A

Seminar Report On

“Fused Deposition Modeling”

For the Degree of Bachelor of Technology in Department of
Mechanical Engineering
Submitted By
Vishal Anil Jadhav [Roll No: 9]
Patil Nitin Chandrakant [Roll No: 10]
Ingale Kalpesh Satish [Roll No: 11]
Jadhav Sushant Ganesh [Roll No: 12]

Class: SE (Mech)
Under The Guidance of
Mr. Milind Ovhal
Head and Assistant Professor, Department of Mechanical Engineering

Department of Mechanical Engineering

PCET-NMVPM’S,
NUTAN COLLEGE OF ENGINEERING AND
RESEARCH,
TALEGAON, PUNE 401507
“To be recognized as a department of academic excellence through skill
development and innovation in fine blend with quality work culture.”

2020-2021
 LIST OF FIGURES

Figure No. Description of Figures Page No.

Diagram of FDM 3Dprinted PLA part fused 3

Figure No.1.1
Interface

Figure No.1.2 Model of the component. 6

Bond formation process between two fused 8

Figure No.2.1
PLA filaments

Figure No.2.2 Maximum stress values for interface 9

strength in PLA parts

Figure No.3.1 Concept illustration 13

13
Figure No.3.2 a. Bending load-deflection plot
b. optical micrograph of fractured section

FigureNo.3.3 a. Schematic of the experimental setup 14

b. variation of fracture energy for various pre-heating
conditions

Figure No.3.4 Impacted fractured surfaces of PLA 15

components via FDM

Figure No.3.5 Stress–strain response of 0.1-mm layer 17

thickness, 20% infill components heated for
various times of 0–60 min at 100 °C

Figure No.3.6 a. Build orientations in Cube software 18

b. S–N curves for three build orientations (X, Y, and45 °C)
orientations

[iv]
 Page
Figure No. Description of Figures
No.
Figure No 4.1 Differential scanning calorimetry (DSC) cooling curve of pure 20
PLA and PLA/PEG 10,000 blends at a rate of 10 °C/min
Figure No 4.2 Schematic diagrams of hypothesized factors leading to CNT 22
misalignment during 3D printing.
a. radial flow as the material overfills the gap

b. geometry-based fusion between adjacent roads

Figure No 4.3 a. tensile tests on 3D printed dogbone samples made from 22

non-irradiated control PLA,
b. tensile tests on 3D printed dogbone samples made from
10 wt.% TAIC sensitized PLA irradiated at 20°C and 60
°C
Figure No 4.4 a. 3D - printed parts tend to display weak tensile property 23
in the Y and Z directions due to poor interface welding.
To address this, we coated thermoplastic filament with a
CNT-rich layer; the resulting 3D-printed part contains
RF-sensitive nano fillers localized on the interface,
b. when a microwave field is applied, the interface is
locally heated to allow for polymer diffusion and
increased fracture strength

Figure No 4.5 Tensile and flexural strength of MWCNT/PLA composites 25

Figure No 4.6 Simplified schematics depicting the process of graphene-based 25

3D printing using the technique of FDM

[v]
 LIST OF TABLES

Page
Table. No. Description of Table
No.
Table No 1.1 Properties of PLA filaments (*DSC = Differential 4
Scanning Calorimeter).

Table No 1.2 Experimental schedule. 6

Table No 3.1 Experimental conditions (reprinted with permission) 15

Table No 3.2 Infill parameters and tensile strength 16

[vi]
 CONTENT

Chapter Title Page

No. No.

Certificate i

Acknowledgement ii

List of figures iii

List of tables iv

Content vi
viii
Nomenclatures

1 INTRODUCTION 1

1.1 Flaws And Priorities 3

1.2 Material 4
1.3 Design of the components 4
1.4 Equipment 5
1.5 Testing procedure 5

7
2 POLYLACTIC ACID (PLA)

2.1 Flaws and priorities of PLA 8

2.2PLA as bio‑based plastics 9

3 10
TECHNOLOGICAL STUDIES

3.1 Interface bonding property 12

3.2Mechanical properties and shape precision 15

PLA MODIFICATION STUDY 19

4 4.1 Cross-linking and crystalline ity improvement 20

4.2 Carbon material reinforced modification of PLA 23

4.3 Functional modification of PLA 23

[vi]
5 CONCLUSION 26

REFERENCES

[vii]
 NOMENCLATURE

FDM - Fused Deposition Modeling

PLA - Polylactic Acid
LOM - Laminated Object Manufacturing
SLS - Selective Laser Sintering
ABS - Acrylonitrile Butadiene Styrene
PC - Polycarbonate
NASA - National Aeronautics and Space Agency

[viii]
 Chapter No. 01
INTRODUCTION

Nutan Collage of Engineering & Research, Pune. Page No. 1

 Chapter No. 01
INTRODUCTION
1. Introduction
3D printing, mainly used in additive manufacturing (AM) and Combined with many fields of
materials, mechanical engineering, Computer technology, and electronics, started in the 1980s.
As one of the most representative techniques in the Third industrial revolution, it is also deemed
as a technique Driving the rapid development of the world, exerting an over powering effect on
our day-to-day life. Its matures technologies include fused deposition modeling (FDM),
selective laser sintering (SLS), stereo lithography apparatus (SLA), three-dimensional printing
(3DP), and laminated object manufacturing (LOM) [1]. The FDM technique becomes a research
highlight in 3D printing technology for its non-laser application and low cost in use and
maintenance. In addition, its consumables are mostly the low-melting-point polymer filaments
of polylactic acid (PLA), acrylonitrile butadiene styrene (ABS), polycarbonate (PC), and
polyamide (PA). Moreover, its equipment is small in size and easy in use, with a common
operating interface; the 3D printing of multi-phase compound materials is available by feeding
through multiple nozzles and multichannel, so as to get multifunctional parts. Thus, the FDM
technique is widely used in aerospace, automobile making, bio-medicals, smart home,
stationery and training aid, and creative gifts. It is worth noting that the first FDM 3D printer
named additive manufacturing facility (AMF) was sent to the space for the first time by the US
National Aeronautics and Space Agency (NASA) in 2014, and this printer could print the
spanner in the orbit to be used for maintenance and repair in the space station [2]. Moreover
NASA planned to send the second 3D printer to recycle 10,000 sealed plastic bags sent to the
space [3].
As the substance foundation, 3D printing material is one of the bottlenecks restricting the
further development of 3D printing technology. Currently, as a most promising material, PLA
is most extensively used in FDM 3D printing technology. Scholars at home and abroad
conducted more studies on FDM 3D-printed PLA parts. These studies focus on two aspects:
one is technological studies on optimization of key process parameters; the purpose is to
improve interface bonding property, mechanical properties, and accuracy; the other one the
PLA modification research, which involves the improvement of mechanical properties of PLA
parts by enhancing the cross-linking state and crystalline of PLA molecular chains and applying
reinforced phase; in addition, PLA parts become the ones with such functions as heat stability,
electrical conductivity, biocompatibility, antistatic property, electromagnetic shielding, and
temperature-controlled heating property by the functional compound modification of PLA.
These researches are of importance in improving whole performance, enhancing functional

Nutan Collage of Engineering & Research, Pune. Page No. 2

applications, and expanding or enriching the applications of FDM 3D-printed PLA parts. In this
paper, extensive literature studies are carried out on FDM 3D-printed PLA parts on the basis of
consulting plenty of domestic and overseas data. This paper is expected to give some helps and
references to the researchers who are specializing in this field.

Fig. No. 1.1 Diagram of FDM 3Dprinted PLA part fused interface

1.1 Flaws and priorities of PLA

Apparently, some practical problems encountered in FDM 3D printing of PLA are
unavoidable: firstly, PLA owns volume change and residual stress caused by the crystalline,
both of which may affect its dimensional precision. No crystallization occurs for the
amorphous polymers such as ABS and PC, but they themselves have a bigger shrinking
percentage. Moreover, with the greater melting and printing temperatures than PLA, they have
the bigger temperature gradient and stress during the FDM printing. Thus, their dimensional
precision is more uncontrollable, and even the war page may occur; secondly, the mechanical
strength of PLA is limited compared with such polymers as ABS, PC, and PA. This is because
the molecular chain of PLA is a very simple linear molecular chain structure microscopically,
while ABS, PC, and PA contain more complicated graft structures. However, just
microscopically, the simple structure and abundant open and active loci make it possible for
modified PLA in enhancement of mechanical properties and function extension.
Moreover, PLA has more incomparable advantages against other high polymer materials: (1)
no environmental contamination when it is degraded into H2O and CO2 as its synthetic raw
materials come from reproducible crops rather than petroleum; (2) no poison and irritation
with good biocompatibility, so that is widely used as medical suture material, drug sustained-
release material, and support and repair materials

Nutan Collage of Engineering & Research, Pune. Page No. 3

 1.2 Materials
Filaments in PLLA, ~96 % L-Isomer content, ~1.25 kDa molecular weight, ~1.6
polydispersity index, (Alfaplus, Filoalfa, Ozzero (MI), Italy) with a diameter of 1.75 ±
0.05 mm were used during the experimental tests [21]. The PLLA is modified by the
addition of less than 10 % of an elastomeric material (TPU, thermoplastic polyurethane).
The thermo-physical and mechanical properties of the material are reported

Table No. 1.1 Properties of PLA filaments (*DSC = Differential Scanning Calorimeter).

Properties Value Regulation

Density 124 g/cm3 ISO 1183
Melting Temperature 177 ◦C DSC*
Glass Transition Temperature 57 ◦C DSC*
Charpy 25 kJ/m2 ISO 179-1eU
Elongation at break at 20 ◦C 4, 1 % ISO 527
Tensile strength at break at 20 ◦C 43 MPa ISO 527
Flexure Modulus at 20 ◦C 3070 MPa ISO 527
Heat Deflection Temperature 58 ◦C ISO 75

1.2 Design of the components

The need to create lightweight structures with high stiffness has led to the development of
sandwich-type structures in recent years. They consist of two components: the rigid and
external skin, and the core, mostly consisting of hollow volume. Among the advantages
offered by structures of this type, there is the possibility of composing multiple materials
with different characteristics. In order to create skins and cores of different materials, it is
possible to fill the cavities of the core with light materials such as foams (for example,
flame retardant foams, insulating foams or capable of resisting the energy of an impact).
As a result of the light weight of the resulting components, the first and most frequent uses
of sandwich structures are in the aerospace field or as stress-absorbers in many
technological fields. The choice of the core texture allows to obtain multiple mechanical
properties. A first distinction can be made between in-plane and out-of-plane structures
[22, 23]: the core is the same but the arrangement of the structure changes, with the in-
plane type being of particular interest for the application in which a high stiffness,
especially for applications related to the structure impact resistance, plays a crucial role.
In this work, on-plane structures will be, however, considered. Fig. 1 reports the geometry

Nutan Collage of Engineering & Research, Pune. Page No. 4

 of the sample. The size is approximately 30 × 30 × 30 mm3. The model of the component
has been previously made at CAD. Subsequently, the file was converted to ‘.stl’ format.
Finally, the ‘.gcode’ file was created using the software Ultimate Cura 3.2.1 to be supplied
as input to the 3D printer for the manufacturing of the part.

1.3 Equipment’s

The manufacturing of the samples was performed using an open-chamber 3D printing

(Meeds, Zaturi, Rome, Italy). The system, based on FDM technology, is equipped with an
aluminum frame, an extruder with a diameter of 0.4 mm and a glass-built heated plate.
The filament is located on top of the aluminum space frame. The maximum printing
volume is 200 mm in diameter and 300 mm in height. The maximum temperature at the
nozzle is 260 ◦C. The maximum temperature of the built-in heated plate is 110 ◦C. The
layer resolution is 100 μm. The use of the heated built-in plate is necessary to guarantee
the adhesion of the model during the first steps. The first layers are of fundamental
importance, as their misalignment can cause a propagation of the defect throughout the
vertical extension of the sample.

1.4 Testing procedure

The experimental test consists of two different stages. In the first, the compression tests
of the samples are performed in order to program the new shapes of the samples.
Programming of the samples was performed at ambient temperature. During
programming, the deformation speed of the samples was set at 1 mm/min in order to
achieve the final shape very slowly, thus allowing the samples to gradually adapt to the
new shape. Additionally, the mechanical response of the samples by varying the printing
operating parameters is investigated. In the second, the capacity of the samples to recover
the initial shape varying the printing operating parameters and the activation temperature
to trigger the recovery process was investigated. The experimental procedure can,
therefore, be divided into the following operations:
• Identification of a set of printing parameters (Table 2) and manufacturing of the samples;
• Performing the compression tests on the samples to program them and assess the
mechanical response varying the printing operating parameters and data analysis;

Nutan Collage of Engineering & Research, Pune. Page No. 5

 Fig. No. 1.2 Model of the component.

Table No. 1.2 Experimental schedule.

Nozzle temperature, ◦C printing Speed, mm/s Layer thickness, mm

180 ◦C 40 mm/s 0.15 mm

210 ◦C 80 mm/s 0.30 mm

• Immersion of the sample in a temperature-adjustable water tank to recover the initial

shape at post heating temperature of 65, 75 and 85 ◦C (higher than the glass transition
temperature of the PLA);
• Analysis of the shape recovery for the samples manufactured varying the printing
operating parameters and data processing.

Nutan Collage of Engineering & Research, Pune. Page No. 6

 Chapter No. 02
POLYLACTIC ACID (PLA)

Nutan Collage of Engineering & Research, Pune. Page No. 7

 Chapter No. 02
POLYLACTIC ACID (PLA)
2.1 Flaws and priorities of PLA
Apparently, some practical problems encountered in FDM 3D printing of PLA are unavoidable:
firstly, PLA owns volume change and residual stress caused by the crystalline, both of which
may affect its dimensional precision. No crystallization occurs for the amorphous polymers
such as ABS and PC, but they themselves have a bigger shrinking percentage. Moreover, with
the greater melting and printing temperatures than PLA, they have the bigger temperature
gradient and stress during the FDM printing. Thus, their dimensional precision is more
uncontrollable, and even the warpage may occur; secondly, the mechanical strength of PLA is
limited compared with such polymers as ABS, PC, and PA. This is because the molecular chain
of PLA is a very simple linear molecular chain structure microscopically, while ABS, PC, and
PA contain more complicated graft structures. However, just microscopically, the simple
structure and abundant open and active loci make it possible for modified PLA in enhancement
of mechanical properties and function extension. Moreover, PLA has more incomparable
advantages against other high polymer materials: (1) no environmental contamination when it
is degraded into H2O and CO2 as its synthetic raw materials come from reproducible crops
rather than petroleum; (2) no poison and irritation with good biocompatibility, so that is widely
used as medical suture material, drug sustained-release material, and support and repair
materials

Fig. No. 2.1 a Bond formation process between two fused PLA filaments: (1) surface
contacting, (2) neck growth, (3) molecular diffusion at interface and randomization, b
microphotograph of the cross-sectional area of a FDM part: is the filament’s width, H is the
filament’s height, 2y is the neck length between adjacent filaments

Nutan Collage of Engineering & Research, Pune. Page No. 8

 Fig. No. 2.2 Maximum stress values for interface strength in PLA parts

In tissue engineering; (3) no decline of plasticity and toughness in the long-time service.

2.2 PLA as bio‑based plastics

The predicted production capacity of PLA is nearly 800,000 tons per year in 2020, from the
study by nova-Institute, based in Hurth, Germany. Currently, the overall power of 25
companies’ figures is 180,000 tons [39]. Nature Works shows a capacity of 140.000 tons in the
US and Thailand, the largest. Other producers are comparatively smaller. However, by 2020,
at least 7 locations will be manufacturing at least 50,000 tons of PLA, while the production
capacity will reach a million tons per annum. Lactic acid shall be a fundamental renewable
chemical that can be used more than PLA [40]. Forecasts of 800,000 or even up to 950,000 tons
per year by 2020 indicate that PLA will be the polymer for the future. The study, which
appeared in January 2013, was conducted by the Nova-Institute based on interviews and
discussions with producers of more than 30 different bio-based plastics worldwide and
constructed the latest “Bioplastics Producer Database” [1, 14, 19, 39]. PLA was made in the
1930s by Wallace Carothers, an American chemist well known for creating neoprene and nylon
in the chemical company DuPont. However, it was not till the 1980s that PLA was last made
for use by an American company Cargill [41]. Jan Ravenstijn was a well-known consultant in
the polymers world and specialized in bio‑based polymers. He conducted senior positions in
research and development at Dow Chemical and DSM throughout the past 10 years. Earlier in
the 1980s, he was engaged in the initiative for the advancement of PLA at Dow. He got an

Nutan Collage of Engineering & Research, Pune. Page No. 9

assignment to create an alternative for PS (polystyrene), biodegradable [41, 42]. PLA is a
versatile bio-based polymer used in 3D printers and many other applications. It is an adaptable
bioplastic that is biodegradable with various qualities. It is among the chief bioplastic around
the globe, and the query about its biodegradability is whether it is ideal or not. The most
important quality of PLA is its biodegradability. For many industrial composting installations,
they will fragment to lactic acid, a naturally existing non-toxic compound [43]. So it can be
concluded: responsible bioplastics users should switch from fossil to bio‑based and change their
business models [44, 45].

Nutan Collage of Engineering & Research, Pune. Page No. 10

 Chapter No. 03
TECHNOLOGICAL STUDIES

Nutan Collage of Engineering & Research, Pune. Page No. 11

 Chapter No. 03
TECHNOLOGICAL STUDIES

3.1 Interface bonding property

For PLA parts obtained by FDM 3D printing technology, the fuse has the nearly same
mechanical properties as that of die forming when it is melted, solidified, and continuously
distributed in its X direction, but it is discontinuous between fuses in the parallel distribution in
the Y direction and the gradually accumulating distribution in the Z direction, where the
macroscopic interface exists, as shown in Fig. 1. Obviously, the interface is the most fragile
position of 3D parts [4–6], so that the parts have poor properties with anisotropy as a whole [7,
8]. Moreover, the interface cannot be
removed as it is determined by the FDM printing technological principle. For this reason,
improving the interface bonding property to enhance the whole mechanical properties is an
important way to develop FDM 3D-printed PLA parts. Whether die forming or FDM printing,
it is a root cause for weak interface bonding and poor mechanical properties that the extruded
PLA cannot maintain enough time at the temperature of the melting point [9–12]. In the process
of FDM 3D printing PLA parts, the temperature of the extruded PLA filaments drops quickly
to the melting point or less in a short time due to the impacts of external environment and the
limitation volume of the filaments by nozzle melting. The PLA molecular chains on the
interface are not be diffused completely, so that these extruded PLA filaments cannot be well
fused with the newly extruded PLA filaments on the interface, even the holes occurs to lower
the strength of PLA parts. Figure 2 a indicates the bond formation process between two fused
filaments for FDM 3D-printed PLA parts; Fig. 2 b shows microphotograph of the cross-
sectional area of PLA parts, where the holes can be seen clearly.
It is always one of key tasks for researchers to solve interface molecular chain diffusion
and interface bonding of FDM 3D-printed PLA parts. In the FDM forming process, the control
of cooling speed is a crucial factor for interface bonding [13]. Too slow cooling can lead to the
disorder of fused PLA filaments, poor PLA parts forming ability, bad surface quality, and
serious deformation of parts shape. Too fast cooling may cause the fused PLA filaments
solidified in a short time, poor diffusivity of PLA molecular chains on interface, and bad
interface bonding, so that PLA parts present poor mechanical properties. Thus, the rationally
cooling speed of fused filaments for FDM in printed PLA parts has an important impact on
enhancing the interface bonding and improving surface quality. By this, Partain [14] tried to
blow the heated air to the FDM3D printed whole PLA parts via another nozzle so as to raise
the temperature of working environment and reduce

Nutan Collage of Engineering & Research, Pune. Page No. 12

 Fig. No. 3.1 Concept illustration: the laser local pre-deposition heating approach allows a
laser beam to heat up the plate locally where the new interfaces are forming. In doing so,
higher interface temperatures are obtained which allows more polymer interdiffusion across
the interface to increase FDM part strength in the build direction

Fig. No. 3.2 a Bending load-deflection plot, b optical micrograph of fractured section

It’s cooling speed. It is seen from Fig. 3 that when the air temperature is 65 °C, there is a
maximum interface strength for PLA parts, increasing by 66% against the case before the

Nutan Collage of Engineering & Research, Pune. Page No. 13

method is applied. However, there are practical restrictions for this method. On one hand, the
hot air can heat the PLA parts as a whole, so that the interface cannot be strengthened
accurately; on the other hand, the hot air blown out from the nozzle can produce the turbulent
flow, which leads to the disorder of fused PLA filaments, the damage to PLA parts surface
appearance in the printing process, and even the suspended forming process, especially it is
more serious for small-sized parts. Ravi et al. [15] proposed the synchronous and local laser
heating to the layered zone near the nozzle to raise the interface temperature exceeding critical
temperature of Tg (Fig. 4) by reasonable temperature controlling. By this way, the mutual
interface diffusion of PLA molecular chains was increased, the interface bonding was enhanced
in FDM 3Dprinted PLA parts. It is seen from Fig. 5 a that the test sample with laser pre-
deposition heating has more than 60% increase in strength, near 100% increase in elasticity,
and more than 3 times increase in toughness than the FDM part printed with the same
parameters but without laser pre-deposition heating. Moreover, there is surface reflow and
therefore enhanced infill in the samples using the in-process laser predisposition heating
approach, which also contributes to overall better strength and quality, as shown in Fig. 5 b. By
virtue of the same idea, Kishore et al. [16] realized synchronous and local heating with infrared
ray, as shown in Fig. 6 a. Table 1 exhibits three kinds of experimental conditions, and Fig. 6 b
shows the comparison of average mechanical properties. It is seen from the figures that cases 1
and 2 have a great increase of breaking energy after infrared ray preheating against non-heating,
while case 3 has a decline of average mechanical properties. This is because the PLA surface
exposed in the infrared ray radiation at an excessive intensity of 1 kW is degraded, so that it’s
mechanical

Fig. No. 3.3 a Schematic of the experimental setup, b variation of fracture energy for various
pre-heating conditions

Nutan Collage of Engineering & Research, Pune. Page No. 14

Table. No. 3.1 Experimental conditions (reprinted with permission)

3.2 Mechanical properties and shape precision

Scholars at home and abroad did great many researches on the Relation between the macro-
technological parameters of FDM Printing and the whole mechanical properties and shape
precision of PLA parts [19]. They proposed some macro structuring rules to improve strength
and precision of FDM

Fig. No 3.4 Impacted fractured surfaces of PLA components via FDM, a 0.2 mm, 30 °C
(layer height, plate temperature); b 0.2 mm, 160 °C; c 0.4 mm, 30 C, and d 0.4 mm, 160 °C

Nutan Collage of Engineering & Research, Pune. Page No. 15

Table. No. 3.2 Infill parameters and tensile strength

3D-printed PLA parts. For example, the strength of parts was affected by the printing direction;
the fuse direction of FDM 3D-printed PLA filaments should keep the same with the direction
of main stretching load to a greatest extent [20–22]; the lower layer height might increase the
additional printing time, but better surface quality was available [23]; the bigger the infill
density was, the greater the strength of test piece was
[24]. The temperature gradient could inevitably occur in the FDM 3D-printed PLA process
based on the technological principle of FDM laminated manufacturing and layer-bylayer
accumulation. The decrease of former layer temperature went against the bonding of interfaces,
and even led to deformation, warped edges, and therefore the decline of mechanical properties
of PLA parts. Thus, it is of importance to explore how to reduce the effect of temperature
gradient on the mechanical property and shape precision of PLA parts. At present, temperature
gradient was reduced mainly by controlling plate temperature and printing layer height. Lu et
al. [25] studied the effect of layer height and plate temperature of
FDM printing on impact toughness of FDM 3D-printed PLA parts. It is seen from Fig. 7 that
the PLA interface has better bonding and significantly reduced porosity at a plate temperature
of 160 °C and a layer height of 0.2 mm. So, the mechanical properties are improved remarkably
with no warped edge and high shape precision. But it should be noted that the pores in the
interface are not removed completely. Similarly, the extensive attention is paid to the effect of
such technological parameters as infill pattern and density, post-heat processing time, and
printing direction on the mechanical properties of PLA parts. For example, Patel et al. [26] set
lines, grid, and concentric infill patterns with different infill density, as shown in Table 2, where
line patterns with 60% infill density got the highest tensile strength of FDM 3Dprinted PLA
parts compared with the other two pattern and density values. Torres et al. [27] studied that the

Nutan Collage of Engineering & Research, Pune. Page No. 16

proper post heat processing time also had an important effect on the shear
Stress property of FDM 3D-printed PLA parts as shown in Fig. 8. Too high or low post-heat
processing temperature might exert an adverse effect on the shear stress property of FDM 3D-
printed PLA parts. Afros et al. [28] constructed FDM 3D-printed PLA parts respectively in X,
Y, and 45° orientations, as shown in Fig. 9 a, explored that the FDM 3Dprinted PLA parts with
45° printing orientations had the best fatigue property, as shown in Fig. 9 b. It is currently a
common practice for FDM printing to set a certain proportion of overlaps in the printing fused
PLA filaments track. The FDM device could provide the optional setting of this parameter.
However, the overlap might increase the shape precision of the FDM 3D-printed parts to some
extent, but it had no evident improvement in interface bonding

Fig. No. 3.5 Stress–strain response of 0.1-mm layer thickness, 20% infill components heated
for various times of 0–60 min at 100 °C

Nutan Collage of Engineering & Research, Pune. Page No. 17

 Chapter No. 04
PLA MODIFICATION STUDY

Nutan Collage of Engineering & Research, Pune. Page No. 18

 Chapter No. 04
PLA MODIFICATION STUDY

4.1 Cross-linking and crystallinity improvement

In the microcosmic condition, PLA molecular chains are macromolecular chains with poorer
molecular symmetry, which affects its diffusion ability and crystallinity to some extent [33,
34], particularly within the limited time in FDM printing process; therefore, PLA only has
partial crystallinity as a semicrystalline polymer. Thus, FDM3D-printed PLA parts present
the poor interface bonding property and low mechanical properties.

Fig. No. 4.1 Differential scanning calorimetry (DSC) cooling curve of pure
PLA and PLA/PEG 10,000 blends at a rate of 10 °C/min

In order to improve the diffusion ability of PLA molecules, Levenhagen et al. [35] added a
series of synthetic low molecular weight (LMW) PLA components (8.5 k, 50 k, and 100 k) to
the bimodal mixture (220 k) PLA to obtain FDM 3Dprinted PLA parts whose cross-linking
degree of molecular chains was improved (Fig. 10), As a result, the whole mechanical
properties of the parts were improved. In order to improve the crystallinity of PLA molecules,
a proper proportion of plasticizer was added, and accordingly, the mechanical properties of
FDM3D-printed PLA parts were also improved after the complete crystallinity [36–39]. Li et
al. [40] added polyethylene glycol (PEG) 10,000 to PLA as a plasticizer; the melting

Nutan Collage of Engineering & Research, Pune. Page No. 19

crystallization peak of PLA/ PEG-10,000 blends occurred at 84.9 °C with the PEG content of
10 wt%, indicating PEG could improve the PLA crystallization power effectively. However,
excessive PEG dosage more than 10 wt%, there is an occurrence of PEG crystallization peak,
as shown in Fig. 11. It means the existence of separate PEG, which might limit the mechanical
properties improving of FDM 3D-printed PLA parts.
Patanwala et al. [41] discussed the nucleation and viscosity of PLA modified by carbon
nanotube (CNT), mainly focused on interface flow state described by Qr parameter, as shown
in Fig. 12. When Qr ≦ 1, there were poor flow and small defects on the interface, which were
negative for interface bonding and the whole mechanical properties of FDM 3D-printed parts.
Otherwise, when Qr > 1, there was fine flow on the interface with firm bonding.
However, what needs to be pointed out is that it is very short time for fused PLA filaments
staying in the molecular diffusion and crystallization temperature after they are melted and
extruded through the nozzle in FDM printing. So, it is still insufficient for molecular diffusion
and crystallinity. For this reason, many scholars proposed that the radiation sensitive material
was added in the PLA filaments or on the PLA filaments surface before FDM printing; then,
PLA parts were radiated by electron beam [42], γ ray [43], or microwave [44] respectively after
FDM printing. The sensitive material might absorb the radiation. On one hand, the free radicals
were produced in main chain or side chain of PLA. By further chemical bonding reaction, these
free radicals enabled the molecular chains of PLA parts at the interface to be further cross-
linked and entangled. On the other hand, the temperature was controlled by changing radiation
intensity, so that FDM 3D-printed PLA parts were kept in crystallization temperature for a long
time, so as to increase crystallinity. Shaffer [45] blended trimethylolpropane Tri acrylate
(TMPTA) and trially isocyanate (TAIC) sensitive to γ ray with PLA. After FDM 3D-printed
PLA parts were obtained, they were radiated by γ ray. The temperature of PLA parts could be
kept near Tg by controlling radiation intensity. The results showed that the tensile property of
PLA parts was improved greatly after radiation, as shown in Fig. 13. Sweeney et al. [44] soaked
PLA filaments surface with carbon

Nutan Collage of Engineering & Research, Pune. Page No. 20

 Fig. No. 4.2 Schematic diagrams of hypothesized factors leading to CNT misalignment
during 3D printing: a radial flow as the material overfills the gap, b geometry-based fusion
between adjacent roads

Fig. No. 4.3 a tensile test on 3D printed dogbone samples made from non-irradiated control
PLA,
b tensile tests on 3D printed dogbone samples made from 10 wt% TAIC sensitized PLA
irradiated at 20°C and 60 °C

Nutan Collage of Engineering & Research, Pune. Page No. 21

 4.2 Carbon material reinforced modification of PLA

Both carbon fiber and multi-walled carbon nanotube (MWCNT) were widely used as the
reinforced phase materials in polymer composite materials as they had such advantages as
high specific strength, high specific modulus, low density, and fatigue resistance. They were
used extensively and have been the research hotspots in the FDM field [46, 47]. Li [48] and
Kuan et al. [49] fabricated the filaments of FDM printing with carbon fiber and MWCNT for
the reinforced phase modified PLA, so that such mechanical properties as average tensile
strength and impact toughness of FDM 3D-printed PLA parts were improved to the greatest
extent (Figs. 15 and 16). However, it should be pointed out that both carbon fiber and
MWCNT presented surface chemical inertia and poor infiltration with PLA matrix due to
smooth surface, less active

Fig. No. 4.4 a. 3D - printed parts tend to display weak tensile property in the Y and Z
directions due to poor interface welding. To address this, we coated thermoplastic filament
with a CNT-rich layer; the resulting 3D-printed part contains RF-sensitive nanofillers
localized on the interface,

b when a microwave field is applied, the interface is locally heated to allow for polymer
diffusion and increased fracture strength

4.3 Functional modification of PLA

Scholars at home and abroad also were intended to mix some functional materials with PLA,
trying to print the functional parts by FDM with thermal stability, conductivity,

Nutan Collage of Engineering & Research, Pune. Page No. 22

biocompatibility, antistatic property, electromagnetic shielding, and temperature-controlled
heating, so as to expand the functional applications of FDM 3D-printed PLA parts [50–59]. For
example, Zhang et al. [60] proposed that graphene-based flexible circuit was printed by FDM
with PLA/r-GO composite filaments. And the FDM printed PLA/r-GO circuit presented
excellent conductivity of 4.76 S/cm with the r-GO content of 6 wt%, as shown in Fig. 17.
Considering the same material combination, Yu et al. [61] explored the whole mechanical
properties besides conductivity. At the same time, he proposed that more polymeric materials
such as modified PE and PLA were tested using more metal or ceramic granules such as Cu,
Al, and Al2O3 to obtain more FDM 3D-printed parts with more composite properties.
As a degradable polymer with good biocompatibility, PLA was often printed by FDM to obtain
bone tissues whose biocompatibility was further modified. By this way, its bioactivity
could be obtained greatly [62]. Teixeira et al. [63] used FDM to printed PLA composite porous
scaffold, and carried out the surface treatment for it using collagen (COL) and dopamine-DA
(DOPA) respectively. He planted cells into the scaffold for a 7-day cultivation, and the cells
were still alive. Relative to pure PLA, the scaffolds treated with COL and DOPA had more cells
reproduced and the good biocompatibility was available. However, the products after PLA were
degraded easily was acidic and they often caused human tissue inflammation. Nano-
hydroxyapatite (nHA) had buffer action to the acidic PLA-degraded products as well as good
biocompatibility and bio-activity. Moreover, bone induction and porous structure of nHA could
provide good conditions for cell growth, tissue regeneration, and vascularization. Zhang et al.
[64] printed PLA-nHA composite biomimetic scaffold by FDM, and carried out the cultivation
and reproduction of marrow stroma cells (MSC) in the scaffold. After that, the scaffold was
placed in the unilateral tibia of a white rabbit, successfully promoting growth of the new bone
and no adverse rejection occurring. Dong et al. [65] synthesized starshaped PLA(sPLA) by bulk
ring-opening polymerization of L-lactide with pentaerythritol as a four-arm initiator and
stannous octoate as a catalyst and prepared sPLA-heparin (sPLAHep) by coupling heparin to
the sPLA reaction using carbonyldiimidazole (CDI) chemistry. The sPLA-Hep surface
demonstrated lower protein adsorption and platelet adhesion than control sPLA surface as show
in Fig. 18 a. In addition, fibroblast culture on the sPLA-Hep surface showed the enhanced cell
spreading area compared with the sPLA surface as show in Fig. 18 b. Therefore, sPLA-Hep
could be applie as blood/tissue compatible biodegradable materials for implantable medical
devices and tissue engineering. Apparently, modification of PLA is more potential and
valuable, because it cannot only improve mechanical properties, but also multiply varied
functions, especially biocompatibility applications.

Nutan Collage of Engineering & Research, Pune. Page No. 23

 Fig. No. 4.5 Tensile and flexural strength of MWCNT/PLA composites

Fig. No. 4.6 Simplified schematics depicting the process of graphene-based 3D printing
using the technique of FDM

Nutan Collage of Engineering & Research, Pune. Page No. 24

 Chapter No. 05
CONCLUSION

Nutan Collage of Engineering & Research, Pune. Page No. 25

 Chapter No. 05
CONCLUSION

5.1 Conclusions
The discussed technical parameters and the modification methods in the reviewed literature can
significantly improve the mechanical properties and accuracy of FDM 3D-printed PLA parts.
The potential of fabricating isotropic and enhanced PLA parts can be available directly from
commercial FDM printers with controllable technical parameters; meanwhile, fabricating
functional devices with the multi-properties of modified PLA has created a huge rush for the
new developments of the FDM field. They even can be implemented or referenced in various
3D printing techniques, such as SLA, SLS, and LOM. In conclusion, FDM 3D-printed PLA
part is tremendously promising in turning 3D printing from a prototyping method to a robust
and functional manufacturing technique, and it have gained enormous attention from a broad
range of science industries as a turning point for 3D printing technology. However, most
methodologies for FDM 3Dprinted PLA part are still facing major challenges, which need to
be overcome before becoming a mainstream manufacturing method.

Nutan Collage of Engineering & Research, Pune. Page No. 26

\

REFERENCES

Nutan Collage of Engineering & Research, Pune. Page No. 27

 REFERENCES:

[1] Vaezi M, Seitz H, Yang S (2013) A review on 3d micro-additive manufacturing

technologies. Int J Adv Manuf Technol 67(5–8): 1721–1754
[2] Wall M. Space station’s 3d printer makes wrench from “beamed up” design.
https://www.space.com/28095-3d-printer-spacestation- ratchet-wrench.html. 2014-12-
23
[3] Anderson J. Full Circle: NASA to demonstrate refabricator to recycle, reuse, repeat.
https://www.nasa.gov/mission_pages/centers/ marshall/images/refabricator.html.
2017-08-28
[4] Cuiffo MA, Snyder J, Elliott AM (2017) Impact of the fused deposition (FDM) printing
process on polylactic acid (PLA) chemistry and structure. Appl Sci 7(6):579
[5] Gu P, Li L (2002) Fabrication of biomedical prototypes with locally controlled
properties using FDM. CIRPAnn Manuf Technol 51(1): 181–184
[6] Kishore V, Ajinjeru C, Nycz A, Post B, Lindahl J, Kunc V (2016) Infrared preheating
to improve interlayer strength of big area additive manufacturing (BAAM) components.
Addit Manuf 14: 756–765
[7] Lee CS, Kim SG, Kim HJ, Ahn SH (2007) Measurement of anisotropic compressive
strength of rapid prototyping parts. J Mater Process Technol 188(12):627–630
[8] Levenhagen NP, Dadmun MD (2018) Interlayer diffusion of surface segregating
additives to improve the isotropy of fused deposition modeling products. Polymer
17:546–601
[9] Sungmr Q, Bellehumeur C T, Gu P (2003) Experimental study of the cooling
characteristics of polymer filaments in FDMand impact on the mesostructures and
properties of prototypes. Proceedings of the 14th Solid Freeform Fabrication
Symposium 14:312–323’
[10] Sun Q, Rizvi GM, Bellehumeur CT, Gu P (2008) Effect of processing conditions onthe
bonding quality of FDM polymer filaments. Rapid Prototyp J 14:72–80
[11] Wang YQ, Wang ZM, Shen CJ, Wu YL (2012) Research on enhancement of GFRP-
anchor’s torsional strength. Sci Eng Compos Mater 19(4):423–429
[12] Wang YQ, Guo Y, Wang ZM, Wu YL (2014) Preparation and mechanical properties of
nano-sillicaUPR polymer composite. Sci Eng Compos Mater 21(4):471–477

[13] Bellehumeur C, Li L, Sun Q, Gu P (2004) Modeling of bond formation between polymer

Nutan Collage of Engineering & Research, Pune. Page No. 28

 filaments in the fused deposition modeling process. J Manuf Process 6(2):170–178
[14]Seth Collins P (1985) Fused deposition modeling with localized pre-deposition heating
using forced air. Montana State Univ 41(10):1975–1975
[15] Ravi AK, Deshpande A, Hsu KH (2016) An in-process laser localized pre-deposition
heating approach to inter-layer bond strengthening in extrusion based polymer additive
manufacturing. J Manuf Process 24:179–185
[16] Kishore V, Ajinjeru C, Nycz A, Post BK, Lindahl JM, Kunc V, Duty CE (2016) Infrared
preheating to improve interlayer strength of big area additive manufacturing (BAAM)
components. Addit Manuf 14:321–324
[17] Zhao C, Yang G (2015) Numerical simulation of a new nozzle based on the principle of
FDM forming performance. Int J Control Autom 8:526–536
[18] Behzadnasab M, Yousefi A (2016) Effects of 3D printer nozzle head temperature on the
physical and mechanical properties of PLA based product. Int Semin Polym Sci Technol
11:1256–1435
[19] Bahnini I, Rivette M, Rechia A, Siadat A, Elmesbahi A (2018) Additive manufacturing
technology: the status, applications, and prospects. Int J Adv Manuf Technol 2:1–15
[20]Torres J, Cole M, Owji A, Demastry Z, Gordon AP (2016) An approach for mechanical
property optimization of fused deposition modeling with polylactic acid via design of
experiments. Rapid Prototyp J 22(2):387–404
[21]Shilpesh RR, Harshit KD (2018) Analysis of tensile strength of a fused filament
fabricated PLA part using an open-source 3D printer. Int J Adv Manuf Technol 4:1–12
[22]Yang JH, Zhao ZJ, Park SH (2015) Evaluation of directional mechanical properties of
3D printed polymer parts. International Conference on Control IEEE
[23] Vaezi M, Chua CK (2011) Effects of layer thickness and binder saturation level
parameters on 3D printing process. Int J Adv Manuf Technol 53(4):275–284
[24] Jin ZF, Jin YF, Zhou M (2016) Research of processing property of PLA materials for
3D printing based on FDM. China Plast Ind 50: 369–400
[25] Lu W, William G, Gardner M, Douglas J (2017) Improving the impact strength of
poly(lactic acid) (PLA) in fused layer modeling (FLM). Polymer 114:242–248
[26] Patel DM (2017) Effects of infill patterns on time, surface roughness and tensile strength
in 3D printing. IJEDR 5(3):2321–2341 Torres J, Cotelo J, Karl J, Gordon AP (2015)
Mechanical property optimization of FDM PLA in shear with multiple objectives. JOM
67(5):1183–1193
[27] Afrose MF, Masood SH, Iovenitti P, Nikzad M, Sbarski I (2015) Effects of part build
orientations on fatigue behaviour of FDMprocessed PLA material. Prog Addit Manuf

Nutan Collage of Engineering & Research, Pune. Page No. 29

 1(12):21–28
[28] Dae KA, Jin HK, Jin HC, SeokHL (2011) Relation between surface roughness and
overlap interval in fused deposition modeling. Adv Mater Res 20(11):264–265
[29] Zhu ZJ, Shen JY, Jin JM (2016) The shrinkage analysis and control methods research
of FDMproducts. Manuf Technol Mach Tool 12: 29–32
[30]S M, M K M, E P (2015) Feasibility study of ultrasonic frequency application on fdm
to improve parts surface finish. Mpra Pap 77(32):456–464
[31] Wang DF, Zeng XY (2016) A method for the manufacture of additive in vibration
condition, CN 105458264 A 1–5
[32] Tabi T, Sajo IE, Szabo F, Hajba S (2010) Crystalline structure of annealed polylactic
acid and its relation to processing. Express Polym Lett 4(10):659–668
[33] Jaszkiewicz A, Meljon A, Bledzki AK (2016) Mechanical and thermomechanical
properties of pla/man-made cellulose green composites modified with functional chain
extenders-a comprehensive study. Polym Compos 39:1716–1723 Int J Adv Manuf
Technol
[34] Levenhagen NP, Dadmun MD (2017) Bimodal molecular weight samples improve the
isotropy of 3D printed polymeric samples. Polymer 122:232–241
[35] Tang Z, Zhang C, Liu X, Zhu J (2012) The crystallization behavior and mechanical
properties of polylactic acid in the presence of a crystal nucleating agent. J Appl Polym
Sci 125(2):1108–1115
[36] Dai JX, Yang Q, Liu BJ (2013) Crystallization behavior of PLA/ PEG/nucleating agent
blends. Adv Mater Res 809:578–581
[37] Chen Y (2012) Effect of nucleating agent on crystallization behaviors and mechanical
properties of PLA. Mod Plast Process Appl 4: 235–245
[38] Li Y, Han C, Yu Y, Xiao L, Shao Y (2018) Crystallization behaviors of poly(lactic acid)
composites fabricated using functionalized eggshell powder and poly(ethylene glycol).
Thermochim Acta 663:67–76
[39] Zhang GH, Xiong W, Chen M, Liu XQ (2014) Crystallization behavior and mechanical
properties of PLA/nucleating agent plasticized with PEG. J Shaanxi Univ Sci Technol
9:365 374
[40] Patanwala HS, Hong D, Vora SR, Bognet B, Ma WK (2017) The microstructure and
mechanical properties of 3D printed carbon nanotube-polylactic acid composites.
Polym Compos 10:1–12
[41] Ji SG, Cho D, ParkWH, Lee BC (2010) Electron beam effect on the tensile properties
and topology of jute fibers and the interfacial strength of jute-PLA green composites.

Nutan Collage of Engineering & Research, Pune. Page No. 30

 Macromol Res 18(9): 919–922
[42] Monti MC, Casapullo A, Riccio R (2004) Further insights on the structural aspects of
PLA(2) inhibi tion by gammahydroxybutenolide- containing natural products: a
comparative study on petrosaspongiolides M-R. Bioorg Med Chem 12(6):1467–1474
[43] Sweeney CB, Lackey BA, Pospisil MJ, Achee TC, Hicks VK, Moran AG (2017)
Welding of 3D-printed carbon nanotube– polymer composites by locally induced
microwave heating. Sci Adv 3(6):e1700262
[44] Shaffer S, Yang K, Vargas J, Prima MAD, Voit W (2014) On reducing anisotropy in
3D printed polymers via ionizing radiation. Polymer 55(23):5969–5979
[45] Ferreira RTL, Amatte IC, Dutra TA, Bürger D (2017) Experimental
[46]and micrography of 3D printed PLA and PLA reinforced with short
[47]carbon fibers. Compos B Eng 124:88–100
[48] Tian X, Liu T, Yang C, Wang Q, Li D (2016) Interface and performance of 3D printed
continuous carbon fiber reinforced PLA composites. Compos A Appl Sci Manuf
88:198–205
[49] Li N, Li Y, Liu S (2016) Rapid prototyping of continuous carbon fiber reinforced
polylactic acid composites by 3D printing. J Mater Process Technol 238:218–225
[50] Kuan CF, Kuan HC, Ma CCM, Chen CH (2008) Mechanical and electrical properties
of multi-wall carbon nanotube/poly(lactic acid) composites. J Phys Chem Solids 69(5–
6):1395 1398
[51] Yao YG, Mei-Na XU, Zhou GM (2017) On the development of biodegradable
PLA/PBAT/PHBV blending 3D printing composite materials. J Zhejiang Fashion Inst
Technol 10:458–465
[52] Liu W, Zhou J, Yongsheng LI,Wang J, Jie XU (2017) Influence of addition of ATBC
on the preparation and properties of PLA/PCL filaments for FDM 3D printing. J Funct
Mater 18:256–265
[53] Haq RHA, Mohd NAR, Ahmad MTA, Fahrul HM, Zaini YM, Adzila S (2017)
Characterization and mechanical analysis of PCL/PLA composites for FDM feed stock
filament. IOP Conference Series: Materials Science and Engineering 226(1): 120–138
[54] Mao D, Li Q, Li D, Chen Y, Chen X, Xu X (2018) Fabrication of 3D porous poly(lactic
acid)-based composite scaffolds with tunable biodegradation for bone tissue
engineering.Mater Des 30:268–295
[55] BHChi ,ZWJiao ,FF Liu ,WMYang (2016) Study on fabrication of CNT-based
conductive products via melt differential 3D printer. Plastics 6(45):1–4
[56] Kennedy ZC, Christ JF, Evans KA, Arey BW, Sweet LE, Warner MG (2017) 3D-printed

Nutan Collage of Engineering & Research, Pune. Page No. 31

 poly(vinylidene fluoride)/carbon nanotube composites as a tunable, low-cost chemical
vapour sensing platform. Nanoscale 9(17):5458–5466
[57] Kumaran A, Jeeva PA, Aravindh K (2017) Metallization of PLA plastics prepared by
FDM-RP process and evaluation of corrosion and hardness characteristics. ICMMM
8(4):56–60
[58] Yang Y, Chen Y,Wei Y, Li Y (2016) 3D printing of shape memory polymer for
functional part fabrication. Int J Adv Manuf Technol 84(9–12):2079–2095
[59] Zhao J, Xiangqun Z, Wenhai YU, Tian W, Luo K (2017) Fabrication of starch/PLA
biodegradable 3D printing filaments toughened by glycerol. Mater Rev 6(4):89–99
[60]Daniel F, Patoary NH, Moore AL, Weiss L, Radadia AD (2018) Temperature-dependent
electrical resistance of conductive polylactic acid filament for fused deposition
modeling. Int J Adv Manuf Technol 4:1–10
[61] Zhang D, Chi B, Li B, Gao Z, Du Y, Guo J (2016) Fabrication of highly conductive
graphene flexible circuits by 3d printing. Synth Met 217:79–86
[62] Yu WW, Zhang J, Wu JR (2017) Incorporation of graphitic nanofiller and poly(lactic
acid) in fused deposition modeling. J Appl Polym Sci 134(15):1–11
[63] Narayanan LK, Huebner P, Fisher MB, Spang JT, Starly B, Shirwaiker RA (2016) 3D-
bioprinting of polylactic acid (pla) nanofibers-alginate hydrogel bioink containing
human adiposederived stem cells. ACS Biomater Sci Eng 2(10):1732–1742
[64] Teixeira BN, Aprile P, Kelly DJ, ThiréRMSM(2017) Evaluation of BMSCs response to
PLA scaffolds produced by FDM and coating with dopamine and collagen. Congresso
Latino-Americano de Orgãos Artificiais e Biomateriais 20:560–580 Zhang HF, Du ZJ,
Mao XY, ZhaoD Y, Du C, Jiang WB, Han D (2016) Experimental research of
constructing tissue engineered bone using three-dimensional printed polylactic
acidhydroxyapatite composite scaffolds. Int J Orthop 37(1):57–63
[65] Dong HG (2010) Heparin-conjugated star-shaped pla for improved biocompatibility. J
Biomed Mater Res A 86(3):842–848 Int J Adv Manuf Technol

Nutan Collage of Engineering & Research, Pune. Page No. 32