Synthesis and characterization of graphene

filled PC-ABS filament for FDM applications

Cite as: AIP Conference Proceedings 2057, 020039 (2019); https://doi.org/10.1063/1.5085610
Published Online: 11 January 2019

Vijay Tambrallimath, R. Keshavamurthy, D. Saravanbavan, G. S. Pradeep Kumar, and M. Harish Kumar

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© 2018 Author(s).
Synthesis and Characterization of Graphene Filled PC-ABS
Filament for FDM Applications
Vijay Tambrallimath1, a) R. Keshavamurthy2, b) D. Saravanbavan 3, G. S. Pradeep
Kumar 4 and M. Harish Kumar 5
1
Department of Automobile Engineering, Dayananda Sagar College of Engineering, Bangalore 560078, India
2
Department of Mechanical Engineering, Dayananda Sagar College of Engineering, Bangalore 560078, India
3
Department of Mechanical Engineering, Dayananda Sagar University, Bangalore 560078, India
4,5
Department of Mechanical and Automobile Engineering, Christ University, Bangalore 560074, India
a)
vijay.tambrallimath@gmail.com
b)
keshavamurthy.r@gmail.com

Abstract. Present investigation focuses on development of graphene filled PC-ABS filament for Fused Deposition
Modeling applications. Compounding and twin screw extrusion was employed to synthesis graphene filled FDM filament
of 1.75mm diameter. Percentage of graphene was varied from 0.1 vol% to 0.25 vol% in steps of 0.05. Developed
filaments were subjected to SEM studies, dimensional accuracy and density measurements. In order to achieve filament
of 1.75mm diameter, filament extrusion temperature was optimized using Taguchi’s L25 orthogonal array, microstructure
shows homogeneous dispersion of graphene particles in PC-ABS matrix, density decreases with increased content of
graphene particles

INTRODUCTION

Fused Deposition Modeling (FDM), is a form of widely used Additive Manufacturing (AM) process that uses
numerous kinds of polymers depending on required properties and applications. FDM uses the nature way of
building up of materials layer by layer, this cause’s large reduction in waste and enhancement of productivity. This
method of manufacturing shows a great potential for growth to contend with conventional manufacturing process
[1]. Some of the commonly used filaments are Acrylonitrile Butadiene Styrene (ABS), Polylactic Acid (PLA),
Polyamide (Nylon) and Polyethylene Terephthalate (PET). The usage of these materials has been vastly
implemented in automotive, medical, aerospace and construction sectors. However, the use of composite polymers in
FDM is an opening area for exploration, which gives an upper hand advantages in terms of superior mechanical
properties, flexibility, enhanced strength and thermal properties depending on the kind of filler being used [2]. The
properties of the developed composite filament are greatly influenced by the characters of the filler material. The
advantages of using nano fillers are way greater than micro fillers. Surface to volume ratio, reduced attraction
between fillers and strong bonds between the matrix is noticeable when nano filler is used. However, formation of
polymer network, the nanoscale filler and interfacial region are the main identities for improvisation of desired
properties of the polymer composite [3].
The importance of Additive Manufacturing (AM) and its advantages over conventional manufacturing process is
elaborately discussed in this research chapter. Seven classifications of AM processes are stated and their utilization
and application are disseminated through the work. The discussion concludes by stating the advantages of AM
process over conventional method in terms of increased efficiency, reduction in emission and complex development
of products [4]. An attempt was made to study the morphological properties of composites reinforced with graphene
and carbon nanotubes separately. Plasma surface modification technique was used for surface treatment of filler

Advances in Polymer Composites: Mechanics, Characterization and Applications

AIP Conf. Proc. 2057, 020039-1–020039-8; https://doi.org/10.1063/1.5085610
Published by AIP Publishing. 978-0-7354-1785-4/$30.00

020039-1
materials.the surface modification was basically carried out to get cleaner filler material which was achievable in sp3
hybridization and difficult to achieve in sp2 hybridization. The surface free energy of the composite with modified
carbon nonotubes showed better mechanical properties whereas graphene did not exhibit any considerable changes.
The dispersion of the filler material was notices to form better bonds by avoiding agglomeration in carbon nanotunes
[5]. The development of composite filament has been carried by many researchers for study of various properties;
some researchers have developed a new filament for FDM, with a vision for improvement in physical and
mechanical properties. The addition of filler particles with higher thermal conductivity to the polymer can enhance
the desired properties of product. Iron and Copper were reinforced with ABS polymer at various volume fractions
(5%, 10%, 20%, 30% and 40%). Micro particles of Iron were in irregular shapes and that of Copper was in spherical
shape. The size mixing ratio of ABS/metal particles was maintained in the ratio of 10:1 or above to have effective
packing factor. It was observed that upto 10 volume% addition of Copper particle could not break the thermal
resistance of ABS polymer; however there was an increase in thermal conductivity from 20 vol%. The establishment
of molecular chain with metal fillers was maximum at 30 vol% which enhanced the thermal conductivity of the
material to 3.5 W/m0C. However, iron fillers did not exhibit the thermal property improvement as that of Copper,
due to less thermal conductivity of iron and shape of the filler material also plays an important role. Heat capacity
analysis was also carried out by Differential Scanning Calorimetry, which shows the reduction in heat capacity of
ABS with more than 10 vol% addition of metal filler. It was observed to be directly proportionate to increase in
thermal conductivity [6]. Comparative study of analysis of variation of thermal conductivity for pure ABS and
ABS+Cu mixed in various proportions was carried out. Cu in the form of nano particle was mixed with ABS and the
developed composite filament was tested for thermal conductivity through parallel conductance method. The results
suggest that the thermal conductivity of Cu reinforced ABS was higher [7]. Few other researchers studied the
composite filament by mixing ABS with Cu and Fe particles; the study was carried out with variation of different
properties such as fill density and temperature. The viscous property of the ABS filled metal filler was observed to
decrease with increase in temperature. The increase in metal content led to decrease in the tensile strength of the
material, however, with the variation of fill density there was a variation in tensile strength; 20% fill density had
lower tensile strength where as 60% fill density provided suitable tensile characteristics. Increase in thermal
conductivity of the composite was seen with increase in metal content due to reduction in coefficient of thermal
expansion. It was also noted that with addition of metal filler content the reduction of tensile strength was due to
formation of larger voids with increase in content. [8]
Researchers have considered various parameters like fill angle, fill density and thickness of layer for optimization
of FDM process. L9 orthogonal array of Taguchi’s method was followed for analysis and outcomes were tested for
tensile, strength, manufacturing time and roughness. Experimental results gave appreciable and enhanced results
with optimized parameters. However, the parameters varied for optimized results for each of the outcomes [9]. Many
researchers have tried new filler materials for improvement of properties. A new eco-friendly material was
developed for usage in toy industry considering the parameters of colour change, antimicrobial property,
luminescence and conductivity. Conventional polymer matrix like ABS, PLA and TPU were used with variation of
additive material depending in the desired property [10]. The filler content plays an important role in improvisation
of mechanical and thermal properties and also in creation of 3D printed parts without the formation of voids. Wood
particles was mixed with PLA for from 0% to 50% in weight ratios and it was noted that the tensile strength showed
highest value at 10% loading of wood particles and it decreased drastically with 50% loading. Clogging was noticed
with increase in the wood particle content. There was no observation noted in variation of glass transition
temperature [11].
In this study PC-ABS is chosen as the matrix material because of its higher impact resistance, rigidity and easy
flexibility when compared to ABS in engineering applications. PC is transparent, rigid and tough whereas ABS is
flexible and has higher processability. The addition of appropriate quantity of ABS to PC makes it a good material
for use in 3D printer with glossy finish and high stability of printing. The combination of PC-ABS is in the ratio of
70:30. The experimental strategy to obtain the efficient filament by various combinations is always the goal, but this
greatly depends on various process parameters, the ability of formation of bond between the layers and also on how
effectively the dispersion of filler molecules is occurring in the matrix. In this paper the analysis is carried out on
dispersion characteristics of the Graphene filler in the PC-ABS matrix by micro structure studies using 3D printed
components, SEM and elemental mapping.

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 MATERIALS AND METHODS

The process of development of filament plays very important role in enhancing the desired properties. Dispersion
of filler material, maintenance of optimal temperature range for compounding and extrusion and pre-post process
requirements are the criterions that establish required properties. The extrusion of filament was carried out by
compounding the PC-ABS pellets with variation of graphene content in volume percent basis. PC-ABS in the form
of pellets was procured from M/s Polyshakti Polymers, Bangalore, and was preheated at 1100C in an oven for 3 to 4
hours, for removal of moisture. Pre drying of the pellets helps in reduction of wet ability and also for proper
distribution of filler without agglomeration. The dried pellets was mixed properly in high speed mixer in the ratio
70:30 and five samples were prepared; four with addition of Graphene as a filler material with the volume percent as
0.1, 0.15, 0.2 and 0.25 and one pure PC-ABS. Figure 1(a) and (b) shows photograph of ABS and PC pellets
respectively. Figure 1(c) shows scanning electron micrograph of graphene sheets with Edax pattern.

(a) (b)

(c)

FIGURE 1. (a) ABS pellets (b) PC pellets (c) SEM and EDAX of Graphene

The compounding of the mixture was carried out in 30mm twin screw co-rotating lab extruder at GLS Polymers,
Bangalore, processing temperature was maintained in the range of 200 0C to 2400C. The mixture after compounding
was again dried at 1100C for 3 hours before feeding it to wire extruder, to increase the lenience of easy extraction.
The pellets were then fed into 20mm single screw extrusion machine and were extruded out at 1.75mm diameter
after passing the filament through water cooling process. Figure 2 shows the compounded mixture and filament
extrusion in progress.

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 (a) (b) (c)

FIGURE 2. (a) Compounded PC-ABS with graphene (b) PC-ABS+Garphene filament extrsion (c) PC-ABS filament extrusion

RESULTS AND DISCUSSION

Macro analysis of the filament was studied to quantify the dimensional properties of the filament to be suitable
for the FDM process. Trials were conducted at various lengths of the filament to understand the dimensions, through
digital vernier caliper instrument. There was a maximum tolerance of 0.001mm for averaged values of filament
diameter. Graphene as a nano filler material has bonded with the matrix in proportionate form without variation in
the required diameter. Visual inspection indicated there are no cracks and flaws in the filament, microanalysis of
filament do not show any visible defects.Microstructure results showed decreasing pores with increase in the filler
material. Figure 3 shows the filaments with varied proportions of the filler material. Table 1 indicates the average
values for the diameter of the filament of various proportions. The values suggest the proper dimensional accuracy
for the filament is maintained and hence can be used for FDM process.

Material Filament
PC-ABS

PC-ABS + 0.1vol% Graphene

PC-ABS + 0.15vol% Graphene

PC-ABS + 0.20vol% Graphene

PC-ABS + 0.25vol% Graphene

FIGURE 3 Filament with varied proportions of Graphene

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 TABLE 1. Dimensional accuracy of the filament
Trail 1 Trail 2 Trail 3 Trail 4 Average
PC-ABS 1.7488 1.7503 1.7512 1.7593 1.7524
PC-ABS 1.7601 1.7533 1.7547 1.7572 1.7563
+0.1vol%
Graphene
PC-ABS 1.7589 1.7555 1.7496 1.7623 1.7564
+0.15vol%
Graphene

PC-ABS 1.7663 1.7552 1.7559 1.7622 1.7599

+0.2vol%
Graphene
PC-ABS 1.7531 1.7489 1.7601 1.7532 1.7538
+0.25vol%
Graphene

SEM and Elemental Mapping:

Graphene nanoparticles dispersion in the PC-ABS polymer matrix is being studied, which clearly indicates the
homogenous dispersion of the filler material without agglomeration. The aggregation of the Graphene particles is
also not seen which indicates the superior property of the material having a 2D lattice structure and exemplary
surface-to-area volume ratio. The isometric dispersion is seen with equal spread out of materials throughout the
matrix. The shape of the filler material is seen to be irregular as shown in figure 1. Since, few researchers claim the
surface modification would not greatly effect for Graphene nanofillers, the dispersed fillers as shown in figure 3 are
non surface modified and are multilayer. Figure 4 shows scanning electron micrographs and its corresponding
elemental mapping images for pure PC-ABS and graphene filled PC-ABS nano composites. Internal mixing
(compounding) and twin screw extrusion techniques are capable of dispersing raphene particles homogenously
throughout PC-ABS matrix.
The elemental mapping from figure 4 appropriately indicates the dispersion of filler material with increase in
filler content. There are no traces of agglomeration of the particles which clearly indicates the good interaction of
the molecules of polymer and filler and it also suggest the interaction forces between the nanofillers is maintained to

SEM Elemental Mapping

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 FIGURE 4. SEM images and elemental mapping for PC-ABS, PC-ABS+20wt% Graphene, PC-ABS+30wt% Graphene.

Optimal parameter which would greatly enhance the properties of the composite filament. Hence, this would pave
no way in agglomeration of the nozzle used in FDM. The enthalpic interactions can be concluded to be distributed in
a sequence from polymer chain to nano fillers, which proves out to be well interacted composite.
TABLE 2. Filament production temperature

Filament PC-ABS PC-ABS PC-ABS PC-ABS PC-ABS

+0.1vol% +0.15vol% +0.2vol% +0.25vol%
Graphene Graphene Graphene Graphene
Temperature 254 256 256 258 262
(oC)

Temperature plays an important role in maintaining the required diameter for the extraction of filament through
the nozzle. Trial and error methods were carried out to identify the exact temperature for extracting out the filament
at 1.75mm diameter. Pure PC-ABS had to be maintained at a range of 254 oC to get the filament at 1.75mm, however
the same temperature was not able to yield the same diameter with addition of nanofiller. The temperature had to be
increased slightly to get the filament of the required diameter. 262 oC was the maximum temperature to be seen for
extraction of PC-ABS with 0.25vol% Graphene. The increase in the filler content led to better establishment of
network between molecules of matrix and hence upliftment in transition temperature.

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 Two solid molecules cannot occupy the defined space at same time; hence, the entropy between the molecules
makes it to be attractive at a specified distance; which proves out for well dispersed nanoparticles. The bond strength
and polymer chain formation will reduce the surface free energy of the composite and enhance the properties.
The density of graphene filled PC-ABS filaments were measured as per ASTM D792-13 standard. Further,
theoretical density and voids were evaluated using rule of mixtures. At least five readings were considered for each
composition and the final results are average of all five readings. Figure 5 represents the graphical view of variation
of density theoretically and experimentally for the composite. S1, S2, S3 and S4 states to be the volume percent of
garphene added to PC-ABS in the ratio 0.1, 0.15, 0.2 and 0.25 vol% respectively.

FIGURE 5. Graphical representation of variation of density

The variation in density for increased vol% of filler increases to certain limit and then decreases gradually in
experimental measurements. The agglomeration and uneven dispersion of filler material is claimed for decrease in
density of the composite filament.

CONCLUSION
Graphene nano particles up to 0.25 volume % were successfully reinforced in PC-ABS matrix. Both pure PC-
ABS and graphene filled PC-ABS filaments were extruded using twin screw extrusion technique suitable for FDM
applications. SEM and elemental mapping confirms homogenous dispersion of graphene particles. Density of nano
composite filament increases with increase in graphene content and correlates well with theoretical density upto 0.2
volume % . There is a sudden drop in density for 0.25 volume% of graphene which may be attributed to excessive
void formation. Diameters of the extruded filaments are well within the acceptable limits suitable for FDM
applications.

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