Accepted Manuscript

Title: Feasibility study on additive manufacturing of

recyclable objects for space applications

Authors: Miranda Fateri, Ali Kaouk, Aidan Cowley, Stefan

Siarov, Manel Vera Palou, Fernando Gobartt González,
Romain Marchant, Samantha Cristoforetti, Matthias Sperl

PII: S2214-8604(18)30332-4
DOI: https://doi.org/10.1016/j.addma.2018.09.020
Reference: ADDMA 509

To appear in:

Received date: 22-5-2018

Revised date: 16-8-2018
Accepted date: 18-9-2018

Please cite this article as: Fateri M, Kaouk A, Cowley A, Siarov S, Palou MV,
González FG, Marchant R, Cristoforetti S, Sperl M, Feasibility study on additive
manufacturing of recyclable objects for space applications, Additive Manufacturing
(2018), https://doi.org/10.1016/j.addma.2018.09.020

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 Feasibility study on additive manufacturing of recyclable objects for space
applications

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Miranda Fateri†1, Ali Kaouk†1, Aidan Cowley2, Stefan Siarov2, Manel Vera Palou1, Fernando Gobartt González1,
Romain Marchant1, Samantha Cristoforetti2, Matthias Sperl1

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1-Institut für Materialphysik im Weltraum, Deutsches Zentrum für Luft- und Raumfahrt (DLR), 51170 Köln, Germany

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2- European Astronaut Centre (EAC), 51170 Köln, Germany

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†- Authors contributed equally to the work
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Abstract
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Future exploration missions beyond low-Earth orbit would significantly benefit from a closed loop
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recyclable Additive Manufactured capability, allowing the production of general purpose tools and items
in a time and cost effective manner. To realize this ambition, we present a feasibility study of a Solvent-
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Cast Direct-Write method using Polyvinyl Alcohol as biodegradable material. Process parameters such as
solution viscosity, evaporation rate, print pressure and scan speed are optimized in order to achieve a
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consistent and reliable print outcome. We demonstrate the process by fabricating test complex
geometries of sample specimens. Moreover, we report on the mechanical properties of printed
geometries as well as the recyclability aspects. Physical and chemical properties of the printable solutions
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were investigated and the viability of the method for space is discussed.
INTRODUCTION

Solid Freeform Fabrication (SFF) via Additive Manufacturing (AM) technology has brought about

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a whole new dimension of manufacturing possibilities in different industries, with aerospace being
particularly eager to adopt AM. Recently different AM technologies capable of processing different

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materials have been developed, further accelerating the adoption and development of AM
processes. (1; 2; 3; 4; 5; 6; 7; 8; 9)

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When considered in the context of Space and exploration activities around human spaceflight, AM is
widely seen as the enabler of the In-Space Manufacturing (ISM) capability. Since 2014, extrusion based

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Fused Deposition Modelling (FDM) has been deployed to the International Space Station (ISS) for

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experiments and general usage under microgravity conditions, being a robust and readily achievable
implementation of AM. The 3D printer payload, constructed and made by the company Made in Space, is
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part of an expected larger build of capability and competency to realise ISM. Additionally, the Italian Space
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Agency (ASI) has also launched the POP3D printer to the ISS and samples from both of these systems have
been brought back to Earth for mechanical characterisation. An ISM phased technology roadmap has been
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proposed by NASA (10), within which a clear focus emerges on the topic of recyclability.
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Among the developed AM technologies so far, Fused Deposition Modelling (FDM) is the most
widely adopted and commercialized desktop-scale 3D Printer. FDM was initially developed for
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materials with thermoplastic behavior, working through layer by layer extrusion of a filament fed
through a heated nozzle that moves laterally on a horizontal plane following a sliced 3D CAD file.
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The thermal degradation caused by high processing temperatures and the high viscosity of most
polymer melts make the FDM printers mostly compatible for concept modeling and geometry
prototype fabrication rather than functional parts, with some niche exceptions. (11; 12; 13; 14)
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In addition to the mentioned restrictions, recycling of the waste FDM geometries include
shredding, and re-extruding the thermoplastic material in filament form, which is a time consuming
and costly process and makes FDM limited to entities with the infrastructure and knowledge to
recycle. To overcome these limitations, Solvent-Cast Direct-Write (SC-DW) fabrication method
initially developed by Shuang-Zhuang Guo et al (15; 16), may overcome the non-homogenous
FDM heat distribution difficulties as well as the recycling challenges. Importantly, in this process,
no thermal post treatment is needed. SC-DW consists of electronically controlled micro extrusion
of a concentrated polymer solution, coupled with a controlled solvent evaporation process. So far,
SC-DW is tested and developed for Polyactide (PLA) with Dichloromethane (DCM) as the solvent.
The low boiling point of DCM (39.6 °C) causes a relatively rapid solvent evaporation during the
printing process, however; developing new polymer-solvent mixtures and overcoming the solvent

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extraction challenge may extend the SC-DW to additional applications. The capability to readily
recycle parts printed via the SC-DW process opens up the potential for investigations of its use for

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space exploration applications. Up to now, only FDM technology is tested for International Space
Station (ISS) investigations (17; 18). In this case, for long term mission goals, the filaments should

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be continuously shipped to the ISS, which is a logistically challenging and costly process. With
future exploration targets further stressing the need for greater local autonomy and the de-coupling

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of logistical support from Earth, approaches that allow for the effective use of fabrication material
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While this work illustrates the concept terrestrially, the implementation of SC-DW for space
application has some constraints on the polymers and solvents that can be used for an ISM process.
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Different characteristics of the polymer should be taken into consideration; it should be non-toxic
and recyclable providing ease of handling due to the challenging microgravity environment and
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the confined nature of any space vehicle or habitat. On the other hand, due to the limitation on the
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current solvents allowed on the space station, water becomes an appealing and viable solvent to
use. This makes Polyvinyl Alcohol (PVA), with a chemical formula of (C2H4O)x, an attractive
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polymer for this application due to the properties mentioned below:

1. Stability in solution: PVA does not degrade or mold over extended periods of time. (19)
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2. PVA is non-toxic to humans and animals alike, with no dangerous outgassing components.
(20)
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3. High solubility in water, which makes the control of solution concentration easy.

4. Solubility of PVA in water makes recycling of the material relatively simple.

Experimental

Solution preparation
Solutions used in this study were prepared from 98-98.8 % hydrolyzed PVA (VWR GmbH) and double
distilled water. Solutions of different PVA concentrations were prepared (10 - 40 wt. %). PVA was weighed
and left in the necessary amount of distilled water overnight for liquid absorption (swelling); afterwards

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the mixture was heated to 85 °C under vigorous stirring. The mixture was stirred for 30 minutes;
afterwards, the evaporated amount of water was determined by weighing and eventually compensated

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to reach the desired concentration. Alternatively, the prepared solution is kept in a sealed beaker in order
to minimize the solvent evaporation.

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Mechanical Setup
For this study, modifications on a Prusa desktop 3D printer are conducted in order to provide a layer-wise

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delivery of the print material. In the first step, the print head including the hot-end of the Prusa are

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replaced by a syringe. With regards to this, a fusion 100 syringe pump capable of providing pulseless micro-
flow material delivery from 0.5 μL to 60 mL at flow rates of 100 pl/min to 128 ml/min (depending on
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syringe tip size) is provided. However, results regarding the initial process parameter investigations have
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shown the necessity of having a setup which provides a higher pressure. Towards this end, the Chemyx
fusion 100 syringe pumps is replaced by a fluid dispenser unit. Furthermore, a METCAL DX-250 fluid
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dispenser, adequate for operating via a 5 µm air filter mesh, is connected to dispensing tool capable of
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delivering a maximum output pressure of 27.6 bar while having 10 ml syringe capacity. Finally, the
dispensing system is integrated into the 3D printer by means of a nozzle adaptor as the support structure.
The image of the modified 3D printer setup and its corresponding system diagram for solvent cast 3D
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Printing application is shown in Figure 1.

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Figure 1 Image of the AM-solvent cast experimental setup (top), system layout of the experimental components (bottom)
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Characterization
The viscosities of prepared aqueous PVA solutions were measured by using the metal ball method, where
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the velocity of a metal ball with a known density and volume is used to calculate the static viscosity of the
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liquid it is travelling through. Concentration of the used PVA solutions was calculated post-preparation by
measuring the evaporation of the water from the solution. The weight of the solution and the dried PVA
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are used to calculate the true concentration of all used solutions. Furthermore, the chemical composition
of the as purchased PVA, printed PVA and the recycled-printed PVA were determined using Infrared (IR)
spectroscopy (Perkin Elmer FTIR/IR Spectrum 400) in the range from 400 to 4000 cm-1. Compression tests
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were conducted for 3 samples using a uniaxial PEZ 1.595 servo-hydraulic testing machine. The strain
measurements were completed using a laser extensometer. The test samples were prepared in size of 20
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* 20 * 10 mm. Furthermore, samples are studied using X-ray tomography (Nanotom) in order to study
adhesion among the extruded lines and a possible final part's distortion. Skeletal densities of the powder
were measured using a gas pycnometer Micromeritic AccuPyc II. Printed samples' densities were studied
using an envelope density analyser Micromeritic GeoPyc.
Results and Discussion

Process parameter investigation

Solution viscosity (solvent and the polymer concentration), print speed, applied pressure on the solution
as well as the nozzle diameter size must be optimized in order to achieve the desired material linear flow
rate and consequently a reliable print outcome. All the aforementioned parameters have to be optimized

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to ensure the desired solutions rheological behavior in yielding a fairly rapid solvent evaporation. Solvent
evaporation is a critical factor in the final parts dimensional accuracy, as a steady print procedure is directly

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affected by the rigidity of the print structure. With respect to this, viscosity of the PVA solutions is obtained
in order to realize the rheological behavior of the PVA solutions. Results regarding the viscosity

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measurements of the prepared PVA solutions are presented in Figure 2.

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Figure 2 Viscosity of aqua PVA solutions

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Initial process parameter investigations have been conducted in order to evaluate the solvent evaporation
rate by recording the weight reduction of an extruded line as a function of time. Although the solvent
evaporation rate is a function of the extruded materials volume, the evaporation rate of an extruded single
line could be applied as a reasonable indicator of the drying process of the solution material during the
print process. Results regarding the solvent evaporation test are shown in Figure 3. As it can be seen,
solution content drops down sharply during the first 10 minutes while the extruded line needs
approximately 30 minutes to be dried by natural convection. Based on the obtained results from the
solvent evaporation study, influence of forced convection during the print process has been tested. Results
regarding the evaporation rate using a fan operating with 24 V, 210 mA are shown in Figure 3 in square
dots. As the results show, forced convention leads to approximately three times faster drying of the
printed lines compared to the obtained results from the natural convention drying process. Based on this

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implementation, the solvent is completely evaporated after 10 minutes of printing. As such, the ventilating
tool is integrated into the printer setup.

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Figure 3 Solvent content versus time for natural and forced convection
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The next focus of the development was finding the optimum solvent evaporation strategy regarding
solidification of the printed lines using different reference print temperatures. Reference temperatures
have been selected by considering the glass transition temperature (Tg) of the PVA as well as the
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evaporation temperature of the water (100 °C). With respect to this, Differential Scanning Calorimetry
(DSC) is applied to study the Tg of the PVA material. DSC measurement results for PVA material resulted in
a Tg of 80 °C. Towards this end, single lines using print bed temperatures of less and higher than PVA glass
transition have been generated and compared to the generated lines at room temperature (25 °C). Single
line extrusion test results at 25 ºC, 50 ºC and 110 ºC are shown in Figure 4. The lines are microscopically
monitored for a week after the extrusion process; however, the samples did not change after 30 minutes
of microscopy.

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Figure 4 Bubble formation in extruded lines using different print bed temperatures

In the next step, process parameter investigations have been conducted in order to find the print stability

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zone. We investigated the influence of varying different process parameters such as print speed and
extrusion pressure on the final part quality, via the single line generation test. Respectively, printed single

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lines are morphologically studied regarding the appearance of the balling effect as well as the bubble
formation. Experiments are conducted using different solutions mentioned in Figure 2 while having a
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nozzle diameter of a 200 µm. However, using single print lines led to deformed geometries despite
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applying the minimum dispensing pressure provided by METCAL DX-250 fluid dispenser. Based on this, a
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new solution with 40 % of PVA concentration is prepared; however, using the ball method, the viscosity
measurement of this solution was not achievable.
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Results have shown a balling and deformation free single line using the 4 bar pressure and 600 mm/min
scan speed as the input process parameters. It should be noted that the actual print pressure on the
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solution is approximately four times more using the dispensing tool; while, the pressure is read directly
from the fluid dispenser. Results regarding the single line generation test are shown in Figure 5. Based on
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the presented results in Figure 5, the line width of 400 µm corresponding the process parameters of the 4
bar pressure and 600 mm/min scan speed is set as the hatch spacing for a layer generation.
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Figure 5 Line width measurement results using different scan speeds and print pressures

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In the next step, obtained optimum process parameters are applied in order to fabricate a functional
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geometry. A sample separator is selected as the print element due to its possible application in space
laboratories. Printed geometry using a print pressure of 4 bar, scan speed of 600 mm/min, hatch spacing
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of 400 µm and a layer thickness of 0.15 mm is shown in Figure 6. Moreover, the printed sample is cut in 6
*4 *1 mm in build-up direction in order to study the adhesion between the printed layers. The printed
geometry is fabricated using 30 % infill density while having a rectilinear pattern.
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Figure 6 Cable holder sample (21) additive manufactured using SC-DW of PVA (left), tomography of the cut-section of the
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printed sample (right)

Characterization
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Chemical characterization of the as received PVA material and the 3D printed parts is a reliable approach
to ensure recyclability of the print process. Based on this, as received and 3D printed PVA, IR spectra
(Figure 7) were recorded to identify changes in the chemical composition of the material due to printing,
if present.
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Figure 7 IR Spectra of as received and 3D SC-DW PVA printed samples

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Measured IR spectra of both samples, show no change in major peaks (Figure 7) at 3440, 2930, 1100 and
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850 cm-1 corresponding to O-H stretching, C-H stretching, C-O stretching and C-C stretching, respectively.
(22)
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X-ray tomography showed no crack formation and distortion among the printed layers. Fabricated parts
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resulted in a skeletal density of 1.282 g/cm³ while the pure PVA provided from the supplier has a skeletal
density of 1.299 g/cm³.
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Furthermore, compression test on the samples fabricated using the optimum process parameters is
conducted. Results regarding the compression tests are shown in Figure 8. Two different deformation
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stages can be identified by the results. Plastic yielding appears at 7.5 MPa. At 23 MPa maximum
densification occurs. Parts exhibit a Young's modulus of 41 MPa.
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Figure 8 Compression test results of the SC-DW PVA printed samples

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Understanding the effect of microgravity on such a process is outside the scope of this feasibility study,
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however it bears some comment. Already, ISM demonstrated via the FDM process has been achieved
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onboard the ISS, however this was largely done via empirical testing to the parameters, either via
qualification parabolic flights or actually on orbit. For example, NASA reported that visual feedback was
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used for z-calibration (tip-to-tray distance) during their calibration coupon prints (23). This manual tuning
was not to be changed subsequently, unless there was a disruption or anomaly with the print job. Likely,
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for the SC-DW process, an element of empirical testing under microgravity conditions would be necessary
to correctly account for the effects onboard microgravity stations or exploration vehicles.
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While the challenges to print with this technique in microgravity conditions may be difficult to surmount,
it should also be noted that exploration roadmaps foresee (24) sustainable human presence in the medium
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term on planetary surfaces such as the Moon and eventually Mars. In this context, SC-DW processes would
likely be readily applicable with minimum adaption needed to the terrestrial extrusion system used herein,
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owing to a stronger gravity presence.

Conclusion
40 wt. % solutions of 98-98.8 % hydrolized PVA are created in order to investigate the feasibility of the SC-
DW for printing and recyclability, with a potential application in space exploration. Integration of the
forced convection into the print set up led to a deformation free print track, while enabling the heating
bed resulted in bubble formation within the print lines. Print pressure of 4 bar (fluid dispenser pressure),
scan speed of 600 mm/min, hatch spacing of 400 µm and a layer thickness of 0.15 mm are concluded to
be the optimum process parameters. Fabricated parts resulted in a skeletal density of 1.282 g/cm³. Printed
samples exhibited Young's modulus of 41 MPa. Compression test results showed that, part undergoes
plastic yielding at 7.5 MPa while at 23 MPa maximum densification occurs. The recycled printed samples
showed no change in major peaks at 3440, 2930, 1100 and 850 cm-1 corresponding to O-H stretching, C-H

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stretching, C-O stretching and C-C stretching, respectively. Ultimately, SC-DW is concluded to be a feasible
AM technique for printing recyclable materials for space application.

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Acknowledgement

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This project is a result of collaboration between the Spaceship EAC initiative and the German Aerospace
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Center (DLR). Special thanks to, Alexandre Meurisse from material physics in space institute and Eva Meyer
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from material science institute of DLR in Cologne.
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