Materials Research Express

ACCEPTED MANUSCRIPT

Influence of several binders on the mechanical properties of alumina

parts manufactured by 3D inkjet printing
To cite this article before publication: Nathália Oderich Muniz et al 2019 Mater. Res. Express in press https://doi.org/10.1088/2053-1591/ab4e3a

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Page 1 of 17 AUTHOR SUBMITTED MANUSCRIPT - MRX-118062.R1

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2 INFLUENCE OF SEVERAL BINDERS ON THE MECHANICAL PROPERTIES OF
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4 ALUMINA PARTS MANUFACTURED BY 3D INKJET PRINTING
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7 Nathália O. Muniza, Fernanda A. Vechiettia,b,c*, Luis Alberto L. dos Santosa
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10 a
11 Laboratory of Biomaterials, Materials Engineering Department, Federal University of Rio Grande
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do Sul, Porto Alegre/RS, Brazil
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Center for Translational Bone, Joint and Soft Tissue Research, Medical Faculty Carl Gustav
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16 Carus, Technische Universität, Dresden, Germany
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18 Mechanics and Composite Materials Department, Leibniz-Institut für Polymerforschung, Hohe
19 Straße 6, 01069 Dresden, Germany
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21 _________________________________________________________________________________________________________________
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23 Abstract
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Inkjet printing is a fast, flexible, highly reproducible, and cost effective manufacturing technology
26 that allows the production of both simple and complex 3D geometries from Computer-Aided
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Design (CAD) data without the requirement of extra tooling. In this work, we studied the influence

30 of different binders (polyvinyl alcohol (PVA), polyvinyl acetate (PVAc) and arabic gum) on the
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mechanical and porosities properties of ceramics alumina (Al2O3) parts manufactured via 3D inkjet
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33 printing. Green specimens were printed using Al2O3 powder as a precursor material and PVA,
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35 PVAc and arabic gum suspensions as binder. Green samples were sintered at 1200–1500 °C for 1 h.
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37 The microstructure and porosity of sintered samples were evaluated by scanning electron
38 microscope (SEM). Apparent porosity, apparent density and water absorption were measured and
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40 the influence of the binders on the compressive behavior was investigated. Results showed that the
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42 compositions with best geometric format and mechanical strength were those with polyvinyl
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alcohol and arabic gum. These specimens showed superior values of apparent densities, lowest
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45 porosities, presenting pore size of ≈12 μm, and compression strength of ≈25 MPa.
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47 Keywords: 3D printing; Alumina; Binder; Mechanical properties; Porosity.
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51 1. Introduction
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Manufacturing of ceramic materials through additive manufacturing (AM) technology has being
54 rapidly widespread mainly due to their ability to produce parts with complex geometries without
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56 molds. These materials have been used in aerospace, automotive, medical, electronics, and military
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58 fields [1]. Several researches attempted to improve this processing technique. Ebert et al [2]
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60 Corresponding author: fernanda.vechietti@ufrgs.br
Phone: +49 351 4658 1423; Fax: +49 351 4658 362
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2 produced three-dimensional 3Y-TZP components (zirconia stabilized by 3 mol-% Y2O3 with
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4 dispersant based on polyacrylic and carboxylic acid) by AM; Ebert et al. [3] developed a tailored
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3D printing method to manufacture dental prosthetic restorations from high-strength zirconia.
7 Seerden et al. [4] found that the properties of inkjet printing were positively influenced by
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9 suspension of fine alumina powder dispersed in paraffin wax. Derby et al. [5] discussed the
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11 requirements to successfully manufacture ceramic parts considering the fluid properties and drop
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placement accurately. However, the restricted choice of materials for manufacturing of the
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14 prototype still is a major limitation of additive manufacturing techniques, which limits the reach of
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16 the material properties assigned to the prototype [6].
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18 Inkjet 3D printing technique, one of AM technologies used for ceramic manufacturing,
19 constitutes the construction of a part printing layer-by-layer [7]. For conventional manufacturing of
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21 ceramics, an adhesive element is required. The primary function of a binder is to give mechanical
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23 strength to the structure and serve as a bridge to connect the particles to each other. The binder can
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also provide plasticity depending of the forming method. Several organic substances have been
26 utilized as binders, including vinyl, acrylics, and glycols [8]. Two other ways to add the binder in
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this manufacturing technique are possible: as a formulation for ink or mixing the ceramic powder

30 formulation.
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Several studies have been carried out using different inks with binder, bonding the powder
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33 in the desired areas. Among them, Bergmann et al. [9] developed a combination of β-tricalcium
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35 phosphate and biocompatible glass for bone implants using different combinations of
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37 orthophosphoric acid and pyrophosphoric acid in combination with isopropanol for ink solution.
38 The use of a suspension composed by fine alumina powder and paraffin wax showed to be possible
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40 to pass through the inkjet printer head [10,11] to evaluate the microstructure of parts produced with
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42 silicon nitride (LPS-Si3N4) and poly (ethylene glycol) (PEG) as ink. Song and Nur [12] identified a
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number of defects on the structure, its causes and how prevented it related to the ink properties and
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45 printing conditions which cause and prevention related to the ink properties and printing conditions.
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47 They concluded that non-use of inks results in a higher drying rate of the binder and it was shown to
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49 be more able to prevent droplet penetration and undesirable voids.
50 Despite a large number of studies using inks with a binder, the most common method is to
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52 mix it with ceramic powder. The binder action is activated through the addition of a solvent in the
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54 jetting process, as explained by Utela et al. [13]. Zhang et al. [14] fabricated alumina/glass
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composites by 3D printing using alumina mixed with dextrin powder and then added without
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57 pressure, lanthanum-alumina-silicate glass into the sintered porous alumina. Wang et al. [15]
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59 produced aluminum-nitrate doped silica GRIN lenses from 3D printing formulating silica slurries
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using poly (ethylene glycol) as the binder. The influence of raw powder preparation was examined
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2 by Suwanprateeb et al. [16], comparing spray drying and grinding for 3D printing of hydroxyapatite
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4 (HA). In both cases they used maltodextrin powder as a binder mixed with hydroxyapatite. The
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milled powders showed a better inter- and intra-particle densification in the sintering process than
7 spray-dried powders. The spray-dried powders exhibited high intra-particle densification, but a
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9 lower inter-particle densification. Chumnanklang et al. [17] prepared a slurry from the mixture of
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11 HA, water and natural polymer and evaluated the effect of the maltodextrin binder concentration on
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the mechanical properties of the HA bodies manufactured by 3D printing. The results showed that
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14 the increasing of binder concentration improve strength of the green and sintered bodies. Other
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16 types of binders, such as the already cited dextrin, alkane wax also have been widely used with
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18 alumina for 3D printing [18], polyvinylbutyral [19] and PVA [20].
19 In order to better understand the effects of different binders on the mechanical and physical
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21 properties of 3D-printed alumina structures, which is still yet to be understood, this work focuses on
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23 the design, manufacturing and testing of 3D-printed alumina parts with several binders. The
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influence of polyvinyl alcohol (PVA), polyvinyl acetate (PVAc) and arabic gum (AGu) binders on
26 compressive strength, densification, porosity, pores size, and shrinkage properties are addressed.
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30 2. Experimental details
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2.1 Raw materials
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33 Alumina powder (ALCOA, mean grain size of 3.68 µm), PVA P.S. (SIGMA-ALDRICH),
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35 Arabic gum (SYNTH), PVAc (SCOTCH), Ammonium Polyacrylate (NH4PMA - LAMBRA) were
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37 used as-received directly from the suppliers.
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40 2.2 Alumina formulation preparation
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42 In order to prepare four different powder formulations for the 3D printing process: APVA,
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APVAc, and AGu were used as binder and mixed with the alumina powder and ammonium poly
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45 (methacrylate) (NH4PMA) was used as dispersant. The powder formulation are shown in Table 1.
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47 Firstly, both binders and dispersants were dissolved in 30 w.t. % into distilled water at 60
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49 °C. Then, the alumina powder with glass phase was slowly added and continuously magnetically
50 stirred. After that, the mixture was ball-milled (2 h) and sieved (120 mesh) and dried in an oven (24
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52 h for 40 ºC) to obtain the powder precursors of the 3D printing. To prepare the AGs formulation the
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54 alumina with glass phases and binder were dry-mixed in a ball mill in the same conditions of other
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formulation.
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57 Binder concentration values were chosen based on preliminary tests performed using 1, 2
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59 and 3 wt.% concentration in total formulation. These preliminary results showed that 3 wt% was the
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minimal value, which allows obtaining the best printability in the current work.
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4 Table 1. Formulations of the produced powders.
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6 Formulations (wt. %)
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Components
APVA APVAc AGu AGs
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9 Alumina 96% 96% 96% 97%
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11 NH4PMA 1% 1% 1% -
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13 PVA 3% - - -

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15 PVAc - 3% - -
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17 Arabic gum - - 3% 3%
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Distilled water 30% 30% 30% -
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22 2.3 3D printing
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24 APVA, APVAc, AGu AGs powder formulations were used to obtain eight rectangular green
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samples (40 mm × 7 mm × 6 mm), and twelve cylindrical green samples (dimensions 6 mm × 12
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mm) via 3D inkjet printing (ZCorporation, ZPrinter® 310 Plus 3D printer). Each formulation was
placed on the “feed” platform printer. The quantity value of the released fluid was set at 150%
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31 (considered optimum for printing after some previously tests), as this value was applied to the
32 extern region and to the intern region of the manufactured part. Moon et al. [21] reported that the
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34 preform microstructure could be controlled through determining the saturation value of the released
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36 fluid, resulting in an interaction between the droplet fluid and the specific material for each amount.
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The specimens were removed from the 3D printer and heat treated in an oven (electrical
39 furnace INTI Maitec) for 1 h at 400 ºC with a heating rate of 10 ºC/min to remove organic products
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41 by pyrolysis, maintaining this rate from 400 ºC to 1200 ºC. The specimens were sintered for 1 h
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43 between 1200 ºC and 1500 ºC with a heating rate of 5 ºC/min to achieve the desired mechanical
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properties. At last, the samples were kept in the oven up to room temperature.
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48 2.4 Characterization
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50 The alumina powder with glass phase was evaluated with regards to the particle size
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distribution (particle-size analyzer CILAS, 1180L) and specific surface area (BET). Scanning
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53 electron microscopies (SEM) analysis was carried out in a JEOL equipment (model JSM-6060) to
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55 investigate the powder morphology. The thermal transition of the binders were evaluated by
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thermogravimetric analysis (TGA) in a TA Instruments equipment (model 2050), and differential
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58 scanning calorimetry (DSC) using a TA Instruments equipment (model Q20).
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2 The green samples were measured using a digital caliper (MITUTOYO) and weighed in an
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4 analytical balance (Shimadzu, ModelO AUY220), in order to determine the volumetric density,
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which was calculated from ratio of the bulk value per volume. After sintering, the apparent porosity
7 density and water absorption of the samples were measured following the ASTM B962-13 standard.
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9 Compression tests were carried out in a universal testing machine (Instron, model 3369) at a
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11 displacement rate of 1 mm/min, following the recommendations of ASTM C1424-10 standard. The
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shrinking of sintered samples was performed by quantifying the dimensions of sintered and non-
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14 sintered parts by employing a digital sliding caliper (MITUTOYO).
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18 3. Results and Discussion
19 3.1 Powder results
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21 Table 2 shows the particle size values, which exhibited a mean diameter of 2.51 μm and the
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23 BET analysis showed a specific surface area of 5.21 m2/g. SEM images (Fig. 1) showed that the
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particles of alumina have irregular shapes and their sizes were consistent with the results obtained
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30 Table 2. Particle sizes of the alumina with glass phase
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32 Diameter (µm) 10%< 50%< 90%< Mean diameter
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Alumina with glass phase 0.11 2.03 5.84 2.51
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53 Fig. 1 - Micrograph of the alumina powder with glass phase.
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57 3.2 Thermal stability of the binders

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Thermal stability was studied in order to evaluate the thermal degradation of the polymers,
60 which is a determinant step to achieve parts free of defects [22]. The curves obtained by thermal

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2 gravimetric analysis (TGA) the derivative thermo-gravimetric (−𝑑𝑚/𝑑𝑡) (DTG) of the polyvinyl
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4 alcohol, polyvinyl acetate, arabic gum and are shown in Fig. 2.
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The thermogravimetric analysis (Fig. 2(a)) of the PVA showed that the first mass loss
7 occurred around 110 °C, and that simultaneously there was a small exothermic reaction peak (Fig.
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9 2(b)). Between 200 °C and 500 °C, a sharp mass loss was observed. At the same temperature range,
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11 an exothermic peak at ≈350 °C and a small peak at ≈450 °C were observed. After 500 °C, no
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significant mass loss was reported. Tsuchiya and Sumi [23] showed that the thermal degradation of
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14 the PVA occurs in two stages, the first related to loss of water and volatile components, and the
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16 second involves the breakdown of polyene chains (due to water loss) to form aromatics.
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34 Fig. 2 – Thermal curves: (a) TGA analysis - mass loss; (b) DTG analysis – derived of the binders:
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36 polyvinyl alcohol, polyvinyl acetate and arabic gum.
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The thermogravimetric analysis (Fig. 2(a)) for the polyvinyl acetate binder showed a sudden
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41 mass loss from −25 °C to ≈142 °C, while an exothermic peak was found at ≈142 °C. Afterwards, a
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43 more subtle loss was kept up to ≈330 °C. From this temperature, the speed of mass loss slightly
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45 increased to 500 °C. Another exothermic peak at ≈330 °C is observed in the DTG curve (Fig. 2(b)).
46 The mass loss of the arabic gum started at around 80 °C, and it was accentuated from ≈250 °C (Fig
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48 2(a)). Concomitantly, there was an exothermic reaction peak in the DTG curve (Fig. 2(b)). After
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50 400 °C, the TGA curve did not record a significant mass loss up to 800 °C. Also, the DTG curve did
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not record reaction peaks after 800 °C. An important characteristic introduced by all the binders
53 was the mass loss that occurred in a wide temperature range, showing that organic material was
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55 released slowly. Thus, it is expected that the generated gaseous products will not cause abrupt
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internal pressure inside the part, which could lead to cracks and fractures as described in the
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58 literature [24]. The curve shown in Fig. 2 presents an endothermic transition at 159 °C.
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2 DSC curves show the melting pointing of the binders (Fig. 3), which is an indicator for
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4 selection of solvent temperature during burning of organic products [25,26]. According to the DSC
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analysis, the PVA binder has a glass transition temperature (Tg) of ≈80 °C and a melting point at
7 194 °C. The PVAc showed the first enthalpy variation occurred at about 30 °C, which was the Tg of
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9 the material, while a first-order endothermic peak representing the melting point could be seen at
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11 104 °C. The arabic gum binder showed an endothermic transition at 159 °C (Fig. 3).
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According to TGA of the binders the highest weight loss occurred between 50 °C – 350 °C
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14 and DSC analyses corroborated that the melting point was found between 103.7 °C – 193.9 °C,
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16 which indicates that a particular heating rate is required in this temperature range during binder
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18 burn out. Thus, the green samples were debinded at 400 °C for 1 h at 10 °C/min looking for
19 decomposing of the binders and then sintering was carry out from 1200 °C to 1500 °C for 1 h with
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21 at a rate of 5 °C/min.
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42 Fig. 3 – DSC curve of the polyvinyl alcohol polyvinyl acetate, arabic gum, binder.
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46 3.3 Prototyped sample results
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- Green parts:
49 All parts were measured and weighed in order to obtain their volumetric densities (Fig. 4).
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Density values of the printed samples were lower in relation to pure alumina pressed samples
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53 (density of ~ 3.94 g/cm³). This can be attributed to the fact that the printing process is a method in
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which particles are united only by approximation due to the interaction of existing forces and are
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56 held together by a binder fluid [27] without using external forces to compact them. Thus, the
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58 binders that presented the better particle compaction were the APVA and AGu.
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21 Fig. 4 – Volumetric density of all bars and cylinders.
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24 - Sintered properties
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26 The binder compositions were assessed to determine their influence on the sintered
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properties of both alumina bar and cylindrical specimens. Compact bar and cylindrical specimens
with different shapes (Figs. 5 and 6) and sizes were obtained after sintering. APVA and AGu
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31 formulation showed better printing and surface results in both bars and cylinders. APVAc and AGs
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33 formulations also allowed to print bars and cylinders, although the dimensions varied considerably.
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35 However, for complex shapes such as cylinders, it was observed that all parts had deformities and
36 loss of material (Fig. 6). Both bars formulations with arabic gum (dry and humid process) showed
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38 similar results and APVAc formulation presented more irregular structure. Cylindrical specimens
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40 with APVAc and AGs also presented more irregular structures, whereas APVA and AGu
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formulations had more homogeneous structure.
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54 Fig. 5 – Printed bars with different binders after sintering (APVA = 38.9 mm × 6.7 mm × 5.9 mm,
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56 APVAc = 38.7 mm × 6.7 mm × 5.9 mm, AGu = 38.7 mm × 6.7 mm × 5.5 mm, AGs = 39.8 mm ×
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6.6 mm × 5.6 mm).
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2 Through the arabic gum formulations, it was possible to print samples in bars and cylinders,
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4 but more uniforms samples and with better geometries were obtained from AGu formulation, which
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shows that the binder composition affect the structure of samples.
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24 Fig. 6 – Cylinders obtained for the 3D printing after sintering, using different binders (APVA= 11.8
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26 mm × 5.5 mm, APVAc = 5.5 × 11.2 mm, AGu = 6.1 mm × 10.4 mm, 5.7 mm × 11.7 mm).
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Difficulties in obtaining the theoretical density from ceramic materials are attributed to non-
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31 uniformities existing in green samples. Most of these originate due to the particle size distribution
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and the powder agglomeration degree [28]. Non-uniformities existing in the green samples are
34 directly related to the type of ceramic processing and the way the particles are connected to each
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36 other, which can influence the porosity of the 3D printed specimens. Thus, density results obtained
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38 by the Archimedes method (Figs. 7, 8 and 9) were expected. As can be seen in Figs. 7 and 9, the
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binder compositions influence the apparent density and porosity of the sintered bars and cylinders.
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41 The higher density value for the APVA and AGu sample is attributed to fact that the temperature of
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43 mass loss of the PVA and arabic gum is higher, resulting in a slower burning than PVAc. Fig. 8
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45 shows that lower water absorption for the APVA and AGu samples was found, which is related to
46 the lower porosity of these samples.
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48 As all the manufacturing applied the same printing parameters and all mixtures were also
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50 sieved, this could relate to the agglomeration of grains with the apparent density and apparent
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porosity. It is likely that the binders for both APVA and AGu formulations were easier to wet and
53 cover the particles, thereby presenting higher density values. Furthermore, it could be possible that
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55 as one of the arabic gum compositions was prepared via the dry method and thus did not use a
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dispersant (which was liquid), the particulate may have agglomerated and the binder decanted
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during printing.
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22 Fig. 7 – Mean values of apparent density of bars and cylinders for different binders compositions.
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25 Klawitter and Hulbert [29] reported that the size of the interconnection is critical factor,
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because it can influence the quality of tissue growth with calcium aluminates. In this study, the
required sizes of the interconnections were 4100, 440 and 45 μm for the growth of mineralized
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tissues, osteoid and fibrous tissue, respectively. Corroborating these findings, Lu et al. [30]
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32 concluded that the critical size of the interconnecting pores for bone ingrowth was 50 μm when
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34 using hydroxyapatite or β-TCP. Therefore, the prime factor for bone growth is not pore size, but the
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36 size of the interconnecting pores [31], which is frequently associated to pore size [32] and degree of
37 porosity [33].
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25 Fig. 10 shows the micrographs of the pores for samples with different formulations. The
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average pore size observed was about 12 μm, (Fig. 11) and interconnection of the pores for the
printed samples presented an average porosity of 40 – 45%. This interconnection can be seen in Fig.
30 12, which the colored liquid penetrated through the sample and the permeability is observed in the
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41 Fig. 12 – Interconnection of the pores can be seen when a liquid has contact with the bar. Bar
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46 The compression strength curve in Fig. 13(a) and the volumetric retraction Fig. 13(b) for
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48 sintered samples for each tested formulation (APVA, APVAc, AGu and AGs) shows that the binder
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50 compositions changed the mechanical performance of sintered specimens. As can be seen in Fig.
51
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13(a), the compression strength increases as the degradation temperature of the binders increases
52
53 (APVA = 26 MPa, AGu = 24 MPa and APVAc =18 MPa). The APVAc specimen presented the
54
55 lowest compression strength (18 MPa). According to TGA analyzes (Figs. 2(a) and 2(b)), this
56
specimen loses weight prior to other families of specimens (PVA -110 ºC − 450 ºC), arabic gum (80
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57
58 ºC – 400 ºC) and its faster mass loss results in pore channels that lead to a decrease of mechanical
59
60 properties during the removal of the binder. Moreover, the APVA specimen has a higher

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2 hydrophilic character (OH- groups) than APVAc, which allows a better wettability on the surface of
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4 the particles and dissolution of PVA in water that keep the particles together in the initial stages of
5
6
the burn out (debinding).
7 The AGs formulation presented highest compression strength (27.2 MPa) and volumetric
8

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9 retraction value (53.1 %) and it could be related to lower binder concentration and no addition of
10
11 water. Since the increasing water content promotes decreasing of the compressive strength, because
12
the removal water during sintering should results in pores and the volumetric retraction in the
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14 sintered specimens.
15
16 As expected, among the tested formulations, lower compression strength was observed for
17
18 the APVAc samples due to their high apparent porosity value (around 50%). The volumetric
19 shrinkage (Fig. 13(b)) showed a reducing around 50% for the bars and cylinders unique
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21 composition that differed was the AGu, where mean values were 35 % for bars and 60 % for
22
23 cylinders.
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Fig. 13 – (a) Values of the maximum strength compression - cylinders (MPa); (b) Values of
45 volumetric retraction - bars (%).
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47
48
49 4. Conclusion
50
In this study, the influence of different binders on mechanical properties of alumina
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52 specimens manufactured by 3D inkjet printing was investigated. All binders were successfully
53
54 eliminated during debinding process and the sintering allowed achieving mechanical strength,
55
56 which has proven possible to obtain parts of alumina with different geometries and binders by
Ac

57 additive manufacturing. The compositions that performed best in terms of appearance and structural
58
59 values were APVA (alumina + PVA) and AGu (alumina + arabic gum - humid). These showed the
60
highest mean values of volumetric density (APVA: 0.9 g/cm³ and AGu: 0.8 g/cm³) and apparent
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2 density (APVA: 2 g/cm³ and AGu: 1.9 g/cm³), the lowest mean values of porosity (APVA: ~ 41 %
3
4 and AGu: ~ 42 %), a mean pore size of around 12 μm for both compositions, and a mean
5
6
mechanical strength of ~ 25 MPa, also in both cases. The APVAc showed the worst results for its
7 appearance and structural properties. Regarding volumetric shrinkage, their values do not depend on
8

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9 the binder used in the parts prepared for 3D printing. This study demonstrated that the variation of
10
11 the binders compositions have influenced on the parts built by 3D printing, thermal debinding and
12
mechanical strength of the alumina. Therefore, there is the need to continue investigating these
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14 binders when used in additive manufacturing techniques, in order to achieve better results from
15
16 mechanical strength.
17
18
19 Acknowledgments
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21 The authors gratefully acknowledge CAPES, CNPQ, FAPERGS, and FINEP for thei
22
23 financial support.
24
25
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