Author’s Accepted Manuscript

Microstructure evolution and mechanical properties

of ceramic shell moulds for investment casting of
turbine blades by selective laser sintering

Qian Wei, Jiangwei Zhong, Zilin Xu, Qingyan Xu,

Baicheng Liu
www.elsevier.com/locate/ceri

PII: S0272-8842(18)30804-6
DOI: https://doi.org/10.1016/j.ceramint.2018.03.227
Reference: CERI17864
To appear in: Ceramics International
Received date: 29 January 2018
Revised date: 23 March 2018
Accepted date: 26 March 2018
Cite this article as: Qian Wei, Jiangwei Zhong, Zilin Xu, Qingyan Xu and
Baicheng Liu, Microstructure evolution and mechanical properties of ceramic
shell moulds for investment casting of turbine blades by selective laser sintering,
Ceramics International, https://doi.org/10.1016/j.ceramint.2018.03.227
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 Microstructure evolution and mechanical properties of ceramic shell

moulds for investment casting of turbine blades by selective laser

sintering
Qian WEI, Jiangwei ZHONG, Zilin XU, Qingyan XU*, Baicheng LIU

Key Laboratory for Advanced Materials Processing Technology (MOE), School of Materials Science and

Engineering, Tsinghua University, Beijing 100084, China

*
Corresponding author.

scjxqy@tsinghua.edu.cn

Abstract: Ceramic shell moulds fabricated by traditional shell-making technology have relatively
low strength, and often crack during the casting process due to the low strength. In addition, the
traditional shell-making process requires long period and high cost. In this work, qualified mullite
ceramic shell moulds with enhanced strength were fabricated by selective laser sintering (SLS)
combined with high-temperature sintering process. The effects of SLS process parameters on
dimensions were investigated, and process optimization was proposed by orthogonal experiments.

The effect of sintering temperature on strength at room temperature and 900 °C were studied. X-ray

diffraction analysis (XRD) and scanning electron microscopy (SEM) analysis suggested that
mullitization behavior was influenced by sintering temperature. Furthermore, the content of mullite
phase, mullite grain sizes, and mean length-diameter ratio of the mullite grains increased with the

sintering temperature. Mechanical testing results showed that the samples sintered at 1610 °C had

an excellent compressive strength of 99.01 MPa at room temperature and over 172.02 MPa at 900 °

C. These values far exceed those of ceramic shell moulds fabricated by the traditional shell-making
process (40.43 MPa).

Keywords: ceramic shell mould; SLS; mullite; mechanical properties

1. Introduction

Turbine blades operating in extremely harsh conditions fail either due to creep,

corrosion, oxidation, low-cycle fatigue (LCF), or high-cycle fatigue (HCF) [1]. The

quality of turbine blades relies heavily on the quality of ceramic shell moulds. The
________________________

1
fabrication of ceramic shell moulds is therefore a significant step for investment casting.

Traditional ceramic shell mould materials include zircon sand, fused alumina, Al-Si

refractory materials, and fused silica. Ceramic shell moulds fabricated by traditional

shell-making method for investment casting often crack while casting due to their low

strength [2]. Therefore, strength is the most reliable performance indicator of ceramic

shell moulds. Strength characterization at room temperature is inadequate in illustrating

ceramic shell mould behavior at high service temperatures. Therefore, hot strength is

essential to withstand the impact of liquid metal [3]. In addition, ceramic shell moulds

are prepared by dipping the shape in ceramic slurry, stuccoing and drying; the whole

process is repeated 6 to 7 times, requiring long production cycles and high costs.

Selective laser Sintering (SLS), one of the most significant additive manufacturing (AM)

advancements in the past 20 years, can produce parts with complex shapes. Invented by

Dr. Carl Deckard at the University of Texas in 1980s [4], its application has flourished

in various fields [5-10]. SLS can produce parts with qualified dimensional precision and

is not limited by the complexity of parts; it is particularly suitable for single and small

batch production [11].

In recent years, researches have made remarkable process on the application of

SLS to metals, polymers and ceramics [6, 12-20]. Laser sintering of ceramic materials is

hindered by the high melting points of ceramics. Song et al [6] investigated the effect of

process parameters on the forming qualities of silica sand patterns. Wen et al [21]

obtained binder-coated Al2O3 sand mould with complex shape by SLS, and investigated

2
the effects of binder content, raw sand type, and post-curing process on the strength and

gas evolution of sand moulds. Liu et al [22] prepared kaolin ceramic by combining SLS

with cold isostatic pressing (CIP) and obtained consolidated parts. It was found that

SLS products represented acceptable shrinkage and high density when the laser energy

density was 0.3300 - 0.3763 J/mm2. Kaolin and other Al-Si refractory materials

experience high volume shrinkage during sintering, have relatively low refractoriness,

and are incapable of producing casts with high precision. On the other hand, as a kind of

abundant and cheap material, mullites experience lower shrinkage and have higher

refractoriness. However, there are few reports on mullite ceramics by SLS, especially on

the mullite ceramic shell moulds used for investment casting.

Therefore, this work aims to develop a quicker and more efficient method to

fabricate ceramic shell moulds by combining SLS with the sintering process, and

achieve design, manufacturing integration. Mullite powder, which is a traditional and

widely used ceramic shell mould material, are used. Ceramic shell mould samples based

on SLS process are subjected to orthogonal experiments, where the effects of laser

power, scanning speed, scanning space, and layer thickness on the dimensional accuracy

of SLS parts are investigated. In addition, the strength of ceramic shell moulds greatly

improves when the process of fabrication is integrated with proper sintering process,

compared to the traditional shell-making technology [2].

3
2. Experimental procedure

2.1 Raw materials preparation

The mullite material was provided by Yidu Chuxiong Kaolin Co. Ltd. As a kind of

Al-Si refractory material, mullite powder has outstanding properties such as high

temperature strength, thermal shock resistance, low thermal expansion, low thermal

conductivity, fine chemical stability, and favorable fluidity for the sintering formality of

SLS parts [23]. The composition of mullite powder is shown in Table 1. The solid

polymer binder epoxy resin (ER06), provided by Guangzhou Shinshi Metallurgy and

Chemical Co. Ltd, has favorable melt viscosity. The particle size distribution of mullite

powder and ER06, depicted in Fig. 1, have mean particle sizes of 79 m and 12 m,

respectively, measured by a laser particle size analyzer (Mastersizer 2000, Malvern,

UK). Based on previous experiments, the content of ER06 content is at 10 wt%.

Table 1 The composition and mass fraction of mullite powder

Composition SiO2 Al2O3 Fe2O3 TiO2 CaO+MgO K2O+Na2O

Mass fraction (%) 62.18 35.22 0.99 0.93 0.40 0.28

Fig. 1 The particle size distribution of mullite powder (a) and ER06 (b)

4
2.2 Experimental process

2.2.1 Experimental apparatus for SLS

SLS is one of the most widely used branches in additive manufacturing. The

process, utilizes a computer-aided design (CAD) model that is sliced into cross-sections,

and is converted to a STL file. The STL data is then input back into the SLS forming

machine. To manufacture the 3D part, a levelling roller spreads a thin layer of powder,

then a continuously controllable CO2 laser beam scans along the path of the 2D-section

profile by the rotation of scanning mirror. After finishing the current layer, the

fabrication chamber descends a height of layer thickness, while one of the powder

delivery chambers raises the same thickness to supply the powder, and then the process

repeats. The cycle continues until the part is completed [24].

Three dimensional model cylinders φ20×20 mm were fabricated. To investigate

the effects of laser powder, scanning speed, scanning space, and layer thickness on the

dimensions of samples, orthogonal experiments were conducted [25]. The four factors

and three levels (L9 (43)) of orthogonal experiments is shown in Table 2. Nine

combinations containing four factors were carried out, and each group of samples were

denoted P1 to P9, as shown in Table 3. After laser sintering, the diameter and height of

fifteen samples from each group were measured thrice using a Vernier caliper (0-150

mm, Guanglu Co Ltd, China). The average value was recorded in the final results.

Table 2 Four factors and three levels of orthogonal experiments design

Factors
Level
A B C D

5
 Laser power/W Scanning speed/mm·s-1 Scanning space/mm Layer thickness/mm
1 8 3500 0.10 0.10
2 16 4000 0.15 0.15
3 24 4500 0.20 0.20

2.2.2 High-temperature sintering process

The SLSed parts have low initial compressive strength, and cannot be used as

ceramic shell moulds in investment casting. Therefore, a sintering process was adopted

to enhance their strength. Three groups of optimum samples were sintered by heating to

1000 °C at a heating rate of 6 °C/min, and then heated further to 1450, 1550, or 1610 °

C at a heating rate of 3 °C/min. All the sample groups were held for 30 min at the peak

temperature, subsequently cooled in a box-type furnace, and then denoted ST1, ST2,

ST3, accordingly. For reference, unsintered samples, ST0 were adopted, as seen in Fig.

2.

Fig. 2 A schematic diagram illustrating the heating cycles for the sintering process of the SLSed samples

6
 2.3 Characterization
The particle size distribution was determined using a laser particle size analyzer

(Mastersizer 2000, Marlvern, UK). The phase composition and content of the samples

were identified by X-ray diffraction (XRD) with Cu-Kα radiation (D/max-2550, Rigaku,

Japan) over the 2θ range 10 to 90° at a scanning rate of 8°/min. The morphology and

microstructure of the samples were observed by scanning electron microscope (SEM)

(ZEISS, Merlin Compact, Germany). The cylindrical samples prepared by sintering

process were subjected to isothermal uniaxial compression tests using a Gleeble-1500D

mechanical simulator. Since most ceramic materials are not conductive, we

independently developed a heating-insulating apparatus compatible with the

Gleeble-1500D mechanical simulator [26]. The average sizes of ST0, ST1, ST2, and

ST3 were φ19.89 mm × 20.23 mm, φ18.43 mm × 18.15 mm, φ15.17 mm × 14.25 mm,

and φ14.68 mm × 13.80 mm, respectively. Following the national standard GB/T

1964-1996 [27], the compression tests were conducted in open air at a strain rate of

10−4/s for both room temperature and high temperature (900 °C) conditions. The

compressive tests were repeated 5 to 8 times, considering the inhomogeneity of the

ceramic samples.

3. Results and discussion

3.1 Effect of process parameters on dimensional precision of SLS samples

Table 3 Design and results of orthogonal experiments

Samples Laser Scanning Scanning Layer Dimensions

7
 power/W speed/mm·s-1 space/mm thickness/mm Diameter/mm Height/mm

P1 8 3500 0.10 0.10 19.58±0.13 20.20±0.06

P2 8 4000 0.15 0.15 19.73±0.07 19.88±0.06

P3 8 4500 0.20 0.20 19.84±0.12 19.27±0.10

P4 16 3500 0.15 0.20 19.64±0.04 20.13±0.12

P5 16 4000 0.20 0.10 19.89±0.09 20.23±0.05

P6 16 4500 0.15 0.15 20.20±0.15 20.50±0.05

P7 24 3500 0.20 0.15 20.10±0.07 20.40±0.07

P8 24 4000 0.10 0.20 20.67±0.14 20.42±0.10

P9 24 4500 0.15 0.10 20.70±0.08 20.57±0.05

Nine sets of experiments with two experimental indexes (diameter and height)

were performed. The orthogonal experiment design and results are shown in Table 3.

Fig. 3 shows the dimensions of P1 to P9 SLS samples under different process

parameters from the orthogonal experiments. It can be seen that P5 exhibits an

acceptable dimensional deviation with respect to the original dimension of the 3D

model.

8
 Fig. 3 Dimensions of each group of SLSed samples

Fig. 4 shows the dimensional variations of SLSed parts under different single

factor. It shows that laser power, scanning speed, scanning space, and layer thickness

exert different influences on diameter (radical) and height (axial). The dimensions of the

samples were smaller than the theoretical dimensions due to the low laser energy input.

The polymer binder, ER06, melts and consolidates the mullite ceramic particles under

8W. By increasing laser power, the heat-affected zones broaden, causing ER06 to gasify

and lose its bonding capability [22]. Consequently, weak rearrangement of ceramic

particles occurs, and the dimensions of samples enlarge (Fig. 4 (a)). The laser energy

input only melts polymer binder particles, because ceramic particles have high melting

point. Owing to the binding effect of ER06, the mullite grain boundaries migrate and

discrete mullite particles bond together, eventually consolidating to the pre-designed

shape. It can be inferred that the degree of influence of laser power is similar for both

9
diameter and height as it is evenly distributed in the micro-regions.

Scanning speed also affects the distribution of laser and heat. As the scanning

speed increases from 3500 mm/s to 4500 mm/s, the diameter of the samples increases,

while the height decreases. This can be attributed to smaller heat transferred per unit

area and lower heat transferred per unit time at higher scanning speeds, resulting in an

incomplete re-melting of the interlayer zones. Consequently, the pores between

composite powders enlarge, leading to larger sample dimensions (Fig. 4 (b)).

Scanning space, the distance between two adjacent parallel scanlines, influences

laser energy input per unit area. Fig. 4 (c) illustrates that both diameter and height of

samples decrease with increasing scanning space. With smaller scanning space, heat

accumulates at the heated zones caused by overlapping scanlines, which accelerates the

gasification of ER06. Subsequently, it loses bonding capacity, the grain boundary

migration slows down, and mullite particles spread, leading to larger sample dimensions.

Conversely, broader scanning space provide larger gaps between two neighboring

scanlines, resulting a more uniform heat transfer zone [28], which leads to smaller

sample dimensions.

10
 Fig. 4 Dimensional variation of SLSed parts under different single factor

Layer thickness, the vertical distance between two neighboring sintering layer,

affects the height of samples more significantly, as seen in Fig. 4 (d). In general, thicker

sintering layers produces smaller samples. Layer thickness is closely associated with

laser energy per unit volume. The high absorbance of laser energy induced by thin

sintering layers results in efficient fusing of the polymer binder. Consequently, the

drastic rise in the temperature of the heat-affected zone expedites the gasification of

binder, which leads to an increase in the height of samples. In contract, the diameter is

not as affected by the variation in layer thickness, because laser energy absorbed per

unit volume (in vertical direction) is more affected than the laser energy per unit area (in

horizontal direction).

Overall, the process parameters during SLS process are all equally significant. The

11
coupling effects of multi-factors must be fully considered. Furthermore, the

optimization of process parameters allows the regulation and achievement of desired

dimensional characteristics.

Table 4 The range analysis of results based on diameter

Scanning Scanning
Indicators Laser power/W Layer thickness/mm
-1
speed/mm·s space/mm

K1j 59.15 59.32 60.45 60.17

K2j 59.73 60.29 60.07 60.03

K3j 61.47 60.74 59.83 60.15

k1j 19.717 19.773 20.150 20.057

k2j 19.910 20.097 20.023 20.010

k3j 20.490 20.247 19.943 20.050

Rj 0.773 0.474 0.207 0.047

Factors Primary A>B>C>D Secondary

Table 5 The range analysis of results based on height

Scanning Scanning Layer

Indicators Laser power/W
-1
speed/mm·s space/mm thickness/mm

K1j 59.35 60.73 61.12 61.00

K2j 60.86 60.53 60.58 60.78

K3j 61.39 60.34 59.90 59.82

k1j 19.783 20.243 20.373 20.333

k2j 20.287 20.177 20.193 20.260

k3j 20.463 20.113 19.967 19.940

Rj 0.680 0.130 0.406 0.393

Factors Primary A>C>D>B Secondary

Tables 4 and Table 5 report the range analysis of results based on diameter and

12
height, respectively. It is observed that choosing different experimental index receives

different comprehensive combination. From the range analysis, the optimum value of

the process parameters for samples with regard to diameter of high dimensional

accuracy follows A2B2C2D1, corresponding to laser power, scanning speed, scanning

space, and layer thickness of 16 W, 4000 mm/s, 0.15 mm, and 0.10 mm, respectively.

Moreover, the degree of influence of each parameter on diameter arranged in the

decreasing order is as follows: laser power, scanning speed, scanning space, and layer

thickness. For height accuracy, the optimum process parameters combination is

A1B3C2D2, corresponding to laser power, scanning speed, scanning space, and layer

thickness of 8 W, 4500 mm/s, 0.15 mm, and 0.15 mm, respectively. In addition, the

degree of influence of each parameter on height arranged in decreasing order is as

follows: laser power, scanning space, layer thickness, and scanning speed. Hence, for

both dimensions, laser power is the primary factor that greatly affect the dimensional

accuracy in this experiment.

Kij = for the intended factor (j=A, B C or D), sum of the average values for level i

= 1, 2, 3; ̅̅̅̅= for the intended factor (j=A, B, C, or D), average of the Kij values for

level i = 1, 2, 3; Rj= ̅̅̅̅̅̅̅ ̅̅̅̅̅̅, larger R value indicating more significant effect

degree [29].

From range value Rj listed in Tables 4 and Table 5, height is more sensitive to the

variation of process parameters than diameter due to the accumulating principle layer by

layer for additive manufacturing. Furthermore, the average deviation in the z-axis

13
should be controlled within a reasonable range, which means height should be

considered primarily.

3.2 XRD analysis

The XRD patterns of ST0, ST1, ST2, and ST3 under optimized process conditions

are shown in Fig. 5. The XRD pattern of the unsintered sample, ST0, shows that mullite

(JCPDS card no.82-0037) and -quartz (JCPDS card no.79-1910) are the major phases,

while -cristobalite (JCPDS card no.76-0940) is the minor phase. The crystal

quantitative analysis of the samples is measured using reference intensity ratio (RIR)

method [30]. It reveals that the mullite phase with orthorhombic structure is dominant.

The calculated contents of the mullite phase,-quartz, and -cristobalite are 53.5, 33.2,

and 13.3 wt%, respectively. The sample obtained at 1450 °C (ST1), exhibits identical

phase compositions with that from ST0. However, the content of -quartz phase

declines and the content of -cristobalite phase increases. Accordingly, the content of

mullite phase,-quartz and -cristobalite are 62.4, 12.7, and 25.0 wt%, respectivelyIt

was acknowledged that-cristobalite formed from -quartz over 1050 ° C, and

stabilized between 1470 ~ 1728 °C. Subsequently, it experienced a displacive phase

transformation to -cristobalite at ~ 250 °C [31]. So -quartz converts to -cristobalite

(restructive transformation) at 1450 °C, then goes on transformation (displacive

transformation) with temperature cooling to room temperature. Effectively, the content

of -cristobalite phase increases, and the content of -quartz phase decreases. Moreover,

ST2 consists only of mullite and -cristobalite, demonstrating that quartz constituents

14
are completely converted to cristobalite. The mullite content significantly increases to

88.0 wt%. Its spectrum reveals an evident amorphous characteristic peak between 10

and 30° after sintering at 1550 °C. Part of the cristobalite (a crystalline form of silicon

dioxide) transform to glass phase during the supercooling process, i.e., some of the

cristobalite amorphized without mullite formation. This is consistent with the findings

of YU et al [32]. Mullite formation occurs through the reaction of amorphous SiO2 with

-Al2O3 particles. The phase composition of ST3 is identical with that of ST2. During

sintering, -cristobalite, which is recognized as dynamic and unordered crystalline

phase [33], melts under 1610 °C. It continuously transforms to glass phase during the

undercooling process, with only 4.6 wt% -cristobalite remained. Consequently, the

content of mullite increases to 95.4 wt%. Mullite phase exhibits high strength, which

manifests in the resulting ceramic shell moulds.

15
Fig. 5 XRD patterns of samples ST0, ST1, ST2 and ST3

3.3 SEM analysis

Ceramic shell mould based on mullite is a multiphase and inhomogeneous material.

The microstructures of ST1, ST2, and ST3 are depicted in Fig. 6. As sintering

temperature increases from 1450 to 1550 °C, the open-pore volumes grow (Fig. 6 (a)

and (c)), At 1610 °C (Fig. 6 (e)), the surface of ST3 seems to melt and the open-pores

interconnect with each other as the grains densify. According to the calculation of

porosity, the open porosities of ST1, ST2, and ST3 are 38.11%, 21.55%, and 18.89%,

respectively, demonstrating that the density of ceramic shell moulds improve with the

increase of temperature. Solid-phase sintering is the transformation of bulk powders

from microscopic discrete particles to continuous solid-state structure through material

diffusion at high temperature. As a results, the overall surface energy in the system

decreases, while both the sample density and strength improve. Before sintering, the

green body is composed of many individual grains, with large surface area and plenty of

pores. During the sintering process, the growth of crystal grains and the reduction of

total surface energy on the sintered body lead to shrinkage of pores. Initially, grain

boundaries are formed by point contact or surface contact between grains, and the

sintered neck is formed as substances diffuse towards the contact. Furthermore, the

sintered neck grows, and adjacent grains compact. An interconnected pore network is

gradually formed as the grains continue to grow and densify. Finally, the pore network

stabilizes, and the final densification of the sample concludes through the discharge of

16
pores. A closer observation of morphologies of ST1, ST2, and ST3 can be seen in Fig. 6

(b), (d), and (f). In Fig. 6 (b), the mullite grains of ST1 are barely observed despite

having 53.5 wt% mullite content (Fig. 5). This is because the mullite grain sizes are too

small to be identified. As sintering temperature increases to 1550 °C (Fig. 6 (d)), the

partially oriented columnar mullite grains can be detected in the matrix

distributed non-uniformly , demonstrating the rapid growth of the mullite grains. It is

also found through SEM observation that the columnar mullite grains continue to grow

up at 1610 °C, as shown in Fig. 6 (f).

17
Fig. 6 Microstructures of samples sintered at different temperatures: (a) and (b) ST1, (c) and (d) ST2, (e) and (f) ST3

At high magnifications, the mullite and -cristobalite crystals can be detected, as

shown in Fig. 7. The mullite grains of ST1 present short columnar shapes with a

mean length-diameter ratio of mullite of 2-3. Oriented columnar mullites are surrounded

by translucent -quartz (Fig. 7 (a)). At 1550 °C, secondary mullites form at the outer

edge of the fully developed mullites via secondary mullitization behavior. Their mean

length-diameter ratio are 3-4, they are more developed than the primary mullites. White

18
spots of -cristobalite with tetragonal structure are uniformly distributed in the matrix.

A horizontal big crack, attributed to fast heating, is observed in the micrograph of ST2

(Fig. 7 (b)). Larger columnar mullites are shown in Fig. 7 (c) with mean length-diameter

ratio of ~5, while the grain sizes of -cristobalite remain unchanged. Mullites tend to

exhibit anisotropic growth due to their orthorhombic unit cell structures. This

observation and the high degree of orientation lead to a biased crystal growth towards

the crystallographic direction (parallel to the c-axis) [34].

Fig. 7 The shape of mullite crystal of sintered samples ST1, ST2 and ST3

Schematic diagram of phase transformation from quartz and cristobalite is

illustrated in Fig. 8. Phase transformation of quartz and cristobalite occur during

high-temperature sintering process. The mullite and quartz particles are surrounded by

small amounts of the amorphous phase above 1470 °C [35-36]. The external surface of

19
quartz activates and forms reaction zones prompted by the existence of defects, pores,

and cracks. Quartz is gradually converted into cristobalite as large differences between

their crystal structures and requires large energy for transition. So the transformation

time is long, and the transformation speed is slow. Smilowitz proposed the existence of

nucleation and crystal growth in the process of crystal transformation [37]. With no or

little mineralizer, α-quartz is converted to α-cristobalite. The impurity elements in

amorphous SiO2 reduce the formation temperature of cristobalite and accelerate the

reaction process [38-40]. Regarded as defect location, these impurity elements enhance

the free energy of the system and increase the reactivity of the amorphous SiO2, which

is favorable to reduce the formation temperature of cristobalite phase. Meanwhile, the

mullite grains grow to a certain extent. With the increase in sintering temperature, the

amount of cristobalite increases, and the formation of its crystal morphology proceeds

further. Simultaneously, mullite grains continue to grow and their length-diameter ratio

increase further. At a certain temperature, the quartz constituents are completely

converted to cristobalite.

Fig. 8 Schematic of phase transformation from quartz to cristobalite

3.4 Sintering temperature on the compressive strength of SLS samples at room

temperature

20
 Fig. 9 presents the stress-strain curves of ST0, ST1, ST2, and ST3 subjected to

quasi-static compressive load. The stress-strain curves of ST1 (Fig. 9 (b)) is found to be

resembles that of the unsintered samples ST0 (Fig. 9 (a)), both behaving extremely low

strength. The curves of ST2 displays a typical elastic behavior at low strain and then

indicates a collapse at a certain strain value (Fig. 9 (c)). In the elastic range, the slope is

linear and is defined by the elastic modulus, or Young's modulus, E. The stress-strain

curves of ST3 sintered under 1610 °C also exhibits elastic behavior at small strain.

Furthermore, brittle fracture is evident at a certain strain value, and the stress plunges to

zero, as illustrated in Fig. 9 (d).

Fig. 9 Stress-strain curves of samples at room temperature. (a) ST0, (b) ST1, (c) ST2, (d) ST3

21
 Fig. 10 represents the compressive strength and elastic modulus of ST0, ST1, ST2,

and ST3. It shows that all values increase with the increase of sintering temperature.

The average compressive strength and elastic modulus of ST0 are 2.58 MPa, 55.86 MPa,

and the average compressive strength and elastic modulus of ST1 sintered at 1450 °C

are 3.18 MPa, 123.41 MPa, both exhibiting low strength. A significant increase in

compressive strength and elastic modulus is achieved by ST2 with 91.68 MPa and

1904.37 MPa, respectively. It reflects that the high-strength mullite phase forms and

greatly enhances the strength of samples (Fig. 5). The compressive strength and elastic

modulus continue to increase at 1610 °C for ST3 with 113.09 MPa and 2497.67 MPa,

respectively. This is due to the fact that the contents of mullite phase continue to form

and mullite grains grow further (Fig. 5 and Fig. 6 (f)). Both ST2 and ST3 show high

compressive strength compared to the traditional fabrication method of mullite ceramic

shell moulds for investment casting [2].

22
Fig. 10 Compressive strength and elastic modulus of samples at room temperature

3.5 Sintering temperature on the hot compressive strength of SLS samples at 900 °C

23
 Fig. 11 Stress-strain curves of samples at 900 °C. (a) ST0, (b) ST1, (c) ST2, (d) ST3

To simulate the real casting conditions, multiple samples of ST0, ST1, ST2, and

ST3 were compressed at 900 °C. Each group of samples was repeatedly tested by 4 to 6

times. Fig. 11 displays the stress-strain curves of ST0, ST1, ST2, and ST3 at 900 °C

experimental conditions. The curves of ST0 and ST1 display low maximum

compressive strength (Fig. 11 (a) and (b)), while exceeding the maximum value, the

stress gradually decline to lower value. The curves of ST2 exhibits elastic behaviors at

small strain, with stress dropping to zero following the ultimate stress value (Fig. 11 (c)).

This behavior is not observed for the ST2 curves obtained from compression tests at

room temperature. The stress-strain curves of ST3 reveals a continuously increasing

stress without signs of fracturing, as shown in (Fig. 11 (d)). This signifies that the

24
maximum compressive strength of ST3 is beyond the maximum load capacity of

Gleeble-1500D mechanical simulator, which is ~172.02 MPa. Hence, ST3 exhibits

sufficiently high strength that the ceramic shell mould based on it will not crack during

the metal pouring process.

Fig. 12 plots the hot compressive strength and elastic modulus of all samples at

900 °C. The unsintered samples, ST0, possess low compressive strength (4.26 MPa) and

elastic modulus (322.02 MPa) at 900 °C, indicating the phase transition from -quartz

to -cristobalite at experimental temperature only slightly improves the compressive

strength compared to ST0 performed at room temperature (Fig. 10). ST1, which were

sintered at 1450 °C, also present low-strength characters at high temperature, with hot

compressive strength of 6.80 MPa and elastic modulus of 348.33 MPa. The hot

compressive strength and elastic modulus of ST2 are 99.01 MPa and 1846.43 MPa,

respectively. For ST3, the hot compressive strength exceeds 172.02 MPa and the elastic

modulus is 2167.56 MPa. Both are considerably greater than those tested at room

temperature. Therefore, the hot compressive strength and the elastic modulus both

increase with the increase of sintering temperature, and there is a dramatically increase

with sintering temperature changing from 1450 to 1550 °C. This is attributed to the

sharp increase in mullite content, which contributes to the high compressive strength. In

addition, the conversion of -cristobalite to -cristobalite at the experimental

temperature of 900 °C, in accordance with the phase diagram of quartz, -cristobalite

crystals distribute in the matrix, and contributes to the skeleton of fused silica between

25
the grains, which leads to the excellent hot compressive strength of ST2.

Fig. 12 Compressive strength and elastic modulus of samples at 900 °C

4. Conclusions

In this study, mullite ceramic shell moulds were obtained by SLS. The strength of

ceramic shell moulds were successfully enhanced by sintering. Process optimization

based on dimensional accuracy was investigated. Phase analyses, microstructure

observations, and mechanical properties of samples at room temperature and high

temperature were performed. The results revealed that mullite ceramic shell moulds

prepared meet the strength requirement of ceramic moulds for investment casting.

(1) Different process parameters exert different effects on the dimensional

precision of the SLS parts. The optimum combination of process parameters was

determined by a set of orthogonal tests. The optimum laser power, scanning speed,

scanning space, and layer thickness in this experiment were discovered to be 8 W, 4500

26
mm/s, 0.15 mm, and 0.15 mm, respectively.

(2) The increase in mullite content and its mean length-diameter ratio due to the

secondary mullitization mechanism was confirmed to be caused by the increase of

sintering temperature.

(3) Samples sintered at 1550 and 1610 °C exhibited excellent compressive

strength (91.68 MPa and 113.09 MPa) at room temperature. At high temperature (900 °

C), the hot compressive strength of samples improved further, with 99.01 MPa and

~172.02 MPa, respectively. These greatly exceed those of mullite ceramic moulds

fabricated by traditional shell-making techniques.

(4) The present work illustrated that ceramic shell mould parts can be obtained by

integrating SLS with proper sintering process. This presents a quicker and more

efficient approach to producing shell mould parts with excellent strength. It opens the

opportunities for application in other engineering fields.

Acknowledgements

The authors gratefully acknowledge the support by National Science and

Technology Major Project (2017ZX04014001-002), China-EU (European Union)

Science & Technology Cooperation in Aviation, Horizon 2020 Framework Programme

for Research and Innovation (2014-2020) of EU as well as National Natural Science

Foundation of China (Grant No. 51374137).

References
[1] R.K. Mishra, J. Thomas, K. Srinivasan, V. Nandi, R. Raghavendra Bhatt, Failure analysis of an
un-cooled turbine blade in an aero gas turbine engine, ENG FAIL ANAL, 79 (2017) 836-844.

27
 [2] Z. Xu, J. Zhong, X. Su, Q. Xu, B. Liu, Experimental study on mechanical properties of silica-based
ceramic core for directional solidification of single crystal superalloy, CERAM INT, 44 (2018) 394-401.
[3] S. Amira, D. Dubé, R. Tremblay, Method to determine hot permeability and strength of ceramic shell
moulds, J MATER PROCESS TECH, 211 (2011) 1336-1340.
[4] M. William, Steen, Laser Material Processing, 3rd ed., Springer Verlag, London, 2003.
[5] J. Yang, Y. Shi, Q. Shen, C. Yan, Selective laser sintering of HIPS and investment casting
technology, J MATER PROCESS TECH, 209 (2009) 1901-1908.
[6] J.L. Song, Y.T. Li, Q.L. Deng, D.J. Hu, Rapid prototyping manufacturing of silica sand patterns
based on selective laser sintering, J MATER PROCESS TECH, 187-188 (2007) 614-618.
[7] Y. Du, H. Liu, Q. Yang, S. Wang, J. Wang, J. Ma, I. Noh, A.G. Mikos, S. Zhang, Selective laser
sintering scaffold with hierarchical architecture and gradient composition for osteochondral repair in
rabbits, BIOMATERIALS, 137 (2017) 37-48.
[8] F. Liu, R. Lee, W. Lin, Y. Liao, Selective laser sintering of bio-metal scaffold, Procedia CIRP, 5
(2013) 83-87.
[9] M. Silva, R. Felismina, A. Mateus, P. Parreira, C. Mal A, Application of a hybrid additive
manufacturing methodology to produce a metal/polymer customized dental implant, Procedia
Manufacturing, 12 (2017) 150-155.
[10] E. Vijayaragavan, L.M. Kurian, H. Sulayman, T.V. Gopal, Application of rapid prototyping in the
treatment of clubfoot in children, Procedia Engineering, 97 (2014) 2298-2305.
[11] K. Jiang, Y. Guo, D.L. Bourell, W. Zeng, Z. Li, Study on selective laser sintering of eucalyptus/PES
blend and investment casting technology, Procedia CIRP, 6 (2013) 510-514.
[12] Z. Wang, Y. Shi, W. He, K. Liu, Y. Zhang, Compound process of selective laser processed alumina
parts densified by cold isostatic pressing and solid state sintering: Experiments, full process simulation
and parameter optimization, CERAM INT, 41 (2015) 3245-3253.
[13] K. Shahzad, J. Deckers, S. Boury, B. Neirinck, J. Kruth, J. Vleugels, Preparation and indirect
selective laser sintering of alumina/PA microspheres, CERAM INT, 38 (2012) 1241-1247.
[14] M. Cabrini, S. Lorenzi, T. Pastore, S. Pellegrini, D. Manfredi, P. Fino, S. Biamino, C. Badini,
Evaluation of corrosion resistance of Al–10Si–Mg alloy obtained by means of Direct Metal Laser
Sintering, J MATER PROCESS TECH, 231 (2016) 326-335.
[15] S.M. Nazemosadat, E. Foroozmehr, M. Badrossamay, Preparation of alumina/polystyrene core-shell
composite powder via phase inversion process for indirect selective laser sintering applications, CERAM
INT, 44 (2018) 596-604.
[16] A. Ahmadi Dastjerdi, M.R. Movahhedy, J. Akbari, Optimization of process parameters for reducing
warpage in selected laser sintering of polymer parts, Additive Manufacturing, 18 (2017) 285-294.
[17] P. Bai, W. Wang, Selective laser sintering mechanism of polymer-coated molybdenum powder, T
NONFERR METAL SOC, 17 (2007) 543-547.
[18] M. Schmidt, D. Pohle, T. Rechtenwald, Selective Laser Sintering of PEEK, CIRP Annals, 56 (2007)
205-208.
[19] C. Yan, Y. Shi, J. Yang, J. Liu, Preparation and selective laser sintering of nylon-12 coated metal
powders and post processing, J MATER PROCESS TECH, 209 (2009) 5785-5792.
[20] M. Benedetti, M. Cazzolli, V. Fontanari, M. Leoni, Fatigue limit of Ti6Al4V alloy produced by
Selective Laser Sintering, Procedia Structural Integrity, 2 (2016) 3158-3167.
[21] S. Wen, Q. Shen, Q. Wei, C. Yan, W. Zhu, Y. Shi, J. Yang, Y. Shi, Material optimization and

28
post-processing of sand moulds manufactured by the selective laser sintering of binder-coated Al2O3
sands, J MATER PROCESS TECH, 225 (2015) 93-102.
[22] K. Liu, H. Sun, Y. Shi, J. Liu, S. Zhang, S. Huang, M. Wang, Research on selective laser sintering of
Kaolin–epoxy resin ceramic powders combined with cold isostatic pressing and sintering, CERAM INT,
42 (2016) 10711-10718.
[23] I.A. Aksay, D. Dabbs, M. Sarikaya, Mullite for structural, electronic, and optical applications, J AM
CERAM SOC, 74 (1991) 2343-2358.
[24] H.C.H. Ho, I. Gibson, W.L. Cheung, Effects of energy density on morphology and properties of
selective laser sintered polycarbonate, J MATER PROCESS TECH, 89-90 (1999) 204-210.
[25] A. Dey, Orthogonal fractional factorial designs, Wiley, New York, 1985.
[26] Q. Xu, Z. Xu, J. Zhong, X. Su, H. Shao, External auxiliary heating device and test device for
measuring the hot compressive properties of materials. Chinese Patent no. 201710332245, 2017.
[27] Test method for crushing strength of porous ceramic, GB/T 1964-1996, Standards Press of China,
Beijing, 1996.
[28] Y. Pupo, J. Delgado, L. Serenó, J. Ciurana, Scanning space analysis in Selective Laser Melting for
CoCrMo powder, Procedia Engineering, 63 (2013) 370-378.
[29] G. Zou, J. Xu, C. Wu, Evaluation of factors that affect rutting resistance of asphalt mixes by
orthogonal experiment design, International Journal of Pavement Research and Technology, 10 (2017)
282-288.
[30] R. Snyder, The use of reference intensity ratios in X-ray quantitative analysis, POWDER DIFFR, 4
186-193.
[31] R.S. Darling, I.M. Chou, R.J. Bodnar, An occurrence of metastable cristobalite in high-pressure
garnet granulite, SCIENCE, 276 (1997) 91-93.
[32] P. Yu, Y. Tsai, F. Yen, W. Yang, C. Huang, Thermal characteristic difference between α-Al2O3 and
cristobalite powders during mullite synthesis induced by size reduction, J EUR CERAM SOC, 35 (2015)
673-680.
[33] I. Swainson, M. Dove, Molecular dynamics simulations of α-and β-cristobalite, Journal of Physics
Condensed Matter, 9 (1995) 1771-1788.
[34] M. Yan, Y. Li, Y. Sun, L. Li, S. Tong, J. Sun, Controllable preparation and synthetic mechanism of
mullite from the bauxite with Fe-rich oxide content, MATER CHEM PHYS, 202 (2017) 245-250.
[35] H. Graetsch, H. Gies, I. Topalovi, NMR, XRD and IR study on microcrystalline opals, PHYS CHEM
MINER, 21 (1994) 166–175.
[36] J. Dubois, M. Murat, A. Amroune, X. Carbonneau, R. Gardon, High-temperature transformation in
kaolinite: the role of the crystallinity and of the firing atmosphere, APPL CLAY SCI, 10 (1995) 187-198.
[37] L.B. Smilowitz, B.F. Henson, B.W. Asay, P.M. Dickson, J.M. Robinson, Kinetics of the beta-delta
phase transition in PBX 9501, AIP CONFERENCE PROCEEDINGS2002. pp. 1077-1080.
[38] E.L. Calacal, O.J. Whittemore, The sintering of diatomite, AM CERAM SOC BULL, 66 (1987)
790-793.
[39] L.H. Wang, B.J. Tsai, The sintering and crystallization of colloidal silica gel, MATER LETT, 43
(2000) 309-314.
[40] H. Nanri, N. Takeuchi, S. Ishida, K. Watanabe, M. Wakamatsu, Mineralizing action of iron in
amorphous silica, J NON-CRYST SOLIDS, 203 (1996) 375-379.

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