Accepted Manuscript

3D-printed PEEK-Carbon Fiber (CF) composites: Structure and thermal properties

А.А. Stepashkin, D.I. Chukov, F.S. Senatov, A.I. Salimon, A.M. Korsunsky, S.D.
Kaloshkin

PII: S0266-3538(18)30087-3
DOI: 10.1016/j.compscitech.2018.05.032
Reference: CSTE 7235

To appear in: Composites Science and Technology

Received Date: 11 January 2018

Revised Date: 17 May 2018
Accepted Date: 18 May 2018

Please cite this article as: Stepashkin АА, Chukov DI, Senatov FS, Salimon AI, Korsunsky AM,
Kaloshkin SD, 3D-printed PEEK-Carbon Fiber (CF) composites: Structure and thermal properties,
Composites Science and Technology (2018), doi: 10.1016/j.compscitech.2018.05.032.

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 ACCEPTED
3D-printed PEEK-Carbon MANUSCRIPT
Fiber (CF) composites: structure and thermal

properties

Stepashkin А.А.1, Chukov D.I.1, Senatov F.S.1, * Salimon A. I.1, Korsunsky A.M.2,

Kaloshkin S.D.1

1
- National University of Science and Technology «MISIS», 119049, Leninskiy pr. 4,

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Moscow, Russian Federation

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2
- Department of Engineering Science, University of Oxford, Parks Road, Oxford,

OX13PJ, United Kingdom

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* - corresponding author, a.salimon@misis.ru, 119049, Leninskiy pr. 4, Moscow,

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Russian Federation
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Keywords: A. Carbon fiber A. Polymer-matrix composites (PMCs) B. Thermal

properties D. Thermal analysis E. Lay-up (manual/automated)

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Highlights
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• Successful 3D printing of Carbon Fiber-reinforced PEEK matrix composites is

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reported
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• Process-induced porosity of 3DP CF-PEEK structures results in the reduction of

density and thermal conductivity compared to cast composites

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• Large pores lie at the interfaces between consequently deposited layers and lead
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to damage localization and multiple crack formation under load

• Fine imperfections formed within individual deposited layers likely to arise due

to process-induced temperature gradients give rise to small-scale cracks under

load
 • Hierarchical porosityACCEPTED MANUSCRIPT
of PEEK matrix induces additional thermal conductivity

anisotropy of 3DP CF-PEEK structures compared to their cast counterparts

Abstract

CF-PEEK composites were manufactured by 3D-printing using a novel FDM

methodology and customized printer and were compared with their cast counterparts.

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The characterization of composite thermal properties in the range 25-300 ºC revealed

that 3D-printed CF-PEEK composites manifest 25-30 % lower thermal conductivity

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than cast composites. Short carbon fibers used for reinforcement showed orientation

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along the polymer flow both in cast and 3-D printed samples causing the anisotropy of

thermal properties. The hierarchical nature of 3DP CF-PEEK porosity was observed by

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SEM imaging, which allowed the identification of large scale inter-layer gaps and
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cracks, and fine scale intra-layer defects that are likely to be induced by the thermal and

mechanical gradients within the deposit that arise during fabrication. Purpose lay-up of
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long continuous carbon fibers during 3D-printing opens a way to fabricate tailored
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mechanical parts with desired anisotropy of thermal properties.

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Introduction
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Layer-wise Additive Manufacturing (AM) technology allows the production of

complex metal, ceramic and polymer-based components from digital computer models,
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obviating the need for costly tool and workpiece fabrication, producing near net-shape
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objects, thus minimizing the requirement for further machining [1]. Various ‘flavors’ of

Additive Manufacturing exist, ranging from Selective Laser Sintering (SLS) to Fused

Deposition Modelling (FDM) to Stereo-Lithography (SL). Recent decades have

witnessed continuous improvement in the accessibility and flexibility of these methods,

expanding the range of printable materials, enhancing the manufacturing precision and

increasing the degree of perfection of ready parts.

 ACCEPTED
Composites produced MANUSCRIPT
using traditional technologies provide a significant

improvement of mechanical properties in comparison with unfilled materials. There is a

strong motivation to demonstrate that the application of additive technologies for

composite materials combining polymer matrices and discrete or continuous high

modulus fibers can follow the same trend [2]. The application of 3D printing to the

modern high-performance thermoplastic polymers, such as PEEK, PPS, PSU,

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possessing high chemical resistance, good mechanical characteristics and heat

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resistance, opens unprecedented possibilities for successful manufacturing of high

performance engineering and biomedical articles. Successful 3D printing of implants

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made with biocompatible unfilled PEEK has recently been reported [3-6].

In general, 3D printing of PEEK filled with continuous carbon fibers is a challenging

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task, since the high temperature of printing requires oxidation protection before and

during the process. Furthermore, good adhesion between the carbon fibers and the
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surrounding matrix must be ensured to achieve optimal property improvement [7].

There is a very limited range of reported data on 3D-printed PEEK-base

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composites [8]. So far, low-temperature extrusion free forming 3D printing technology

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has been the approach addressed by the researchers [9] for PEEK/HA composites. In the

present study we concentrate on the use of FDM as the means of creating fiber-
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reinforced CF-PEEK composites, and carry out initial characterization of the

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mechanical and thermal properties of 3D-printed composite parts. By carrying out

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careful microscopic SEM imaging we reveal the multi-scale, hierarchical nature of

porosity within these structures. This serves both to improve our understanding of the

process, and provides an indication of further directions for process optimization

required to obtain 3DP composite parts with desired properties.

Fig.1 provides a schematic illustration of the 3D printing process, and the

hierarchical structure of the resulting 3DP CF-PEEK composite and its inherent porosity

. It proposes a scenario of the formation of systems of pores and imperfections: A) at the

 ACCEPTED
interface between consequently MANUSCRIPT
deposited layers – i.e. in the direction of vertical

growth; B) at the interface of nozzle passes within a single deposited layer – i.e. in the

direction of intraplanar growth, C) at the interface of polymer-carbon yarns or single

fibers within a single nozzle pass – i.e. in the direction of nozzle movement. The

hierarchy of imperfections is the intrinsic feature of 3D printing. It is possible to

surmise that different physical mechanisms are responsible for each system of

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imperfections, each requiring specific investigation.

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The coarsest system A) is likely formed mainly due to the shrinkage of polymer

at solidification (that reaches 1.3%, as reported in [10]) that occurs on top of the cold

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substrate composed of a previously deposited layer. The mismatch of specific volumes

of hot and cold layers results in material separation that is manifested as porosity.

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The contribution of thermal shock and temperature gradient that cause tensile

stresses in the core zone of the underlying cold layer needs to be carefully quantified
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with the help of a numerical model considering many factors (nozzle speed, mass flow

through nozzle, thermal properties of polymer or composite). Tensile stresses may be

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released through microcracking or the formation of other imperfections within the

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deposited layer, somewhat removed from the layer interface. It is obvious that both

mechanisms are more pronounced in the direction vertical growth, where the highest
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temperature gap between previously and currently deposited material is expected.

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The formation of system B) is governed by qualitatively similar mechanisms, but due to

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the shorter time between forward and reverse nozzle passes, the system of imperfections

that arises is much less pronounced.

The system C) is closely related to the wetting of the interface between polymer

matrix and carbon reinforcement that is present either in the form of single short fibers

having thickness of tens microns, or as much thicker yarns of continuous carbon fibers.

The latter generate specific coarse inter-yarn porosity caused by the imperfect

impregnation with polymer.

 ACCEPTED
Below we demonstrate MANUSCRIPT
how this hierarchy of imperfections characteristic of 3D-

printing manufacturing technology affects the thermal and mechanical properties of CF-

PEEK composites, including fracture and strength.

Material and methods

A custom-made FDM Z2 3D printer purposely developed in SkolTech, Moscow,

Russia by Professor S.G. Psakhye was used to produce the samples of CF-PEEK

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composites filled with discrete or continuous carbon fibers. Unfilled PEEK and CF-

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PEEK composite filaments (20 % of carbon fibers; the mass % are used hereinafter)

having diameter 1.7 mm were produced by means of extrusion and the discrete fiber

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content was achieved through the dilution of ready CF-PEEK composite Victrex 150

CA30 (30 % of discrete carbon fibers) [11] with unfilled PEEK Victrex [12]. In this

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series of experiments it was not possible to print CF-PEEK composites with fiber

content higher than 20 %, since fiber content exceeding this threshold caused excessive
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melt viscosity of melt at temperatures in the range 350 – 370 оС. Higher printing

temperatures, on the other hand, led to unacceptable oxidation and degradation of

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polymer structure and mechanical strength.

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Unidirectional composites with fiber content of 5 % were 3D-printed in the

regime when printer nozzle was fed with continuous carbon fibers Tenax –J HTA40
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H15 1k simultaneously with unfilled PEEK filament. Ultimately, 3D printing was

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applied to produce the plates which were machined afterwards to obtain specimens of
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necessary shapes and dimensions for further testing.

The reference samples of unfilled PEEK grade Victrex 150UF and CF-PEEK

composite Victrex 150 CA30 were injection-molding cast using the Thermo Scientific

Haake MiniJet machine in accordance with the instructions from material manufacturer

(Victrex), namely, injection piston temperature 390 оС, injection pressure 500 bars,

mold temperature 190 оС. All measurements were carried out for a series of at least 5

specimens cut from different sample zones. The averaged data is given in Results.
 ACCEPTED
Density measurements MANUSCRIPT
[13] were performed using high precision analytical

balance AND GR 202 equipped with the set up for hydrostatic weighting in distilled

water for specimens with dimensions of 30х30х4 mm x mm x mm. Water absorption at

25°С was determined in accordance with Method 1 [14]. The measurements of thermal

diffusivity were carried out in the range of 25-300 ºC in accordance with [15] by the

Flash Method using NETZSCH LFA447 NanoFlash device using cylindrical (Ø12.7 x

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1..1,5 mm) and prismatic (8х8х2 mm) specimens, carefully cut from bigger samples.

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When strong anisotropy of thermal diffusivity was expected, as in the case of

unidirectional PEEK+ 5 % of continuous carbon composite, prismatic specimens were

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also prepared as a set of 2х2х8 mm bars. A film of thermally conductive carbon (0.3 -

0.4 mm thick) was deposited on the surface of the plate sample (KONTAKT CHEMIE

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® GRAPHIT 33 spray). This allows assuming that the energy deposited by the laser

flash is distributed in the carbon film first, and heat is further transmitted by conduction
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to the opposite side of the plate specimen.

The thermal conductivity was calculated in accordance with formula (1):

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λ (t ) = a(t ) ⋅ d k ⋅ C p (t ) (1)
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where λ(t) – thermal conductivity at temperature t, W/m·K;

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a(t) - thermal diffusivity at temperature t, mm2/s;

dk - material density, g/cm3;

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Cp(t) – heat capacity at temperature t , J/g·K.

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Heat capacity Ср was experimentally measured in the range 25 to 300 оС in

accordance with [16] using differential scanning calorimeter NETZSCH DSC 204

Phoenix F1 with sapphire reference sample.

SEM structure studies were conducted using Hitachi TM-1000 and Tescan Vega

3 microscopes at fracture surfaces obtained using cryogenic brittle cracking.

 FT-IR spectroscopy ACCEPTED
was performed MANUSCRIPT
using Nicolet 380 IR-Fourier spectrometer

(the spectral range 4000-450 cm-1 with a resolution of about 0.9 cm-1, the accuracy of

the wave number 0.01 cm-1) in attenuated total reflection (ATR) mode.

Results and Discussion

Structure. 3D printing of CF-PEEK composites allows manufacturing of the

parts with complex shapes (see Figure 2 a and b). Cut specimens are exemplified in the

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Figure 2 c. This technology, as previewed, induces both pores in the matrix polymer

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(Figure 3 a-d) and discontinuities at matrix and carbon fiber yarn interfaces (Figure 3 e-

f) due to the lack of impregnation.

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The density of 3D printed samples is lower than that of cast composites; the

latter have density in accurate accordance with the supplier technical specifications as

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seen in the Table 1. The decrease of density in 3D printed samples is related with

additional porosity of about 1,0 – 1,15 %. This additional porosity as seen in the Figure
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4 a, b is represented by two systems of pores – the coarse discontinuous flaws (thickness

is 20-40 µm) at the interfaces of fused deposited layers and the fine tracks (thickness is
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1-5 µm) within a single fused deposited layer (the layer thickness is about 250 µm).
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Table 1 – Physical properties of PEEK-based composites

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Unfilled PEEK + 30% PEEK + 20 % PEEK + 5 %

PEEK discrete CF discrete CF continuous CF

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(Victrex (Victrex 150 (Victrex 150 UF (Victrex 150 UF

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150UF) CA30) + Victrex 150 + Tenax –J

CA30) HTA40 H15 1k)

Density by supplier technical 1,3 1,4 1,367 1,322 (calculated)

specification, g/cm3 (calculated)

Density of cast samples (as 1,302 – 1,304 1,431 – 1,434 1,377 – 1,381 -

measured), g/cm3
Density of 3-D printed 1,266 – 1,281 1,276 – 1,289 1,365 – 1,371 1,168 – 1,266

samples (as measured), g/cm3

 Porosity of 3-D printed ACCEPTED
1,0 – 1,02 MANUSCRIPT
1,11 – 1,13 0,99 – 1,01 1,05 – 1,14

samples, %
Water absorption of 3-D 0,05 – 0,06 0,05 – 0,06 0,06 – 0,07 0,08 - 0,09

printed samples, %
Since the values of water absorption reveal almost no difference between cast

(0,04-0,05 as specified by supplier [16]) and 3D printed composites one can presume

that the predominantly close-cell type of porosity is formed in 3D printed samples. This

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conclusion is supported by microscopy data on flaw’ appearance in Figure 4.

The exceptionally high value of water absorption (up to 0,09 %) for the unidirectional

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composite reinforced with continuous carbon fibers is believed to be caused by the

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imperfect impregnation of yarns with polymer matrix that leaves easier access of

moisture along the yarn filler. The latter, obviously, might be a detrimental factor in the

durability of composite articles.

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Additional porosity represented by two systems of pores causes the localization

of mechanical failure as seen in the Figure 4 c and d. The coarse and wide cracks are
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separating fused deposited layers having thickness about 250 µm, while thinner cracks
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and shear steps within a single layer are likely related with the system of fine tracks.
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Figure 3 shows a satisfactory wetting of short carbon fibers with PEEK. Although SEM

reveals some delamination at the matrix-fiber interface and pulling of fibers from the
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matrix it is not believed to affect the strength of composites. The length of discrete

carbon fibers in the range 60 - 100 µm may not be sufficient to interconnect the layers
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of the multilayered structure with the thickness of layers about 250 µm. Moreover, the
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partial alignment of discrete fibers along the polymer flow causes the anisotropy and

non-uniformity of mechanical properties leaving the likelihood for fiber interconnection

of layers even less than that in case of stochastic spatial distribution of fiber orientation.

The characteristic FT-IR peaks in 3D-printed and cast PEEK samples are

presented in Figure 5: C=O stretching vibrations at 1650 cm-1, aromatic skeletal

vibrations at 1594, 1490 and 1413 cm-1, C–C(=O)–C bending vibrations at 1305 cm-1,
 ACCEPTED
asymmetric stretching of C–O–C MANUSCRIPT
at 1280 and 1185 cm-1, aromatic hydrogen in-plane

deformation bands at 1157 and 1103 cm-1, diphenyl ketone band at 927 cm-1 [17]. The

presence of these peaks manifest that the oxidation level of both cast and 3D printed

samples is almost the same and, moreover, there was no noticeable difference in the

oxidation level between the core zones in cast samples and sites of increased porosity in

3D printed samples. FT-IR does not provide reliable evidences of localized oxidation.

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Since we did not firmly detect any localized oxides their contribution in fracture

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behaviour is questionable. Taking into account than the spatial resolution of FT-IR

device, i.e. about 2-3 µm, it can be concluded that the thickness of suggested oxidized

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layers is much smaller than the thickness of coarse porosity system and therefore

localized oxidation does not seem to contribute to coarse cracks. One can however

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speculate about comparable contribution of fine tracks (thickness is of 1-5 µm) and

suggested oxidized layers having thickness below 2 µm into secondary microcracking.

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Thermal properties. The temperature dependence of the specific heat capacity

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Cp(t) for CF-PEEK composites is represented in Figure 6 where in the range 25-300 ºC

DSC curves reveal the only peculiarity upon heating – the jump at glass transition
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temperature Tg (in the interval 144,9 -151,9 ºC). The transition of basic polymer to
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highly elastic state is also traceable as the peculiarity at Tg in temperature conductivity

a(t) and thermal conductivity λ(t) curves.

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The slope of Cp(t) curves remains unchanged at temperatures below and above
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Tg. Some increase of heat capacity in the vicinity of 300 ºC is related with the pre-

melting processes in the polymer [18]. The heating-cooling cycling in inert atmosphere

did not lead to any change of heat capacity dependence. The values of Cp of composites

were in good accordance with the general rule of mixture for all filler contents studied.

The data on thermal diffusivity a(t) which are represented in the Figure 7

demonstrate that thermal diffusivity in 3D-printed unfilled PEEK and PEEK + 20 % CF

composite is lower than thatACCEPTED MANUSCRIPT
in cast counterparts over the whole temperature range. We

believe that the decrease of a is caused by additional porosity in 3D-printed samples.

Since this decrease is more pronounced in unfilled PEEK (for about 20-25 %) than in

CF-PEEK composite (for about 8-13 %) having equal porosity it is suggested that

partial percolation of highly conductive carbon fibers may compensate the detrimental

effect of additional porosity.

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Figure 7 b also shows that thermal diffusivity at 25 ºC in the specimens cut from

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the thick (15 mm) cast samples of PEEK + 30 % CF composite is for 50 % higher than

in specimens cut from 2 mm thick cast plate (0,6 and 0,4 mm2/s respectively). It is

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believed that the predominant alignment of short carbon fibers along the direction of

polymer flow causes the significant difference in the values of measured thermal

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diffusivity. In thin cast samples polymer flow is laminar and obviously parallel to the

sample plane. The predominant fiber alignment parallel to the sample plane returns in
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the direction perpendicular to the sample plane the values of thermal diffusivity of about

0,39 – 0,42 mm2/s. When 8 х 8 х 2 mm samples prepared as the set of 2х2х8 mm

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overturned lamellae the values of thermal diffusivity at 25 ºC reach 0,6 – 0,63 mm2/s
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that is close to values of thermal diffusivity (about 0,6 mm2/s) in the specimens cut from

thick cast samples where laminar type of polymer flow is less expressed. Therefore,
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high viscosity of highly filled composites becomes an important factor for casting as
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technology. Correct design and service of both composite parts and casting molds must
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take into account this anisotropy.

The anisotropy of thermal diffusivity is even more pronounced in unidirectional

3D-printed CF-PEEK composite filled with 5% of continuous carbon fiber yarns. Figure

7b depicts close values of thermal diffusivity in thin cast CF-PEEK filled with 30% of

short discrete carbon fibers and in unidirectional 3D-printed CF-PEEK composite filled

with 5% of continuous carbon fiber yarns. In both composites highly temperature

conductive carbon fibers are aligned parallel to the sample plane and in the direction
perpendicular to the thermalACCEPTED
flow directionMANUSCRIPT
– purposely in 3D-printed composite and

unintentionally, due to the technology causing predominant spatial distribution of fiber

orientation, in cast composite.

The percolation threshold for thermal diffusivity takes place at filler content

between 20 and 30 % of discrete carbon fibers. The filling of PEEK with 20 % of

discrete carbon fibers leads to the modest increase of thermal diffusivity for about 20-25

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% (from 0,17 to 0,22 mm2/s at 298 K) in comparison with unfilled PEEK that is in good

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agreement with the general rule of mixture. The filler content of 30 % leads to triple

value of thermal diffusivity (about 0,5 mm2/s if averaged between the values measured

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in parallel and perpendicular to polymer flow direction in thin samples) in comparison

with unfilled PEEK.

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The a(t) dependence (downward trend) demonstrates a peculiarity in the vicinity

of Tg, however, this dependence is linear at temperatures lower Tg and it tends to

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saturate close to the melting temperature for unfilled PEEK and all composites.

Figure 8 summarizes the data on calculated thermal conductivity λ(t). As it was

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expected thermal conductivity in 3D-printed composites is lower than this of cast

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composites due to the higher porosity in the range of 25-300 ºC. Thermal conductivity

grows for 11-19 % in unfilled PEEK over the temperature range for both technologies,
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e. g. for 3D-printing it rises from 0,21 to 0,25 W/m·K, and for casting it rises from 0,27
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to 0,30 W/m·K.
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The increase of filler content leads to weaker growth of λ against temperature for

both technologies - only for 3 – 9% depending on the filler content (the decrease of

density due to the thermal expansion was taken into account). The calculated value of

thermal conductivity of 0,92 W/m·K for thick samples of cast PEEK+30 % CF filled

with 50-100 µm long discrete carbon fibers is in good agreement with the values found

in Cambridge Engineering Selector database [19] for the same composition but filled

with much shorter carbon fibers (5 µm) – 0,87-0,97 W/m·K. This presumes rather
uniform spatial distribution ACCEPTED MANUSCRIPT
of fiber orientation and sufficient percolation in the thick

samples studied. The peak of thermal conductivity in the vicinity of Tg becomes

smoother with the increase of filler content that obviously reflects smaller contribution

of polymer into thermal conductivity of composites.

Taking into account the technological difficulties in 3D printing of CF-PEEK-

composites highly filled with discrete carbon fibers we consider the use of continuous

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carbon fibers as a promising option. In particular, thermal diffusivity and conductivity

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of the composite containing 5 % of continuous fibers is almost equal to the same of cast

composite containing 30 % of discrete carbon fibers. Applying the general rule of

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mixture we can estimate the value of thermal conductivity for unidirectional CF-PEEK

composite filled with 5% of continuous carbon fibers (having own thermal conductivity

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as high as 10 W/m·K [20]) in the direction of fiber orientation as 0,67 W/m·K.

Somewhat lower measured value about 0,6 W/m·K suggests insufficient impregnation
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of yarn with matrix polymer and existing brakes of single carbon fibers inside yarns.

Provided the latter technology problems are solved we forecast the level of
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thermal conductivity in the range of 5 – 6 W/m·K for Tenax –J HTA40 H15 1k yarn
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(and even up to 10-15 W/m·K for other carbon yarns) in desirable direction for

purposely designed unidirectional 3D-printed composite materials. The use of high

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modulus continuous carbon fibers and peck carbon fibers having high thermal
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conductivity along the fiber and higher filler contents will allow to reach this
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challenging target. This sort of 3D-printable lightweight, strong and refractory materials

can be useful for numerous ground and aerospace applications as well as for

personalized heavily loaded skeleton implants.

Conclusions

CF-PEEK composites can be successfully FDM 3D-printed using a specialized

set-up applicable for highly filled polymers that allows introducing continuous carbon

yarns into nozzle. The density of 3D-printed CF-PEEK composite is lower than for its
cast counterparts due to the ACCEPTED MANUSCRIPT
additional porosity (about 1 %) and imperfections

introduced into the material between consequently deposited layers and within single

deposited layers. The additional porosity is closed and does not result in additional

water absorption. On the other hand, additional water absorption in 3D printed CF-

PEEK composites reinforced with continuous carbon yarns does take place, and is

related to the lack of impregnation of continuous carbon yarns with matrix polymer that

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provides moisture access to the core of material.

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The thermal diffusivity and conductivity of 3D-printed composites are 25 – 30

% smaller than in cast composites due to the presence of additional porosity and

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imperfections.

The thermal diffusivity and conductivity in cast composites show strong

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anisotropy due to the predominant alignment of carbon fibers along the direction of

polymer laminar flow. In contrast, 3D-printing of CF-PEEK composites filled with

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continuous carbon yarns allows directed control over the anisotropy of thermal

properties in order to satisfy specific design requirements.

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Acknowledgement
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This work is supported by the Federal targeted program “Research and

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development in priority directions of development of scientific-technological complex

of Russia” in 2014- 2020 years under agreement 14.581.21.0005,

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(RFMEFI58114X0005).
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Figure 1. The model of imperfection hierarchy in 3D-printed CF-PEEK composites.
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Figure 2 – The outlook of 3D printed CF-PEEK articles (a,b) and specimens (c) cut

from the samples printed at SkolTech FDM Z2 3D printer.

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Figure 3 – Structure details in 3D-printed CF-PEEK composites – a)-d) the appearance

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of cryogenic cracking surfaces in PEEK+20% CF composite; e)-f) interfaces of PEEK

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matrix and Tenax carbon yarn in UD PEEK+5% CY composite.

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Figure 4 – The appearance fracture surfaces of 3D-printed PEEK+20 % CF composite.

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White arrows correspond to the axes given in the Figure 1. The surface a) and b) were
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obtained after mechanical delamination of layers visible in c) and d).
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Figure 5 The FT-IR spectra for 3D-printed and cast PEEK.

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Figure 6 – Heat capacity of cast CF-PEEK composites.
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Figure 7 – Thermal diffusivity of cast and 3D-printed CF-PEEK composites.

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Figure 8 – Thermal conductivity of cast and 3D-printed CF-PEEK composites.