymers like PLA and PA6 form
crystallites depending on the thermal processing of these materials. FFF
printing delivers a complex thermal process to polycrystalline thermo­
plastic polymers that can drive anisotropy and heterogeneity in crys­
tallinity [43]. Prior work has demonstrated statistical but nominal
improvements to the thermal conductivity of PLA and PA6 by increasing
the amounts of crystallinity in these systems [17,18,44]. As seen in
Fig. 7d, the weak axis thermal conductivity of the Cu-PLA system
increased by ~20 % as the crystallinity content went from ~5 % to
~50 %. Such an increase can be predicted using effective medium the­
ory models. Similarly, the weak-axis of the PA6 system increased by
~15 % as crystallinity content went from 32 % to 58 %, consistent with
prior findings. In both cases, the crystallites appear to be increasing the
thermal conductivity as a bulk effect, and not creating percolation or
reducing phononic dispersion at particle-matrix interfaces. A similar
trend holds for the strong axis Cu-PLA measurement showcasing an
10
Additive Manufacturing 89 (2024) 104265
isotropic thermal conductivity for the printed part. However, the effect
of crystallization on thermal conductivity within the printed Cu-PLA
system was relatively small, especially in comparison to the higher
conductivities of the hot-rolled specimen. This lower effect of crystal­
linity on the thermal conductivity of printed Cu-PLA was likely due to
the creation of micro-porosity during the printing process which would
limit percolation and increase thermal resistances.
The strong axis measurements of Graphite-PA6 show something
remarkably different. Annealed Graphite-PA6 parts that were slow-
cooled at − 1 ℃/min from 135 ℃ to increase the formation of crystal­
lites within the polymeric matrix exhibited strong axis thermal con­
ductivities of 6.36 W/m⋅K. Likely, the crystallites are forming local to
the particle-polymer interface, allowing for a more effective phononic
transition from the basal planes of the particles or the crystallites are
serving as a phononic bridge between the sidewalls of neighboring
particles. Post-annealing followed by a slow-cooling step is easy to
implement and can achieve thermal conductivities even above the
manufacturer listed values.
Though crystallinity improves thermal conductivity, the FFF printing
process instills cooling rates that are too fast to encourage the growth of
crystallites. Analyzing the measured crystallinity of the as-printed parts
in Table 1, shows that both Cu-PLA and Graphite-PA6, as-printed parts
exhibit reduced levels of crystallization as compared to slowly cooled
melts of these materials. Cu-PLA likely undergoes a cooling rate between
− 1 ℃/min and − 20 ℃/min during the print process and allows for some
formation of spherulites, consistent with prior work on PLA [20,45,46].
The reduced crystallinity in as-printed Graphite-PA6 suggests that the
cooling rate experienced by the extrudate during printing was poten­
tially faster than − 20 ℃/min, which could be in part due to the high
strong axis thermal conductivity of the Graphite-PA6 that would pull
heat quickly through the extrudate dropping the temperature quickly.
Without subsequent annealing and slow-cooling steps, parts made from
Graphite-PA6 would not exhibit properties consistent with those re­
ported in Fig. 7e. The thermal conductivity of a printed part can be
dramatically improved by conducting a facile annealing and slow
cooling post-process. Using a controlled cooling rate to enhance the
thermal conductivity of a TCPC part appears to be an underappreciated
yet facile approach in the field.
In considering formulations for next generation TCPCs, crystallinity
should be a primary consideration. Selecting polymer grades that have
high inherent crystallinity, or formulating with additives to enhance
crystallinity, are strategies that could further enhance conductivity. In
fact, the conductive particles themselves, particularly faceted particles
like graphite, might also encourage polymer crystallization or be func­
tionalized to encourage polymeric crystallization (consistent with pre­
vious work [47]). In all cases, post-processing is essential and printed
parts should be annealed and slow cooled to improve part thermal
conductivities.
4.4. Practical implications for thermal engineering
In this work, the process-structure-property learnings were applied
to produce TCPC heat sinks with FFF that could be measured for per­
formance. Through tuning the printing process, designing the print
paths relative to the part geometry, and conducting optimized thermal
post-processing, application-relevant heat sinks were produced as
shown in Fig. 8. For this design problem, the resulting ΔT for the top-
performing printed heat sink was within a few degrees of a machined
aluminum heat sink. This result is particularly impressive considering
that the printed heat sink was 44 % lighter than the aluminum heat sink.
In addition, because of the geometric freedom afforded by additive
manufacturing, heat sinks produced via FFF could likely outperform the
aluminum heat sink if the fins were topologically designed in more
efficient geometries. FFF heatsinks can be comprised from lattice
structures including protrusions with narrowing fin thicknesses or fine
holes and hollows within the structure to promote convective heat
D.J. Braconnier et al.
transfer. Many of these features would be challenging to implement in
machined aluminum or would add significant cost to fabrication.
Meanwhile FFF can produce geometric complexity with no additional
costs provided the geometry follows the required design guidelines of
the FFF platform.
5. Conclusions
In this work, we uncover key process, structure, property relation­
ships in the fused filament fabrication (FFF) of thermally conductive
polymer composites that can be tuned to improve the abilities of this
manufacturing method and of these composite materials to help address
thermal management challenges in industry. We relied on two disparate
off-the-shelf FFF filaments that exhibited high thermal conductivity and
low batch-to-batch variability. A strong dependency on print quality and
print orientation was shown to affect structural morphologies and
resultant thermal conductivities within the FFF parts. With optimized
printing parameters, the function of low temperature (< Tm , melt tem­
perature) annealing was demonstrated to partially heal inter-layer and
intra-layer defects. Further, the role of crystallinity within the polymeric
matrix was shown to be integral to improvements to the thermal con­
ductivity of the final part. Thermal post-processing both to anneal a
printed part and to tune the crystallization state of the pertaining
polymer matrix greatly increased the thermal conductivity of the ther­
mally conductive polymer composites studied in this work. While
annealing alone produced smaller improvements in thermal conduc­
tivity, print quality, orientation, and crystallinity developed thermal
conductivities within the Graphite-PA6 thermally conductive polymer
composite to rival the performance of an aluminum heatsink tested with
a developed heatsink testing apparatus. This exciting performance
further highlights the potential additively manufactured thermally
conductive parts have for use in thermal management technologies. As
densities and processing complexities become greater considerations in
the development of high energy density electronics, the application of
additively manufacturable thermal solutions can provide answers to
such challenges.
CRediT authorship contribution statement
Randall M. Erb: Writing – review & editing, Writing – original draft,
Supervision, Resources, Project administration, Methodology, Investi­
gation, Funding acquisition, Formal analysis, Data curation, Conceptu­
alization. Daniel J. Braconnier: Writing – review & editing, Writing –
original draft, Visualization, Validation, Methodology, Investigation,
Formal analysis, Data curation, Conceptualization. Eric D. Wetzel:
Writing – review & editing, Resources, Methodology, Investigation,
Funding acquisition, Data curation, Conceptualization. Ryan M. Dunn:
Validation, Methodology.
Declaration of Competing Interest
The authors declare the following financial interests/personal re­
lationships which may be considered as potential competing interests:
Randall Erb reports financial support was provided by Army Research
Office. Randall Erb, Daniel Braconnier, Eric Wetzel, Ryan Dunn has
patent pending to Northeastern University. If there are other authors,
they declare that they have no known competing financial interests or
personal relationships that could have appeared to influence the work
reported in this paper.
Data availability
Data will be made available on request.
11
Additive Manufacturing 89 (2024) 104265
Acknowledgements
We would like to give special thanks to Sandra Chai, Isabella Ste­
panek, and Evan Toth for their help with creating and testing TIM
samples. We would like to thank In-Chul Yeh for providing the PLA
crystallite conductivity value from molecular dynamics simulations.
Research was sponsored by the Army Research Office under Cooperative
Agreement Number W911NF-22–2–0261 and by the DEVCOM Army
Research Laboratory Cooperative Agreement W911NF-20–2–0024. The
views and conclusions contained in this document are those of the au­
thors and should not be interpreted as representing the official policies,
either expressed or implied, of the Army Research Office or the U.S.
Government. The U.S. Government is authorized to reproduce and
distribute reprints for Government purposes notwithstanding any
copyright notation herein.
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.addma.2024.104265.
References
[1] M. Smith. 3D Printing Allows for Complex, High Surface Area Geometries
Optimized for Convection Cooling. Electronics Cooling. 〈https://www.electronic
s-cooling.com/2019/07/3d-printing-allows-for-complex-high-surface-area-geom
etries-optimized-for-convection-cooling/〉 (accessed 2022).
[2] U. Ankalkhope. Design Optimization for Heat Sinks Using nTopology. Excel3D. 〈htt
ps://www.excel3d.com/post/topology-optimization-for-heat-sinks-using-ntop-soft
ware〉 (accessed 2022).
[3] B.J.M. Paudel, Mohammad; Thompson, Scott M., "Multi-Objective Topology
Optimization of Additively Manufactured Heat Exchangers," presented at the Solid
Freeform Fabrication Symposium – An Additive Manufacturing Conference, 2019.
[4] I. Blanco, G. Cicala, G. Recca, and C. Tosto, Specific Heat Capacity and Thermal
Conductivity Measurements of PLA-Based 3D-Printed Parts with Milled Carbon
Fiber Reinforcement, Entropy, vol. 24, no. 5, 〈doi:10.3390/e24050654〉.
[5] A. Gurijala, R.B. Zando, J.L. Faust, J.R. Barber, L. Zhang, R.M. Erb, Castable and
printable dielectric composites exhibiting high thermal conductivity via
percolation-enabled phonon transport, 2020/04/01/, Matter vol. 2 (4) (2020)
1015–1024, https://doi.org/10.1016/j.matt.2020.02.001.
[6] T.J. Quill, et al., Thermal and mechanical properties of 3D printed boron nitride –
ABS composites, Appl. Compos. Mater. vol. 25 (5) (2018) 1205–1217, https://doi.
org/10.1007/s10443-017-9661-1.
[7] G.-W. Lee, M. Park, J. Kim, J.I. Lee, H.G. Yoon, Enhanced thermal conductivity of
polymer composites filled with hybrid filler, 2006/05/01/, Compos. Part A: Appl.
Sci. Manuf. vol. 37 (5) (2006) 727–734, https://doi.org/10.1016/j.
compositesa.2005.07.006.
[8] T. Nguyen, Thermal Conductivity of Filler and Un-filler Materials, in 2022 IEEE
Electrical Insulation Conference (EIC), 19-23 June 2022 2022, pp. 419-423, 〈doi:10.
1109/EIC51169.2022.9833203〉.
[9] T. Flaata, G.J. Michna, T. Letcher, Thermal conductivity testing apparatus for 3D
printed materials, Online]. Available (2017), https://doi.org/10.1115/HT2017-
4856.
[10] C. Shemelya, et al., Anisotropy of thermal conductivity in 3D printed polymer
matrix composites for space based cube satellites, 2017/08/01/, Addit. Manuf. vol.
16 (2017) 186–196, https://doi.org/10.1016/j.addma.2017.05.012.
[11] J.E. Seppala, S. Hoon Han, K.E. Hillgartner, C.S. Davis, K.B. Migler, Weld formation
during material extrusion additive manufacturing, 10.1039/C7SM00950J, Soft
Matter vol. 13 (38) (2017) 6761–6769, https://doi.org/10.1039/C7SM00950J.
[12] C. Zhang, Y. Li, W. Kang, X. Liu, Q. Wang, Current advances and future
perspectives of additive manufacturing for functional polymeric materials and
devices, SusMat vol. 1 (1) (2021) 127–147, https://doi.org/10.1002/sus2.11.
[13] P. Roudný, T. Syrový, Thermal conductive composites for FDM 3D printing: a
review, opportunities and obstacles, future directions, 2022/11/01/, J. Manuf.
Process. vol. 83 (2022) 667–677, https://doi.org/10.1016/j.jmapro.2022.09.026.
[14] X.C. Tong, Advanced Materials for Thermal Management of Electronic Packaging,
Springer, 2011.
[15] K. Hart, R. Dunn, E. Wetzel, Increased fracture toughness of additively
manufactured semi-crystalline thermoplastics via thermal annealing, 12/01,
Polymer vol. 211 (2020) 123091, https://doi.org/10.1016/j.
polymer.2020.123091.
[16] K.R. Hart, R.M. Dunn, J.M. Sietins, C.M. Hofmeister Mock, M.E. Mackay, E.
D. Wetzel, Increased fracture toughness of additively manufactured amorphous
thermoplastics via thermal annealing, 2018/05/23/, Polymer vol. 144 (2018)
192–204, https://doi.org/10.1016/j.polymer.2018.04.024.
[17] C.L. Choy, Thermal conductivity of polymers, 1977/10/01/, Polymer vol. 18 (10)
(1977) 984–1004, https://doi.org/10.1016/0032-3861(77)90002-7.
D.J. Braconnier et al.
[18] H. Chen, et al., Thermal conductivity of polymer-based composites: fundamentals
and applications, 2016/08/01/, Prog. Polym. Sci. vol. 59 (2016) 41–85, https://
doi.org/10.1016/j.progpolymsci.2016.03.001.
[19] C.L. Choy, F.C. Chen, W.H. Luk, Thermal conductivity of oriented crystalline
polymers, 1980/06/01, J. Polym. Sci.: Polym. Phys. Ed. vol. 18 (6) (1980)
1187–1207, https://doi.org/10.1002/pol.1980.180180603.
[20] Y. Jia, Z. Mao, W. Huang, J. Zhang, Effect of temperature and crystallinity on the
thermal conductivity of semi-crystalline polymers: a case study of polyethylene,
2022/08/01/, Mater. Chem. Phys. vol. 287 (2022) 126325, https://doi.org/
10.1016/j.matchemphys.2022.126325.
[21] V. Foundry. Copper Filament(TM). 〈https://shop.thevirtualfoundry.com/produc
ts/copper-filamet?variant=12351243288659〉 (accessed.
[22] TCPoly, Ice9(TM) Rigid, ed, 2019.
[23] B. Wunderlich, Thermal analysis, Boston: Academic Press, 1990.
[24] R.Z. Khoo, H. Ismail, W.S. Chow, Thermal and morphological properties of poly
(Lactic Acid)/nanocellulose nanocomposites, 2016/01/01/, Procedia Chem. vol.
19 (2016) 788–794, https://doi.org/10.1016/j.proche.2016.03.086.
[25] D.J. Braconnier, R.E. Jensen, A.M. Peterson, Processing parameter correlations in
material extrusion additive manufacturing, 2020/01/01/, Addit. Manuf. vol. 31
(2020) 100924, https://doi.org/10.1016/j.addma.2019.100924.
[26] D.M. Braconnier, Kristin, Maynard, Mila, Fabrication and properties of novel
polymer-metal composites using 3D printing, Worcest. Polytech. Inst. (2017).
[27] C.A. Butler, R.L. Mccullough, R. Pitchumani, J.W. Gillespie, An analysis of
mechanisms governing fusion bonding of thermoplastic composites,
J. Thermoplast. Compos. Mater. vol. 11 (1998) 338–363.
[28] F. Yang, R. Pitchumani, Interlaminar contact development during thermoplastic
fusion bonding, 02/01, Polym. Eng. Sci. vol. 42 (2002) 424–438, https://doi.org/
10.1002/pen.10960.
[29] K. Pietrak, T.S. Wiśniewski, A review of models for effective thermal conductivity
of composite materials, J. Power Technol. Vol 95 (No 1) (2015). 〈https://papers.itc.
pw.edu.pl/index.php/JPT/article/view/463〉, 12/23 2014. [Online]. Available.
[30] L.E. Nielsen, The thermal and electrical conductivity of two-phase systems, 1974/
02/01, Ind. Eng. Chem. Fundam. vol. 13 (1) (1974) 17–20, https://doi.org/
10.1021/i160049a004.
[31] A. Gobor. THERMAL COMPOUND GUIDE. EKWB. 〈https://www.ekwb.com/blog/
thermal-compound-guide/#:~:text=A%20thermal%20pad%20with%203W,high
%20grade%20and%20quite%20expensive〉. (accessed 2022).
[32] T. Poly. Technical Data Sheet Ice9™ NYLON. 〈https://tcpoly.com/wp-content/
uploads/2023/11/TDS_NYLON_V5.1.pdf〉 (Accessed 23 November 2023).
[33] T. Tábi, I. Sajó, F. Szabo, A. Luyt, J. Kovacs, Crystalline structure of annealed
polylactic acid and its relation to processing, 10/01, EXPRESS Polym. Lett. vol. 4
(2010) 659–668, https://doi.org/10.3144/expresspolymlett.2010.80.
[34] D.D. Phan, J.S. Horner, Z.R. Swain, A.N. Beris, M.E. Mackay, Computational fluid
dynamics simulation of the melting process in the fused filament fabrication
additive manufacturing technique, 2020/05/01/, Addit. Manuf. vol. 33 (2020)
101161, https://doi.org/10.1016/j.addma.2020.101161.
12
Additive Manufacturing 89 (2024) 104265
[35] B.G. Compton, J.A. Lewis, 3D printing: 3D-printing of lightweight cellular
composites, 6043-6043, 2014/09/01, Adv. Mater. vol. 26 (34) (2014), https://doi.
org/10.1002/adma.201470235.
[36] J. Lin, X. Ku, Fiber orientation distributions in a suspension flow through a parallel
plate channel containing a cylinder, 2009/06/01, J. Compos. Mater. vol. 43 (12)
(2009) 1373–1390, https://doi.org/10.1177/0021998308105424.
[37] G.B. Jeffery, L.N.G. Filon, The motion of ellipsoidal particles immersed in a viscous
fluid, 1997/01/01, Proc. R. Soc. Lond. Ser. A, Contain. Pap. A Math. Phys.
Character vol. 102 (715) (1997) 161–179, https://doi.org/10.1098/
rspa.1922.0078.
[38] A.A. Balandin, D.L. Nika, Phononics in low-dimensional materials, 2012/06/01/,
Mater. Today vol. 15 (6) (2012) 266–275, https://doi.org/10.1016/S1369-7021
(12)70117-7.
[39] R.M. Dunn, K.R. Hart, E.D. Wetzel, Improving fracture strength of fused filament
fabrication parts via thermal annealing in a printed support shell, 2019/09/01,
Prog. Addit. Manuf. vol. 4 (3) (2019) 233–243, https://doi.org/10.1007/s40964-
019-00081-x.
[40] M. Pugatch, et al., Accelerated annealing of fused filament fabricated (FFF)
thermoplastics via an improved core–shell filament, 2023/08/19, Sci. Rep. vol. 13
(1) (2023) 13538, https://doi.org/10.1038/s41598-023-40855-6.
[41] K.R. Hart, R.M. Dunn, E.D. Wetzel, Tough, additively manufactured structures
fabricated with dual-thermoplastic filaments, 2020/04/01, Adv. Eng. Mater. vol.
22 (4) (2020) 1901184, https://doi.org/10.1002/adem.201901184.
[42] B. Koker, et al., Enhanced interlayer strength and thermal stability via dual
material filament for material extrusion additive manufacturing, 2022/07/01/,
Addit. Manuf. vol. 55 (2022) 102807, https://doi.org/10.1016/j.
addma.2022.102807.
[43] S. Petersmann, P. Spoerk-Erdely, M. Feuchter, T. Wieme, F. Arbeiter, M. Spoerk,
Process-induced morphological features in material extrusion-based additive
manufacturing of polypropylene, 2020/10/01/, Addit. Manuf. vol. 35 (2020)
101384, https://doi.org/10.1016/j.addma.2020.101384.
[44] L. Bai, X. Zhao, R.-Y. Bao, Z.-Y. Liu, M.-B. Yang, W. Yang, Effect of temperature,
crystallinity and molecular chain orientation on the thermal conductivity of
polymers: a case study of PLLA, 2018/07/01, J. Mater. Sci. vol. 53 (14) (2018)
10543–10553, https://doi.org/10.1007/s10853-018-2306-4.
[45] M.L. Di Lorenzo, C. Silvestre, Non-isothermal crystallization of polymers, 1999/
08/01/, Prog. Polym. Sci. vol. 24 (6) (1999) 917–950, https://doi.org/10.1016/
S0079-6700(99)00019-2.
[46] A. Keller, M.J. Machin, Oriented crystallization in polymers, 1967/03/01,
J. Macromol. Sci., Part B vol. 1 (1) (1967) 41–91, https://doi.org/10.1080/
00222346708212739.
[47] J.L. Faust, G.A. Winter, M.L. Minus, R.M. Erb, Polypropylene crystallization at an
alumina interface using single walled carbon nanotubes, 2019/05/01/, J. Colloid
Interface Sci. vol. 543 (2019) 9–16, https://doi.org/10.1016/j.jcis.2019.02.020.