Professional Documents
Culture Documents
Method of Formulating Geopolymer For 3D Printing For
Method of Formulating Geopolymer For 3D Printing For
H I G H L I G H T S G R A P H I C A L A B S T R A C T
a r t i c l e i n f o a b s t r a c t
Article history: An innovative methodology is presented for formulating geopolymer-based material for the requirements and
Received 8 July 2016 demands of commercially available powder-based 3D printers. Different key powder parameters such as particle
Received in revised form 15 July 2016 size distribution, powder bed surface quality, powder true/bulk densities, powder bed porosity, and binder drop-
Accepted 28 July 2016
let penetration behavior were used to quantitatively evaluate the printability of prepared geopolymer-based ma-
Available online 29 July 2016
terial. Results indicated the prepared geopolymer-based material achieved sufficient printability to be used in a
Keywords:
powder-based 3D printer. 3D printed specimens from the geopolymer were assessed for printing accuracy, ap-
Additive manufacturing parent porosity and mechanical property. All printed cubic specimens exhibited an anisotropic phenomenon in
Powder-based 3D printing dimensional accuracies and mechanical properties. Before further post-processing, the printed cubic structure
Construction gained compressive strength of up to 0.9 MPa with an acceptable low dimensional expansion of b4%. Post pro-
Geopolymer cessing by immersion in saturated anhydrous sodium metasilicate solution at 60 °C gained compressive strength
of up to 16.5 MPa.
© 2016 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.matdes.2016.07.136
0264-1275/© 2016 Elsevier Ltd. All rights reserved.
M. Xia, J. Sanjayan / Materials and Design 110 (2016) 382–390 383
Fig. 1. Schematic illustrations of the 3DP process: (a) 3DP inkjet printing system, (b) Enlargement of the area in red rectangle: powder/binder interaction between adjacent layers.
an increased level of safety, (2) reduce on-site construction time by op- panels, permanent formworks and interior structures that then can be
erating at a constant rate, (3) minimize the chance of errors by highly assembled on site.
precise material deposition, and (4) increase architectural freedom The work presented in this paper focuses on powder-based 3DP
which would enable more sophisticated designs for structural and aes- technique as this method is capable of producing building components
thetic purposes [2,3]. with fine details and intricate shapes. There is a demand in construction
In the last few years, a variety of technologies has been developed to industry for such components which can only be made with expensive
adopt AM in construction industry. These techniques can be divided formwork systems with the currently available construction systems.
into two forms. Powder-based 3DP technique needs to be developed so that they can
produce robust and durable components at a reasonable speed to satisfy
1.1. Extrusion printing this industrial demand. Hence the urgency for research in this area.
A schematic of the powder-based 3DP process is illustrated in Fig. 1.
The extrusion printing technique is analogous to the Fused Deposi- At the start, a roller, mounted together with a print head, spreads a layer
tion Modelling (FDM) method by extruding cementitious material of powder to cover the base of the build plate. The base layer is about
from a nozzle mounted on a gantry to print a structure layer by layer. 3 mm in thickness. Then, according to the layer thickness setting of
Examples such as Contour Crafting, developed by Khoshnevis [4,5] the 3D printer, a thin layer of powder (approximately 0.1 mm) is spread
and Concrete Printing, designed by Lim et al. [6,7]. and smoothed by the roller over the powder bed surface. Once a layer is
completed, the binder solution is delivered from binder feeder to the
1.2. Powder printing print head and jetted by nozzles mounted in the print head. The mech-
anism of controlling the binder solution is a non-continuous approach
The powder printing technique, also named powder-based three di- called drop-on-demand (DoD) technique [11] which has been widely
mensional printing (3DP), is another typical AM process that creates ac- used in contemporary desktop printing systems. In the print head, the
curate structures with complex geometries by depositing binder liquid binder solution is pushed out through nozzles either thermally by a
(or "Ink") selectively into to powder bed to bind powder where it im- thermal bubble or mechanically by a piezoelectric actuator. Then binder
pacts the bed [8]. Two typical examples are the D-shape technique de- droplets are formed and are selectively applied on powder layer, caus-
veloped by Cesaretti et al. [9] and Emerging Objects [10]. ing powder particles to bind each other (Fig. 1b). Repeating the de-
Both of the two techniques are designed for construction purpose scribed steps, the built part is completed and removed after a
and have many similarities. However, each technique has distinct fea- particular drying time and unbound powder is removed by using an
tures in construction industry. The extrusion printing technique has air blower.
been aimed at on-site construction applications such as large-scale Powder-based 3DP is a versatile AM technique characterized by a
building components with complex geometries, while the powder wide range of potentially suitable materials in powder form, including
printing technique is an off-site process designed to manufacturing pre- ceramics, polymers, metals and composites [12,13]. Powder-based
cast components. It is the authors' belief that powder-based 3DP tech- 3DP technique has a great potential to make a significant and positive
nique is highly suitable for small-scale building components such as contribution to the construction industry. There are mainly two
Table 1
The chemical composition of slag (wt%).
Chemical Al2O3 SiO2 CaO Fe2O3 K2O MgO Na2O TiO2 SO3 L.O.I.a
Component 12.37 32.76 44.64 0.54 0.33 5.15 0.22 0.51 4.26 0.09
a
Loss on ignition (unburnt carbon content).
384 M. Xia, J. Sanjayan / Materials and Design 110 (2016) 382–390
limitations to prevent this technique performing at its maximum poten- type of alkali aluminosilicate cement which can have superior mechan-
tial for application in construction industry: the printer and the printing ical, chemical and thermal properties compared to Ordinary Portland
material. Cement (OPC), and with significantly lower CO2 emission. Geopolymers
As most powder-based 3D printers are in small or medium sizes, are synthesized by activation of an aluminosilicate source (metakaolin,
consideration needs to be given for the feasibility of making large size fly ash and slag) with alkaline activators.
printers for the large-scale manufacturing requirement in construction In recent years, geopolymer has attracted considerable attention be-
industry. In recent years, several large-scale powder-based 3D printers cause of its high compressive strength, excellent resistance to sulfate at-
have been developed. For example, the one designed by D-shape has a tack, good acid resistance, low creep and minimal drying shrinkage
dimension of 15 × 4 × 1 m, and the VX4000 printer from Voxeljet behavior. The utilization of industrial by-products such as slag and fly
which is capable of making sand casts as large as 4 × 2 × 1 m. ash in geopolymer is considered particular beneficial, as the disposition
In addition to the printer size, printing speed is another important of industrial by-products has always been a global issue.
consideration. In powder-based 3DP process, several factors will affect However, the applications of geopolymer have been restricted to
printing speed, such as the movement on X, Y and Z axes of the gantry small areas using conventional manufacturing techniques. A novel
system, velocity of the binder jetting in the print head and velocity of method of manufacturing geopolymer component, such as powder-
the powder spreading. As shown in Fig. 1, the binder jetting process based 3DP technique, should be taken into consideration to expand
and powder spreading process are not in parallel and this nonsynchro- the application of this eco-friendly material.
nous process has become the most critical issue that affects the printing This paper presents an innovative methodology to adopt
speed in powder-based 3DP process. Designing a system which can geopolymer-based material for the requirement and demand of com-
make these two processes operate in parallel will improve the printing mercially available powder-based 3D printers, intended for the expan-
speed. Future research works in this area need to focus on such im- sion of the limited scope of materials that can be used in a powder-
provements to increase printing efficiency. based 3D printer in construction industry. In this study, printable
Another limitation lies in the low availability of printing materials. geopolymer-based material was prepared by blending slag, anhydrous
Until recently, only a small range of cement-based materials have sodium metasilicate and fine sand. Different key parameters such as
been explored such as rapid hardening Portland cement (RHPC) [14], particle size distribution, powder bed surface quality, powder true/
calcium aluminate cement (CAC) [15], magnesium oxychloride cement bulk densities, powder bed porosity, and binder droplet penetration be-
(also known as Sorel cement) [9], fiber reinforced cement polymer [10] havior were used to evaluate the printability of geopolymer-based ma-
and ultra-high performance concrete (UHPC) [16]. As such, it is urgently terial quantitatively and compare with the commercially available
needed to expand the current severely limited scope of materials that plaster-based material. The printing accuracy, apparent porosity and
can be used in a powder-based 3D printer. mechanical property of the printed structures were investigated and
Geopolymer [17], also known as an inorganic polymer, is an alterna- benchmarked against with those printed from a commercially available
tive material that acts as the binding agent in concrete. Geopolymer is a plaster-based powder.
Fig. 3. Schematic illustrations of drop penetration behavior test: (a) Drop penetration apparatus, (b) Drop penetration parameters.
M. Xia, J. Sanjayan / Materials and Design 110 (2016) 382–390 385
2. Materials and methods for inspecting powder bed surface quality, true/bulk and in-process
bed densities, and a drop penetration measurement apparatus for char-
2.1. Materials acterizing wettability of the powders.
2.1.1. Powders
Two powder systems, slag-based geopolymer powder (marked as 2.2.1. Particle size distribution
GP) and commercially available plaster-based powder (marked as ZP), The particle size and particle size distribution of the powders were
were used in this study. A mixture of slag (Building Products Supplies measured by using a laser diffraction particle analyzer (Cilas 1190,
Pty Ltd., Australia), silicate-based activator (Redox Pty Ltd., Australia) CILAS, France). Each powder was measured three times to find out the
and fine sand (TGS Industrial Sands Pty. Ltd., Australia) was used to pre- D10, D50 and D90 values, which indicate 10%, 50% and 90% of the particles
pare the printable geopolymer-based material. The chemical composi- are below those sizes.
tion of the slag, determined by X-ray fluorescence (XRF) analysis, is
shown in Table 1. The total does not sum up to 100% due to rounding off.
The silicate-based activator used in this study was composed of 2.2.2. Powder bed surface quality
beaded anhydrous sodium metasilicate with a chemical composition After preparing the powder bed in the printer, the build plate with
of 50.66 wt% Na2O, 47.00 wt% SiO2 and 2.34 wt% H2O. TGS Industrial powder bed was removed from the 3D printer. The surface qualities of
70 Grade Sand was classified as semi-sharp sand with a median size of the two powder beds were inspected by using a Nikon D810 camera.
184 μm. The incorporation of TGS sand was aimed to function as an The inspection direction was 45° to the top of the powder bed.
inert filler in the GP powder to improve its printability.
The GP powder was prepared as follows: Firstly, anhydrous sodium
metasilicate beads were dry milled for 5 min in a planetary ball mill 2.2.3. True, bulk and in-process bed densities
with ceramic balls. Then slag, ball milled anhydrous sodium metasilicate True (ρtrue.power) and bulk (ρbulk.powder) densities of the powders
and fine sand were dry mixed in a Hobart mixer until a homogeneous were measured according to Australian Standard AS 1774.6-2001
mixture was obtained. The process of preparing GP powder is shown (R2013) for determination of true density and Australian Standard AS
in Fig. 2. 1774.2-2001 (R2013) for determination of bulk density. In-process
For comparison, a commercial plaster-based powder (Zp® 150, Z- bed density (ρbed.powder), first proposed by Zhou et al. [22], is the density
Corp, USA) was used in this study without further treatment. The ZP measured after the powder being spread to the build plate. It is an im-
powder was supplied by the same company manufacturing the 3D portant characteristic to ensure high-quality print quality in powder-
printer used in this study. The composition of the ZP powder was mainly based 3DP process.
calcium sulfate hemihydrate (CaSO4·1/2H2O) by X-ray diffraction Prior to 3DP process, the powder was spread by a roller from the
(XRD) analysis [18] and energy dispersive spectroscopy (EDS) analysis powder feeder to the build plate. Then the build plate was removed
[19]. from the 3D printer. The volume of the powder bed and the mass of
powder in the build plate were measured to determine the in-process
2.1.2. Binder bed density. The measurement was conducted three times for each
An aqueous solvent (Zb® 63, Z-Corp, USA) was used as binder during powder. Using the in-process bed density and true powder density,
the 3DP process. The binder was an aqueous commercial clear solution
with the viscosity similar to pure water. The composition of the binder
was mainly water with 2-Pyrrolidone as identified by Fourier transform
infrared (FTIR) spectroscopy analysis [20].
Table 2 remove the unbound powder. These two parameters were measured
Properties of ZP and GP powders. after each drop penetration time measurement.
Powder properties ZP GP
Fig. 7. Sequential images of binder droplet impacting on surfaces of (a) ZP and (b) GP powder bed. The number at the bottom of each frame indicates the time (ms).
Y-orientation is the direction of new layer spreading and Z-orientation contained more fine particles than the ZP powder. These fine particles
is the direction of layer stacking (Fig. 1a). have a tendency to agglomerate during the deposition process, causing
macro voids or "bubble voids" within the powder bed [23], and thus in-
2.4.2. Apparent porosity creasing the powder bed porosity. The slight difference between in-pro-
The apparent porosity of printed cubic structures was measured cess bed density and bulk density indicated both powders had not been
based on Australian Standard AS 1774.5:2014. First of all, samples compressed significantly by the roller during the printing process. Pow-
were weighted in dry state (Mdry) using a precision balance with an ac- der particles were deposited in a close condition to the free-flowing
curacy of 0.001 g, and then submerged in immersion liquid for 30 min. state [22].
Then, the weight of the sample suspended in an immersion liquid In 3DP process, one crucial requirement is the powder depositability,
(Msusp) was measured. Subsequently, each sample was taken out from which depends heavily on powder particle size [12,13]. For dry deposi-
the immersion liquid and dabbed with a wet cloth to remove excess im- tion, the suggested powder particle size is N20 μm [12]. Due to the pre-
mersion liquid and weighted to determine the wet weight (Mwet). The dominance of inter-particle attraction force, fine powder particle
bulk density (ρbulk.cube) and apparent porosity (Pcube) was calculated (b20 μm) tends to adhere to one another and form agglomerates,
by Eq. (3) and Eq. (4) respectively. which will result in insufficient depositability [24].
The surface quality of ZP and GP powder bed after deposition are
Mdry shown in Fig. 6. It was noted that the GP powder bed exhibited rough
ρbulk:cube ¼ ρliquid ð3Þ
Mwet −Msusp but even surface, while the ZP powder bed surface was smooth and ho-
mogenous. In this study, the surface quality of the GP powder bed was
ρbulk:cube already sufficient for printing [25].
P cube ¼ 1− 100% ð4Þ
ρtrue:powder In 3DP process, another crucial requirement is the wettability of
powder by the binder solution. Fig. 7 shows a series of images taken
from the footage of typical drop penetration behavior of Zb® 63 binder
2.4.3. Mechanical property on ZP and GP powder.
To evaluate the mechanical property of the printed cubic structure, As is shown in Fig. 7, the impaction and penetration behavior of the
uniaxial compressive strength was carried out at a loading rate of binder droplet on both powder bed surfaces were quite similar. Upon
0.03 kN/s. In this study, uniaxial compressive strength was measured impact the powder surface, the binder droplet elastically deformed
in both X-orientation and Z-orientation. and made a shallow crater. Solids spreading around the droplet surface
did not occur. Then the droplet reached its maximum spreading diame-
3. Results and discussions ter and started to penetrate into the powder bed driven by capillary
forces. At the end of penetration, a flat granule with a slightly higher
3.1. Powder characterizations rim was formed within the powder bed because the rate of penetrating
was slower than that of spreading. In this measurement, the penetration
The particle size distributions of the ZP and GP powders are present- time of GP powder was 350 ms, which was longer than that of the ZP
ed in Fig. 5. powder.
The ZP and GP powders exhibit similar multimodal distribution, cov-
ering approximately the same size range of 0.1 to 100 μm. However, the
GP powder curve is slightly shifted to the left, indicating that the pres-
ence of particles with smaller diameters than the ZP powder.
Table 3
The PSD analysis result showed the average particle size of ZP and GP
Drop penetration test results of ZP and GP powders.
powders were 37.85 μm and 24.60 μm respectively. The ZP powder had
a particle size distribution as D10 = 1.50, D50 = 31.64 and D90 = Powder Binder Drop penetration parameters
69.51 μm, while the GP powder had D10 = 1.23, D50 = 17.24 and tp (ms)a dp (mm)b φp (mm)c
D90 = 52.75 μm. ZP ®
Zb 63 316 ± 14 1.23 ± 0.05 2.42 ± 0.12
True, bulk and in-process bed densities are listed in Table 2. GP 344 ± 20 2.10 ± 0.11 1.95 ± 0.16
Results showed the GP powder exhibited lower in-process bed den- a
Drop penetration time.
sity and bulk density but higher powder bed porosity, compared to the b
Drop penetrating depth.
ZP powder. The PSD analysis result (Fig. 5) shows that the GP powder c
Drop spreading diameter.
388 M. Xia, J. Sanjayan / Materials and Design 110 (2016) 382–390
Fig. 8. 3D printed structures using geopolymer-based material. (a) Plate structure, (b) Cubic structure.
A summary of the drop penetration test results is given in Table 3. deeper in the powder bed to complete the whole penetration process.
Ten replicates were performed for each powder. Each value is presented This also explains the longer penetration time on GP powder bed.
as average ± standard deviation.
Results showed the GP powder had longer drop penetration time of
344 ± 20 ms than the ZP powder. In general, the drop penetration time 3.2. Characterizations of 3D printed structures
is sensitive to the powder bed structure. The drop penetration time will
be longer for powder formulation with a finer average particle size than The 3D printed structures using geopolymer-based material are
coarser one [22,26,27]. The presence of macro voids formed by fine par- shown in Fig. 8. The plate structure presented in Fig. 8a shows that the
ticles agglomeration within the powder bed will increase the drop pen- prepared geopolymer-based material allowed the production of struc-
etration time. This is because binder liquid tends to flow through ture with a minimum rectangle-shape pore size of 1 mm via the pow-
capillary pores rather than macro voids [26]. der-based 3D process. The quality of 3D printed cubic structure was
For the GP powder, the spreading diameter (1.95 ± 0.16 mm) was determined by three characteristic features: printing accuracy, apparent
smaller than that of the ZP powder (2.42 ± 0.12 mm). Spreading is porosity and mechanical property. Table 4 summarizes the DDR mea-
the first stage of drop penetration. The droplet is flattened and spread surement results of 3D printed cubic structures in three orientations.
out horizontally into a pancake shape after impacting. In a very short Thirty replicates were performed for each powder. Each value is pre-
time, the droplet reaches to its maximum spreading diameter, which sented as average ± standard deviation.
is sensitive to the physical properties of the binder liquid and wettability According to the results listed in Table 4, the lengths of all printed
of the powder [28]. cubic structures were longer than CAD model (20 mm). The dimension-
Compared with the ZP powder, the GP powder had a higher pene- al deviation ratios in three orientations were b4%. Moreover, Z-orienta-
trating depth (2.10 ± 0.11 mm), indicating that the binder droplet dem- tion had the highest deviation among three orientations. The positive
onstrated more vertical penetrating behavior in the GP powder bed. For and different deviation values indicated all cubic structures exhibited
a single fixed-volume binder droplet, the smaller spreading diameter, anisotropic expansion in all orientations. This anisotropic phenomenon
the higher penetrating depth. Meanwhile, the capillary paths in the might be associated with the bleeding mechanism in printing process
finer particle powder bed for binder droplet will become more irregular [29] and preferential orientation of the powder particles [30] in the de-
due to the presence of macro voids. The binder droplet has to penetrate position process.
Table 4
Dimensional deviation ratio of 3D printed cubic structures.
Table 5
Dimensional deviation ratio (DDR) (%) Apparent porosity of 3D printed cubic structures.
Powders X-orientation Y-orientation Z-orientation Cubic structure Bulk density (g·cm–3) Apparent porosity (%)
ZP 1.05 ± 0.55 1.75 ± 0.60 3.65 ± 0.95 ZP 0.99 ± 0.03 61.9 ± 1.8
GP 0.85 ± 0.25 1.65 ± 0.35 2.65 ± 0.85 GP 1.20 ± 0.04 57.1 ± 1.4
M. Xia, J. Sanjayan / Materials and Design 110 (2016) 382–390 389
at the Global Innovation in Construction Conference, Loughborough University, [23] M. Fayed, L. Otten, Handbook of Powder Science & Technology, Springer Science &
Leicestershire, UK, 2009 13–16. Business Media, UK, 2013.
[7] S. Lim, R.A. Buswell, T.T. Le, R. Wackrow, S.A. Austin, A.G. Gibb, T. Thorpe, Develop- [24] Q. Li, V. Rudolph, B. Weigl, A. Earl, Interparticle van der Waals force in powder
ment of a viable concrete printing process, Proceedings of the 28th International flowability and compactibility, Int. J. Pharm. 280 (2004) 77–93.
Symposium on Automation and Robotics in Construction, (ISARC2011), Seoul, [25] S. Spath, H. Seitz, Influence of grain size and grain-size distribution on workability of
South Korea 2011, pp. 665–670. granules with 3D printing, Int. J. Adv. Manuf. Technol. 70 (2014) 135–144.
[8] E.M. Sachs, J.S. Haggerty, M.J. Cima, P.A. Williams, Three-dimensional printing [26] K.P. Hapgood, J.D. Litster, S.R. Biggs, T. Howes, Drop penetration into porous powder
techniques(U.S. Patent No. 5,204,055. Washington, DC: U.S. Patent and Trademark beds, J. Colloid Interface Sci. 253 (2002) 353–366.
Office) 1993. [27] T. Nguyen, W. Shen, K. Hapgood, Drop penetration time in heterogeneous powder
[9] G. Cesaretti, E. Dini, X. De Kestelier, V. Colla, L. Pambaguian, Building components for beds, Chem. Eng. Sci. 64 (2009) 5210–5221.
an outpost on the lunar soil by means of a novel 3D printing technology, Acta Astro- [28] E. Nefzaoui, O. Skurtys, Impact of a liquid drop on a granular medium: inertia, vis-
naut. 93 (2014) 430–450. cosity and surface tension effects on the drop deformation, Exp. Thermal Fluid Sci.
[10] R. Rael, V. San Fratello, Developing concrete polymer building components for 3D 41 (2012) 43–50.
printing, Proceedings of the 31st Annual Conference of the Association for Computer [29] M. Castilho, B. Gouveia, I. Pires, J. Rodrigues, M. Pereira, The role of shell/core satu-
Aided Design in Architecture, (ACADIA 11), Banff, Canada 2011, pp. 152–157. ration level on the accuracy and mechanical characteristics of porous calcium phos-
[11] H.P. Le, Progress and trends in ink-jet printing technology, J. Imaging Sci. Techn. 42 phate models produced by 3Dprinting, Rapid Prototyp. J. 21 (2015) 43–55.
(1998) 49–62. [30] Y. Shanjani, Y. Hu, R.M. Pilliar, E. Toyserkani, Mechanical characteristics of solid-
[12] B.R. Utela, D. Storti, R.L. Anderson, M. Ganter, A review of process development steps freeform-fabricated porous calcium polyphosphate structures with oriented stacked
for new material systems in three dimensional printing (3DP), J. Manuf. Process. 10 layers, Acta Biomater. 7 (2011) 1788–1796.
(2008) 96–104. [31] E. Sachs, M. Cima, P. Williams, D. Brancazio, J. Cornie, Three dimensional printing:
[13] B.R. Utela, D. Storti, R.L. Anderson, M. Ganter, Development process for custom rapid tooling and prototypes directly from a CAD model, J. Manuf. Sci. Eng. 114
three-dimensional printing (3DP) material systems, J. Manuf. Sci. Eng. 132 (2010) (1992) 481–488.
0110081–0110089 (Transactions of the ASME). [32] A. Khalyfa, S. Vogt, J. Weisser, G. Grimm, A. Rechtenbach, W. Meyer, M.
[14] G.J. Gibbons, R. Williams, P. Purnell, E. Farahi, 3D printing of cement composites, Schnabelrauch, Development of a new calcium phosphate powder-binder system
Adv. Appl. Ceram. 109 (2010) 287–290. for the 3D printing of patient specific implants, J Mater. Sci.-Mater. M. 18 (2007)
[15] A.-K. Maier, L. Dezmirean, J. Will, P. Greil, Three-dimensional printing of flash-set- 909–916.
ting calcium aluminate cement, J. Mater. Sci. 46 (2010) 2947–2954. [33] E. Gartner, J. Gaidis, J. Skalny, in: J.P. Skalny (Ed.), Materials Science of Concrete, The
[16] C. Gosselin, R. Duballet, P. Roux, N. Gaudillière, J. Dirrenberger, P. Morel, Large-scale American Ceramic Society, Westerville, OH 1989, pp. 95–125.
3D printing of ultra-high performance concrete – a new processing route for archi- [34] C.K. Yip, G.C. Lukey, J.S.J. van Deventer, The coexistence of geopolymeric gel and cal-
tects and builders, Mater. Design 100 (2016) 102–109. cium silicate hydrate at the early stage of alkaline activation, Cem. Concr. Res. 35
[17] J. Davidovits, Geopolymers and geopolymeric materials, J. Therm. Anal. Calorim. 35 (2005) 1688–1697.
(1989) 429–441. [35] P. Duxson, A. Fernández-Jiménez, J.L. Provis, G.C. Lukey, A. Palomo, J.S.J. Deventer,
[18] A. Farzadi, M. Solati-Hashjin, M. Asadi-Eydivand, N.A.A. Osman, Effect of layer thick- Geopolymer technology: the current state of the art, J. Mater. Sci. 42 (2006)
ness and printing orientation on mechanical properties and dimensional accuracy of 2917–2933.
3D printed porous samples for bone tissue engineering, PLoS One 9 (2014), [36] S.A. Uhland, R.K. Holman, S. Morissette, M.J. Cima, E.M. Sachs, Strength of green ce-
e108252. ramics with low binder content, J. Am. Ceram. Soc. 84 (2001) 2809–2818.
[19] N. Afshar-Mohajer, C.-Y. Wu, T. Ladun, D.A. Rajon, Y. Huang, Characterization of par- [37] M. Vlasea, R. Pilliar, E. Toyserkani, Control of structural and mechanical properties in
ticulate matters and total VOC emissions from a binder jetting 3D printer, Build. En- bioceramic bone substitutes via additive manufacturing layer stacking orientation,
viron. 93 (2015) 293–301. Addit. Manuf. 6 (2015) 30–38.
[20] M. Asadi-Eydivand, M. Solati-Hashjin, S.S. Shafiei, S. Mohammadi, M. Hafezi, N.A.A. [38] W. Zhang, R. Melcher, N. Travitzky, R.K. Bordia, P. Greil, Three-dimensional printing
Osman, Structure, properties, and in vitro behavior of heat-treated calcium sulfate of complex-shaped alumina/glass composites, Adv. Eng. Mater. 11 (2009)
scaffolds fabricated by 3D printing, PLoS One 11 (2016), e0151216. 1039–1043.
[21] A. Butscher, M. Bohner, C. Roth, A. Ernstberger, R. Heuberger, N. Doebelin, P.R. Von [39] M. Asadi-Eydivand, M. Solati-Hashjin, A. Farzad, N.A.A. Osman, Effect of technical
Rohr, R. Müller, Printability of calcium phosphate powders for three-dimensional parameters on porous structure and strength of 3D printed calcium sulfate proto-
printing of tissue engineering scaffolds, Acta Biomater. 8 (2012) 373–385. types, Robot. Cim.-Int. Manuf. 37 (2016) 57–67.
[22] Z. Zhou, F. Buchanan, C. Mitchell, N. Dunne, Printability of calcium phosphate: calci- [40] P. Feng, X. Meng, J.-F. Chen, L. Ye, Mechanical properties of structures 3D printed
um sulfate powders for the application of tissue engineered bone scaffolds using the with cementitious powders, Constr. Build. Mater. 93 (2015) 486–497.
3D printing technique, Mater. Sci. Eng. C 38 (2014) 1–10.