FDM 3D Printing of high performance

composite materials

Anna Costanza Russo Giustiniano Andreassi Achille Di Girolamo

R&D department R&D department R&D department
Comec innovative Comec innovative Skepsis srl
Chieti, Italy Chieti, Italy Pescara, Italy
[Link]@[Link] [Link]@[Link] [Link]@[Link]

Gianluca Barile
Silvio Pappadà Giuseppe Buccoliero Dept. of Industrial and information
Advanced Materials & Processes Advanced Materials & Processes engineering
Consulting Department Consulting Department University of L’Aquila
CETMA CETMA L’Aquila, Italy
Brindisi, Italy Brindisi, Italy [Link]@[Link]
[Link]@[Link] [Link]@[Link]

Francesco Vegliò Vincenzo Stornelli

Dept. of Industrial and information Dept. of Industrial and information
engineering engineering
University of L’Aquila University of L’Aquila
L’Aquila, Italy L’Aquila, Italy
[Link]@[Link] [Link]@ [Link]

Abstract— This work aims to the definition of the

requirements of a new pre-impregnated high-performance
However, the traditional processes of transformation of
material to be 3D printed. The compression molding thermoplastic composites, which are based on the fusion of the
process was used as a reference for the transformation of matrices and reconsolidation of the same thermoplastic
the new prepregs to eco-sustainable matrix to be made matrices with pressure application, limit the production of
flush in order to be fused and deposited with a FDM 3D components in thermoplastic composite in maximum and
printer. Furthermore, the main characteristics that the thickness dimensions.
matrix must have in order to be used to produce prepreg A very interesting technological alternative to the
(viscosity, pot-life, shelf-life, etc.) have been identified and thermoplastics, for the production of composites, has been
here presented. Finally, a commercial printer has been proposed for some years.
modified and used for filament test deposition. In this alternative, precursors monomers and low viscosity
oligomers are used to impregnate different types of
reinforcing fibers, thus following an in-situ polymerization
Keywords — Additive Manufacturing, 3D printing, supports, step. After in situ polymerization, the composite behaves in all
FDM. respects as a thermoplastic composite, with possibility
therefore to be re-melted and re-consolidated a certain number
of times, besides of course the possibility of being recycled as
I. INTRODUCTION a common thermoplastic. The interest in these new matrices is
Thermoplastic composites are characterized by a series of demonstrated by a series of patents developed by large
fundamental advantages compared to classical thermosets, multinational companies operating in the chemical sector [1-
specifically they have: 2], in addition to the recent development of cost-effective
- high toughness, solutions for the automotive sector.
- possibility of using processes characterized by low Van Rijswijk et al. published in 2006 an overview of the MTR
cycle time and high level of automation, matrices being studied and developed. The following Figure 1
- recyclability. shows a schematization of the main known systems. In this
picture, among MTR systems, epoxy-based MTR systems are
missing and have been studied in this work.

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978-1-7281-0429-4/19/$31.00 ©2019 IEEE
 Figure 1: Viscosity and process temperatures of various thermoplastic materials

With reference to thermosetting matrices, resins traditionally FDM technology has taken hold market importance thanks to
used in the automotive sector are non-biodegradable the huge range of application fields [3-11] and printable
thermosetting agents of fossil derivation, such as unsaturated materials, which guarantee more or less printing simplicity
polyester resins, vinylester, epoxy, reinforced with glass and the most varied physical properties (flexibility, impact
fibers. In this work the proposed innovation concerns the use resistance / compression / traction, thermal resistance even to
of materials, analogous from the point of view of chemical electrical conductivity) [12-16]. PLA and ABS are certainly
functionality, but obtained from renewable resources being the most widespread thermo-polymers widely used for this
this material able to be FDM printed. In this case printing technology. Besides these two materials, they have
environmental sustainability concerns not only the possibility great use also the Polycarbonate (PC), the polyvinyl alcohol
of recycling the material, which typically occurs through (PVA), the Polyethylene terephthalate (PET), the Polystyrene
mechanical grinding technologies or chemical digestion, but shockproof (HIPS), Nylon, Laybrick, Laywood and
also the derivation from renewable resources. We here present NinjaFlex.
the development of a modified type of 3D printer with FDM There are currently no FDM printing materials on the market
technology capable of deposit loaded filaments based on MTR whose physical properties depend in a controllable (and
matrices. In this case we want to exploit the capacity of these repeatable) way from the temperature at which they are
systems to operate impregnating reinforcing fibers (also deposited. At the same time the printer has to precisely operate
creating chemical bonds with the fibers) and having a when depositing these kinds of materials.
thermoplastic behavior suitable for FDM 3D printing.

II. FDM 3D PRINTERS III. IMPREGNATION TECHNOLOGIES WITH ECO-SUSTAINABLE

RESINS AND 3D FILAMENT
For low-cost commercial products the resolution ranges from
80μm to 300μm. In this context, it is precisely the layer Regarding the development of impregnation methodologies
thickness to determine the precision limit of this prototyping with eco-sustainable resins, it is necessary to underline how
technology. the use of the type of materials be within the range of the
European regulatory framework for which technical
adjustments are required for reuse, recycling and recovery of

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 Parameter Value

Temperature of the Resin in the tank 80°C

Resin temperature in the delivery system 100°C

Impregnation roller temperature 100 °C

Feed rate 1 m/min

Table I- Parameters optimized for the EPO 02L resin system

Parameter Value

Temperature of the Resin in the tank 70°C

Resin temperature in the delivery system 100°C

Impregnation roller temperature 100 °C

Feed rate 1,5 m/min

Table II- Parameters optimized for the XFN FRS 6002-A/B resin system

plastic materials. In particular the EC Directive EC 2000/53 /

EC imposes restrictions concerning up to 95% of the plastic - the viscosity of the resin during the impregnation phase must
materials contained in the vehicle. be brought to its minimum value (impregnation process
The adoption of 3D printing technologies will allow to window);
introduce the advantages of environmental sustainability - during the whole impregnation process (including heating
connected to Lean Enterprise model thanks to the possibility in the heated tank, the dispensing system itself and the
of developing products and services with a high technological impregnation phase with the heated rollers) the viscosity of
content breaking down the plant barriers and allowing a the resin must not exceed the whole process window. Table I
business model in which production can be localized near the and Table II shows the main optimized parameters for the
end user [16-19]. The impact on environmental sustainability considered materials.
is then very evident if we consider that rapid prototyping, in After the impregnation phase the next step consisted in
general, allows also the reduction of storage in spare parts grinding the solidified mixture; for this purpose a blade mill
warehouses. (model RETSCH SM2000) was used which, by centrifugal
The precise definition of the impregnation process of action, reduces the particle size of the reinforced resin
composite materials with reduced environmental impact has fragments up to dimensions suitable for feeding into the
been carried out as follows: extruder of the final spinning process.
• Analysis of the parameters of the selected resin systems, with The HAAKE RHEOMEX 302P single screw extruder has
particular reference to the parameters that influence the been used connected to a RHEOCORD 300P motor in order
impregnation process; to obtain Fig.2 filament. We started from a commercial 3D
• Impregnation test of two kind materials: 1) XFN FRS 6002- printer (Creality CR10) by redesigning the extruder using
A/B/Green-lite_14415; 2)Elan-tech® EPO 0 2L /HexForce® appropriately integrated purchasing materials to extrude
G0926; abrasive materials with high transition temperatures. For this
Downstream of the impregnation tests, once the impregnation purpose the first hot-end (Fig.3) of the factory was replaced
parameters have been optimized, 100 meters of prepreg have with an E3D V6 completely made of metal and equipped with
been produced for both the systems previously reported. The an oversized, suitably calculated heater, capable of bringing
main aspects considered are listed below:

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the machine to work at more than 350 ° C. A 0.8mm
extrusion nozzle with ruby coating (rather than brass) was
also mounted to prevent its deformation due to the joint action
of high temperatures and material (Fig.4). It was also
necessary to replace the thermistor used for the measurement
of the hot-end temperature with a thermocouple and relative
amplifier that allowed precisely such high temperatures to be
read [20,21]. In order to isolate the high temperature zone, an
indirect guide topology has been designed for the extruder
with a reduction between the motor and the drive gear equal
to 3: 1 to increase the traction torque. The first test carried out
on the filament provided by CETMA was related to the
research of its transition temperature which proved to be Figure 4: Filament deposition example
between 280 ° C and 300 ° C and its deposition phase, see
Fig. 4.

IV. CONCLUSIONS
In this work we have presented the definition of the
requirements of a new pre-impregnated high-
performance material to be 3D printed. A commercial 3D
printer has been redesigned in order to allow the new material
to be FDM printed.

AKCNOLEDGMENTS
The work has been funded by the “Sviluppo di materiali
compositi ad elevate prestazioni e ridotto impatto ambientale
a base di matrici ecosostenibili” project in the framework of
the action “POR FESR Abruzzo 2014 – 2020 – Linea di
azione 1.1.4 - Avviso Pubblico per il Sostegno a progetti di
Innovazione delle Grandi Imprese e delle PMI nelle aree di
specializzazione S3”.

Figure 2: The implemented filament.

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