3D gel-printing—An additive manufacturing method for producing complex
shape parts

Xiangyuan Ren, Huiping Shao, Tao Lin, Hang Zheng

PII: S0264-1275(16)30420-8
DOI: doi: 10.1016/j.matdes.2016.03.152
Reference: JMADE 1630

To appear in:

Received date: 7 December 2015

Revised date: 25 February 2016
Accepted date: 25 March 2016

Please cite this article as: Xiangyuan Ren, Huiping Shao, Tao Lin, Hang Zheng, 3D
gel-printing—An additive manufacturing method for producing complex shape parts,
(2016), doi: 10.1016/j.matdes.2016.03.152

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 ACCEPTED MANUSCRIPT

3D Gel-printing―An Additive Manufacturing Method for Producing Complex

Shape Parts
Xiangyuan Ren, Huiping Shao, Tao Lin and Hang Zheng
Institute for Advanced Material & Technology, University of Science and Technology Beijing, Beijing 100083,
China

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Corresponding author: Huiping Shao. E-mail address: shaohp@ustb.edu.cn (H. Shao)

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Abstract: A new 3D printing process, 3D gel-printing(3DGP) based on methaerylate-2-hydroxy
ethyl (HEMA) gelation system, was proposed in this paper, and as an example, 316L stainless

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steel gear was prepared by 3DGP. The rheological behavior of metal slurry, the surface roughness

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and strength of green sample and sintered sample were researched. The results show that the metal
slurry with a 316L particle content of 62.5vol% can be prepared with a HEMA-based gelation
system, whose rheological behavior is fit for printing. Catalyst can accelerate the gelation so that

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complex shape of parts could be setting in time during printing. The green sample has a strength
of 16.1±2.2MPa and a roughness of 3.5±0.5m on top surface. The sintered sample has a
homogeneous microstructure and no interface between the printed layers and lines was observed.
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The sintered sample has a roughness of 3.8±0.9m on top surface and a tensile strength of 488±
15MPa. Generally, 3DGP based on HEMA gelation system is a promising method for producing
complex shape parts.
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Key words: Additive manufacture; 3D printing; gelation; 316L stainless steel; 3D gel-printing
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1 Introduction
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Today, more and more attentions were attracted on the development of additive
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manufacture (AM), which has a high potential for directly shaping of complex shape
parts from 3D computer-aided design (CAD) database or 3D scanning systems
database. Some 3D printing processes have been developed for producing metal or
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ceramic parts. Such processes as three-dimensional printing (3DP), selective laser

sintering(SLS), selective laser melting(SLM), electron beam melting(EBM),
droplet-based metal manufacturing(DMM) have been used to fabricate 3D metal
structures[1-5].
For metal materials, such as aluminum alloy [3,6],stainless steel [7-10], super
alloy [11] and titanium alloy[12-16], these processes of SLS,SLM and EBM were
typically used to prepare complex shape parts by repeating the steps of stacking
particle layer and directly sintering/melting the selective area of particles. Generally,
these three processes can produce almost fully dense parts for practical applications,
but the printing equipment of these processes are complicated and their maintenance
cost is rather high by use of the laser and electron beam system as well as protective
atmosphere. In addition, since temperature changes very quickly, these processes are
hard to be used to prepare ceramic and composites.
It is considered that DMM is an effective and low cost method for fabricating
parts because it can directly deposit metal droplets without expensive equipment
comparing with the above direct metal prototyping methods [17]. In spite of the
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DMM process has been reported to be used for production of parts of different
materials such as: aluminum alloy parts [18] and Sn-40wt%Pb alloy [5], these
materials have lower values of melting temperature. Most of metals of commercial
importance, such as super alloy applied in aerospace filed, have much higher values
of surface tension and melting temperature. By DMM process, super alloy is difficult

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to melt to form droplets, let alone to get a smooth surface after solidification.
Thermoplastic 3D Printing (3DTP) [19] is a new additive manufacturing

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technique which combines fused deposition modeling (FDM) and robocasting. The
high-load feedstock with thermoplastic binder systems is extruded through a heated

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nozzle with xyz positioning, which is based on low-pressure injection molding. The

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3DTP process has been reported to be used for production of parts of different
materials such as alumina [19], zirconia [19] and steel-zirconia composites [20]. 3DTP
could be used for steel, ceramic and composites, but the device of 3DTP needs a

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complicated extruding nozzle.
Direct Inkjet Printing (DIP) [21] is a generative solid free-forming process where
cross-sections of a three-dimensional model are deposited on a substrate layer by
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layer based on colloidal slurries and virtual models. In former studies, ceramic
suspensions were used as inks for DIP and some 3-D ceramics parts were successfully
printed, such as zirconia [22-23], and silicon nitride [24]. However, there are some
problems constraining the DIP application for metal material, such as preparation of
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uniform and stable metal slurry with high content of metal particles.
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To address some problems of the above additive manufacture process, a new AM

process, named as 3D gel-printing (3DGP), was proposed in this paper in
consideration of the advantages of DIP process and gelation. The principle of gelation
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is based on radical polymerization of organic monomer, forming a macro polymeric

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network to hold particles together [25]. This 3DGP process has some advantages over
other processes. First, the applicable range of materials is wide and includes metal,
ceramic and their composites. Second, the cost of printing equipment is low because
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such as high-energy beam, device of spreading powder are not required. Third, the
cost of printing parts is low because protective atmosphere and heating are not
required. Fourth, the printing efficiency is high because a slurry is used and it has
flow-ability for printing and gets solidification faster.
In this paper, with 316L stainless steel as the raw material, the slurry preparation,
3D printing, sintering, mechanical properties and microstructure of the 3DGP process
were investigated.

2 Experimental

2.1 3DGP process

Fig.1 is the schematic diagram of the 3D gel printing (3DGP) process proposed
in this paper. The 3DGP process is composed of the following steps: premixed
solution preparation, slurry preparation, initiator addition and printing. Table 1 lists
the composition of the raw materials, which is one of the representative ratios
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suggested in our previous work [26-28].It is obvious that the high solid loading of
slurry has lower shrinkage and better forming precision. The 3DGP process will be
described in detail in the next parts.
2.2 Premixed solution and slurry preparation
A non-aqueous solution was used for preventing metals from oxidation, in which

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methaerylate-2-hydroxy ethyl (HEMA, AR, Sinopharm Chemical Reagent Co.,Ltd)
and toluene(AR, Sinopharm Chemical Reagent Co.,Ltd) were selected as the organic

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monomer and solvent respectively. At first, HEMA fully dissolved in toluene to
produce a premixed solution.

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316L particle (Long Ding Trading Company Ltd, China)was added in the above

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premixed solution, and metal slurry was prepared by stirring. Oleic acid (AR,
Sinopharm Chemical Reagent Co. Ltd)was added as a dispersant in order to improve
the dispersion and suspension of the metal particles in the premixed solution.

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2.3 Initiator addition and printing
Benzoyl peroxide (BPO, AR, Beijing Yili Fine Chemicals)was selected as an
initiator of the premixed solution. The metal slurry and BPO were delivered to the
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screw extruder, and were mixed with each other by the screw. In order to adjust the
gelation time, N, N, N', N'-tetramethylethylenediamine (TEMED, AR, Sinopharm
Chemical Reagent Co. Ltd ) was used as a catalyst and was delivered to the screw
extruder along with BPO.
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The screw extruder and the printing nozzle were set on a 3D driving mechanism.
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The mixed slurry left out the nozzle under the action of the screw and solidified to
form a part. For complete solidification, the printed green sample was firstly dried in a
drying box at 60℃for 5 hours.
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2.4 Sintering
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The dried green sample was debinded at a temperature at 450°C for 1 hour in
argon atmosphere in a tube furnace. Finally, sintering was carried out at 1350℃ for
2h in a vacuum furnace[28].
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2.5 Testing of material properties

The particle size distribution was tested by a laser particle analyzer(BT-9300S,
Dandong Better Co.Ltd., China). The viscosity of the metal slurry was tested by a
controlled stress rheometer under the shear rate from 1 s-1 to 1550 s-1at 25℃(Physica
MRC 300 Modular Compact Rheometer, Germany). The density of the printed and
sintered samples was determined by the Archimedes immersion method in water. The
appearance of the 316L particle and the microstructure of the printed and sintered
samples were characterized by a scanning electric microscope (SEM, ZEISS EVO®18,
Carl Zeiss NTS, Germany). The surface roughness of samples was measured by a
confocal laser scanning microscope (CLSM, OLYPUS LEXT OLS4000, Japan).
The bending strength of the printed and sintered samples, which were cut to a
size of 5 mm×5mm×35mm, was measured by the three-point bending test with an
electronic universal testing machine (Instron CMT 4305) at a loading rate of 0.5
mm/min. The hardness of materials was determined by a Rockwell hardness tester
(HR150A, Huayin Instrument Co.Ltd.,China). The thermo-decomposition behaviors
of gel were determined by a thermogravimetric analyzer (TGA, SDT-Q600, TA
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Instruments, America) at a heating rate of 10 ℃ /min under the protection of

high-purity argon gas.

3 Results and discussion

3.1 The rheological behavior of the metal slurry

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According to Table 1, 316L stainless steel particles were dispersed in the
premixed solution which is composed of HEMA and toluene. Oleic acid was added as

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a dispersant to improve the suspension of the metal particles in the premixed solution,
and then the content of the 316L particle can reach a value of 62.5vol.%.

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3DGP requires a stable flow-ability of particle which depends on the size and

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shape of the particles. The ideal particle for the 3DGP could have fine particle size,
spherical shape and high bulk density. The 316L stainless steel particle used here was
prepared by water atomization process. Fig.2 and Fig.3 show the appearance and the

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particle size distribution of the 316L particle, respectively. The shape of the particles
is nearly spherical, and the average particle size is 9.2m. The bulk density and tap
density are 3.2 and 4.1g/cm3, respectively, and the Hauser ratio of the particle is 1.28,
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indicating this particle has a higher packing density and good flow-ability [29].
The rheological curve of the slurry is shown in Fig.4. The viscosity decreases
with increasing the shear rate and reaches a stable state at a shear rate above 60 s-1.
The slurry shows a pseudo plastic behavior, and is close to the classic shear thinning
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fluid. At higher shear rates, viscosity decreases because of the disruption of the
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structures. At lower shear rates, shear forces have no effect on agglomerates and the
viscosity of the slurry is high. The shear rate of the slurry that can be extruded
through a nozzle can be calculated with the Weissenberg–Rabinowitsch–Mooney
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equation [30].
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(1)
where γ is the shear rate (s-1), Q is volumetric flow rate (m3/s), R is the internal radius
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of the tube, n is power law index. From Fig.4, the predicted variation in viscosity was
fitted to the experimental data using the power-law model. The best fit to data is
found at a value of n=0.39263. With the aid of Equation (1), the calculated shear rate
of the slurry is 3.23s-1, at which the viscosity of the slurry has decreased substantially.
This will be helpful for the slurry to flow out from the nozzle and then get viscous for
holding its shape. This rheological behavior shows that the slurry is suitable for being
printed by 3DGP [23-24, 31].
3.2 Printing process
The slurry was delivered to the screw extruder of the 3DGP system under an
appropriate pressure of compressed air. Meanwhile the initiator and catalyst were
delivered to the screw extruder either. These materials were blended well and
extruded out by the screw through a nozzle onto a substrate.
The extrusion rate of the slurry, the printing speed of the nozzle, the layer height
and nozzle size are the key factors affecting the printing quality. The literature [32]
indicated that fill density can affect the quality of the final structure. The speed of
rotation of the screw extruder, the printing head speed and layer height can affect the
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fill density. In spite of the high printing head speed can improve manufacturing
efficiency, it is required to be matched with the extrusion rate .The layer height is
directly related with the size of nozzle .For example, as shown in Fig.5, when the
extrusion rate is high, printed lines overlap and even collapse. Excess printed slurry
cannot solidify in time and may be pushed outward by the nozzle during next

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movement. Finally, printed layers collapse and the part cannot be formed. On the
other hand, when the extrusion rate is low, printed lines cannot be continuous and big

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pores remain in the printed part. The printing speed of the nozzle and the layer height
have the similar effects. The nozzle size mainly affect printing precision and surface

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roughness. Obviously, the printed sample has good dimensional accuracy and surface

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quality with reducing the size of nozzle, but the pressure of extrusion increases with
reducing the size of nozzle. What’s more, the printing equipment becomes
complicated and their maintenance cost is rather high by using a rather small nozzle.

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Finally, the optimum printing conditions in Table 2 were used.
3.3 Gelation process
For the binder of 3DGP, methaerylate-2-hydroxy ethyl (HEMA), benzoyl
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peroxide (BPO) and N, N, N', N'-tetramethylethylenediamine (TEMED) were used as
the organic monomer, initiator and catalyst respectively. After mixed by the screw, the
slurry starts gelation process based on HEMA monomer free radical polymerization.
The whole process of radical polymerization reaction generally consists of three
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elementary reactions—chain initiation, chain propagation and chain termination [33].

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(1) Chain initiation: Chain initiation contains two chemical reactions as follows: First,
the initiator (BPO) decomposes to generate free radicals. Secondly, monomer radicals
generate by the additional reaction of HEMA and primary radicals.
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(2)
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(3)

(2) Chain propagation: The monomer radicals which are produced by chain initiation
continuously combine HEMA monomer molecules to generate chain free radicals,
resulting in the polymer chain growing. Tens of thousands monomer radicals can be
combined with each other to form a polymer chain radical in a very short period of
time, eventually forming a chain structure of macromolecules as follows.

(4)

Where R is . The catalyst of TEMED can be used to accelerate the

polymerization. When TEMED is added, the time of polymerization is significantly
shortened to several seconds.
(3) Chain termination: Because the activity of free radicals is lost, chains no longer
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grow, and stable chains of polymer molecules are formed to hold metal particles
together (Fig.6).
3.4 The green sample prepared by 3DGP
A gear as an example was printed as shown in Fig.7 (a). The printed lines can be
observed from Fig.7 (b) and (c). The top surface is homogenous and no defect is

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visible. The width of a printed line is 0.42mm, which is close to the diameter of the
nozzle. The layer height is 0.21mm from Fig.7 (c), which is also close to the

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parameter of layer height. The shape of the slurry is cylindrical after it was extruded
out of the nozzle, and it is pressed by the nozzle and spreads out to fill the space

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among the printed lines before gelation. The top and side surface roughness of the

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green sample can be up to 3.5±0.5m and 8.3±0.7m, respectively.
Table 3 lists the bending strength of green samples prepared by different
processes with 316L particle. Obviously, 3DGP has great advantage in the bending

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strength of green sample. Fig.10 shows the cross section of the green sample. The
interfaces among the printed layers and lines cannot be seen in Fig.8, indicating that
gelation also took place on these interfaces to form organic crosslinking. This is
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benefit for the bending strength.
It can also be seen in Fig.8 that 316L particles distribute uniformly in the organic
binder and closely contact with each other. The green density is 5.36g/cm3.
3.5 The sintered sample
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The polymeric gel should be burn out firstly before sintering among metal
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particles. TG analysis was performed to determine the appropriate debinding

temperature. Fig.9 is the TG curve of the polymeric gel with a heating rate of 10℃
/min under a flowing argon atmosphere. It can be seen that the polymeric gel begins
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to decompose at about 250℃. When the temperature is in the range of 300-450℃, the
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polymeric gel decomposes violently. So the green sample was debinded at a

temperature of 450℃ for 1 hour in argon atmosphere in a tube furnace in order that
the polymeric gel could decompose completely. Finally, sintering was carried out in
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the tube furnace at 1350℃for 2h in a vacuum furnace[28].

As shown in Fig.10, the appearance of the sintered gear coincides with its design.
The top and side surface roughness of the sintered sample can be up to 3.8±
0.9m and 8.7±0.8m respectively. The top and side surface roughness of parts
produced by other 3D printing processes is also listed in Table 4. The roughness of
parts produced by 3DGP is lower than other 3D printing processes. This is another
great advantage of 3DGP.
The typical properties of 316L stainless steel prepared by different processes are
listed in Table 5. The tensile strength of 316L stainless steel prepared by 3DGP can
meet the MPIF35 and ASTM A240 standards. From this point of view, it is possible
for 3DGP to produce 316L parts with a complex shape in practical applications. The
mechanical properties should be improved in the future.
Fig.11 shows the cross-section of 316L samples sintered at 1350℃ for 2h. No
feature between the printed layers and lines can be visible on the cross-section,
illustrating that the sintered sample has a homogeneous microstructure. Since the
relative density is about 96.8%, some microspores still exist and uniformly disperse in
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the sintered sample.

Fig.12 shows printed samples and Table 6 lists the dimensions of the
three-dimensional model, the green sample and the sintered sample. The dimensions
of the green sample are slight larger than the design value and the difference between
them are close to the track width and layer height, so the printing step in 3DGP can

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well control the dimension. The sample shrinked after sintering.
Generally, 3DGP based on HEMA gelation system is a promising method for

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producing complex shape of parts because of its great advantage of simple structure
of equipment. Furthermore, it can be expected that 3DGP could be used to prepare

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ceramics and metal-ceramic composites.

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4 Conclusions

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A new 3D printing process, 3D gel-printing(3DGP), was proposed in this paper, and
as an example, 316L stainless steel gear was prepared by 3DGP. It can be concluded
as follows:
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(1) A metal slurry with a 316L particle content of 62.5vol. % can be prepared
with a HEMA-based gelation system, whose rheological behavior is fit for
printing.
(2) Catalyst can accelerate the gelation so that complex shape of parts could be
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setting during printing. The green sample has a strength of 16.1±2.2MPa and
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a roughness of 3.5±0.5m on top surface.

(3) The sintered sample has a homogeneous microstructure and no interface
between the printed layers and lines was observed. The sintered sample has a
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roughness of 3.8±0.9m on top surface and a tensile strength of 488±15

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MPa.
(4) Generally, 3DGP based on HEMA gelation system is a promising method for
producing complex shape of parts.
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[41] A. Mertens, S. Reginster, Q. Contrepois, T. Dormal, O. Lemaire, J. L. Beckers,
Microstructures and Mechanical Properties of Stainless Steel AISI 316L Processed by

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Selective Laser Melting, Adv. Mater. Res. 783-786 (2014) 898-903.
[42] MPIF Standard 35,Materials Standards for PM Structural Parts, 2009 ed., Metal

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Particle Industries Federation, Princeton, NJ, 2009.

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[43] ASTM A240, Standard Specification for Chromium and Chromium-Nickel Stainless
Steel Plate. Sheet, and Strip for Pressure Vessels and General Applications, 2005 ed.,
American Society of Testing Materials, West Conshohocken, PA, 2005.

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Figures and Tables

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Fig.1 Schematic diagram of the 3DGP process

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Fig.2 SEM image of the 316L powder
Fig.3 Particle size distribution of the 316L powder
Fig.4 Viscosity of the 316L particle slurry as a function of shear rate

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Fig.5 Green samples printed by 3DGP with: (a) high extrusion rate 8.0cm3/min, (b)optimum
extrusion rate 7.0cm3/min and (c) low extrusion rate 6.0cm3/min
Fig. 6 Schematic diagram of the slurry gelation.
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Fig.7 Green sample of a gear printed by 3DGP : (a) overview, (b) SEM morphology of the top
surface, (c) SEM morphology of the side surface
Fig.8 Fractograph of the green sample made by 3DGP (a) low (b) higher magnification
Fig. 9 TG curves of polymeric gel with a heating rate of 10℃/min
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Fig.10 The sintered 316L gear: (a) overview, (b) SEM morphology of the top surface, (c) SEM
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morphology of the side surface.

Fig.11 Microstructure of 316L sintered sample: (a) overview; (b) detail
Fig.12 Sample at different states: (a) three-dimensional model, (b) green sample, (c) sintered sample
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Table 1 Composition of the raw materials

Table 2 Printing conditions of 3DGP
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Table 3 The bending strength of the green samples prepared by different processes
Table 4 The top surface roughness of parts produced by different 3D printing processes
Table 5 Properties of sintered 316L samples prepared by different processes
Table 6 The dimensions of the three-dimensional model, the green sample and the sintered sample
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Fig. 11

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Fig. 12

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Table 1 Composition of the raw materials

Raw materials Content/vol. %
316L stainless steel powder 62.50
Toluene 26.58
HEMA 8.96

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Oleic acid 1.20

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Benzoyl peroxide 0.36
TEMED 0.40

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Table 2 Printing conditions of 3DGP

Printing condition Value
Nozzle diameter 0.4mm
Layer height 0.2mm

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Extrusion rate 7.0cm3/min
Printing speed 20mm/s

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Table 3 The bending strength of the green samples prepared by different processes

Process Material Binder Bending strength/MPa

3DGP 316L HEMA 16.1±2.2

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SLS[34] Carbon steel Nylon-12 3.12±0.18

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Metal injection molding (MIM) [35] 316L PMMA 4.9-13.3

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Press forming [36] FC-0205(FeCuC) EBS-wax 12-20

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Table 4 The top surface roughness of parts produced by different 3D printing processes
Process Material Ra/μm
Top surface Side surface
3DGP 316L 3.8±0.9 8.7±0.8

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FDM [37] ABS 24.7±4.6 16.1±2.5
SLS [38] Polyamide 10.47±1.7 -

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SLM [39] 316L 13.12±1.12 9.2±1.2
EBSM [40] 316L 7.9 -

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Table 5 Properties of sintered 316L samples prepared by different processes

Process Density Yield strength Tensile strength Rockwell hardness
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/gcm /MPa /MPa (HRB)
3DGP 7.73±0.06 174±13 488±15 88±2

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SLM[41] 7.78±0.08 534±5.7 653±3.4 -
Gel-casting[28] 7.75 162 493 72

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Powder Metallurgy [42] 6.9 210 390 45
Flat –rolled[43] 7.98 170 485 95

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Table 6 The dimensions of the three-dimensional model, the green sample and the sintered sample
Dimension Length Width Height
/mm /mm /mm
Design 32.00 16.00 8.00

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Green sample 32.49±0.02 16.46±0.02 8.21±0.02
Sintered sample 29.16±0.02 14.83±0.01 7.22±0.02

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Graphical abstract
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Highlights:
A new method of 3D gel-printing was developed by combining gelation and 3D
printing.
With optimizing the property of slurry, a stainless steel gear was fabricated as an

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example.
The green sample has a bending strength of 16.1MPa, surface roughness of

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3.5m.
The sintered sample has a surface roughness of 3.8m and tensile strength of

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488MPa.

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