Stereolithography: Review

ME 677 Term Paper

By

Tejas Ladhe
(17D100014)
Under the guidance of
Prof. Deepak Marla

DEPARTMENT OF MECHANICAL ENGINEERING

INDIAN INSTITUTE OF TECHNOLOGY BOMBAY
14th March 2021

1
Abstract

Stereolithography Apparatus (SLA), being the earliest method of additive production, creates 3D
artifacts by selectively solidifying the liquid resin through a photopolymerization reaction.
Stereolithography brings a significant attention to the ability to produce objects with high precision
and a wide range of materials. Over the past 40 years, SLA has experienced four generations of
substantial technical advancement since its discovery in the 1980s. Thus, these advances have
resulted in a diversified range of stereolithography systems for creating complex 3D artifacts and
devices with significantly improved resolution, throughput, and material selection.

The four generations of stereolithography methods, which are scanning, projection, continuous and
volumetric stereolithography, are reviewed in this paper. Along with this, the apparatus and step by
step working of the process is explained. Some insights of mathematical modelling of
polymerization, which is the basis of Stereolithography, are also discussed in this paper..
In depth, representative stereolithography device configurations are also addressed for each
generation. In addition, other derivative technologies are also included in this study, such as
scanning-projection, multi-material, and magnetically assisted stereolithography processes.
Applications of Stereolithography and commercially available SLA systems are also discussed in this
paper.

Standard Tessellation Language (STL) is a file format native to the Computer Aided Design (CAD)
applications for stereolithography produced by 3D Systems. Many other software packages support
this file format; it is commonly used for rapid prototyping, 3D printing and computer-aided
manufacturing. Without any representation of color, texture or other typical CAD model attributes,
STL files describe the surface geometry of a three-dimensional object. Both ASCII and binary
representations are defined by the STL format. Since they are more portable, binary files are more
common. This paper provides the very basic information about history, the types of STLs,
representation of curved surfaces and uses.

Keywords: Stereolithography Apparatus (SLA), Photopolymerization, Standard Tessellation

Language (STL), Computer Aided Design (CAD)

2
Contents

Abstract 2

Introduction 4
1.1 History
1.2 Advantages and Disadvantages 5

Generations of Stereolithography 6
2.1 Evolution
2.2 Working System
a. STL File Format
2.3 Generations of Stereolithography 8
a. Laser Stereolithography
b. Projection Stereolithography 9
c. Continuous Stereolithography 11
d. Volumetric Stereolithography 12

Stereolithography Cure Process Modelling 14

3.1 Model Development
a. Boundary Conditions
b. Photopolymerization Kinetic Model 15
c. Model Parameters 16
3.2 Material Characterization 17
a. Specific Heat Capacity
b. Glass Transition Temperature 19
c. Coefficient of Thermal Expansion 21
d. Density 22
e. Thermal Conductivity
f. Heat of Polymerization
g. Absorption Coefficient 23
3.3 Summary

Applications 24
4.1 Commercially Available SLA Systems

Conclusions 26

References

3
Chapter 1

Introduction

Stereolithography (SLA for Stereolithography Apparatus 1.1 Background

or SL) is a type of 3D printing technique which is used to An early and commonly used 3D printing technology is
manufacture highly complicated designed structures. stereolithography or "SLA'' printing. By using ultraviolet
The process builds a part or product layer-by-layer by light to cure photosensitive polymers, Japanese
using photochemical monomers which in presence of researcher Hideo Kodama first developed the modern
light combine with each other to form a long chain of layered approach to stereolithography in the early
polymers (See Fig 1.1). Since the type of materials used 1980s. Alain Le Mehaute, Olivier de Witte and Jean
for Stereolithography are not capable of the standards of Claude André applied for a patent for the
metals or alloys in terms of strength, durability or stereolithography process in 1984, just before Chuck
reliability, the process is most commonly used to create Hull filed his own patent. The French General Electric
prototypes for products in development, models in Company (now Alcatel-Alsthom) and CILAS (The Laser
medical research or simulations, and computer Consortium) have abandoned the French inventor's
hardware, as well as in many other applications. patent application.
Stereolithography is a quick but expensive technique Chuck Hull coined the word 'stereolithography' in 1984
and can produce almost any complicated design in very when he filed his patent for the technique. As a method
less time in comparison with classical machining of producing 3D objects by successively 'printing' thin
techniques. layers of an object using a medium curable by ultraviolet
light, beginning from the bottom layer to the top layer,
Chuck Hull patented stereolithography.

a - Basic principle of SLA method (Top-Down)

b - Basic principle of SLA method (Bottom-Up)

Fig 1.1

4
 Introduction

A concentrated beam of ultraviolet light centered on the 1.2 Advantages and Disadvantages
surface of a vat filled with a liquid photopolymer is There are several advantages of using Stereolithography
mentioned in Hull's patent. The beam is centered on the as a manufacturing process. The process gives high
surface of the liquid photopolymer, by generation of detailing, smooth surface finishing and better
intermolecular bonds in polymers (crosslinking) to dimensional accuracy than any other process. It is
create each layer of the desired 3D object. It was ideally used for producing visual prototypes as it is not
invented in order to enable engineers to manufacture very time consuming, and can complete a job in a couple
prototypes of their designs more efficiently over time. of hours only. However, depending on the part’s
Hull co-founded the world's first 3D printing company, geometry complexity , it can take several hours or more
3D Systems, to commercialize it, after the patent was than a day.
issued in 1986.
The success of stereolithography in the automotive Although, there are several disadvantages of the process
industry allowed 3D printing to gain industry status, and too. Generally, the produced parts are brittle and don’t
in many fields of research, the technology continues to retain very good mechanical properties such as strength
find innovative uses. In order to decide whether a and toughness. Post processing is required after the
proposed object can be built using 3D printing, attempts process but that also does not improve the mechanical
have been made to create mathematical models of properties a lot. Moving mechanical parts with
stereolithography processes and to develop algorithms. demanding mechanical properties cannot be created
That is why the process is not suitable to produce
functional prototypes. Also degradation of visual and
mechanical properties occur overtime when the parts
are exposed to sunlight.

Keywords: CILAS (The Laser Consortium), Photopolymer

5
Chapter 2

Generations of Stereolithography

The first significant work associated with modern

stereolithography AM systems emerged during the
1970s. Swainson presented a patent for a system in
which 3D objects can be built by two intersecting
radiation beams through either photochemically
cross-linking or degrading polymers. Then, Herbert
introduced a system for building solid objects in a
layer-by-layer method with photosensitive polymers.
However, most people agree that modern
stereolithography began with the work of CW Hull.

2.1 Evolution
The 3D objects are created layer by layer with
photosensitive materials that can be healed by
ultraviolet (UV) radiation, according to Charles W. Hull's Fig 2.1 - Hull’s Stereolithography System
concept. By scanning a laser beam over the liquid
materials, the first generation scanning 2.2 Working System
stereolithography described by Hull's work produced 3D The process of stereolithography (Fig 3) starts with a
products in the early stage. The second generation standard tessellation language (STL) file, which now is
method, also known as projection stereolithography, is the standard for every AM process. By slicing the STL
able to cure each layer simultaneously with the use of file, the 3D model is translated to 2D slices that contain
photomask technology to eliminate the limits of low the information of cross-sections. According to these 2D
performance. In 2015, Tumbleston et al. introduced the slices, the physical model can be produced layer by layer.
continuous stereolithography of the third generation.
They developed a Continuous Liquid Interface 2.2.a Standard Tessellation Language (STL)
Development (CLIP) technique, which makes it possible The STL file consists of a list of details about facets. Each
to manufacture parts in minutes instead of hours at a facet is uniquely described by a normal unit, a line
much higher print speed than previous approaches. perpendicular to the triangle and the length of the unit,
Most recently, a volumetric stereolithography was and three vertices. Three coordinates each specify the
reported that produces 3D artifacts on a time scale of normal and each vertex, so there are a total of 12
seconds with the unit of complex aperiodic 3D volumes, numbers stored for each facet.
and can be seen as the fourth generation. There are,
however, several other methods, such as color Facet Orientation. The facets define the surface of a
stereolithography and thermal stereolithography, which 3-dimensional object. The orientation of the facets is
are also used. specified by two rules -

Keywords: Scanning Stereolithography, Projection Stereolithography, Continuous Stereolithography, Volumetric

Stereolithography, Color Stereolithography, Thermal Stereolithography
6
 Generations of Stereolithography

a) The direction of the normal is outward. Below is the structure of the STL (ASCII) file format -
b) The vertices are listed in counterclockwise order
solid name
when looking at the object from the outside
(right-hand rule).
facet normal n_i, n_j, n_k
outer loop
Vertex-to-Vertex Rule. Each triangle must share two
vertex v1_i, v1_j, v1_k
vertices with each of its adjacent triangles.
vertex v2_i, v2_j, v2_k
vertex v3_i, v3_j, v3_k
All vertex coordinates are required to be positive.
endloop
Direction can be defined with the unit vector. In order to
endfacet
maximize the performance of the slice program, sorting
the triangles in ascending z-value order is
facet normal n_i, n_j, n_k
recommended, but not necessary. Usually, an STL file is
outer loop
saved with the case-insensitive extension 'stl'. This
vertex v1_i, v1_j, v1_k
extension may be required by the slice program or it
vertex v2_i, v2_j, v2_k
may allow for the specification of a different extension.
vertex v3_i, v3_j, v3_k
endloop
endfacet

facet normal n_i, n_j, n_k

outer loop
vertex v1_i, v1_j, v1_k
vertex v2_i, v2_j, v2_k
vertex v3_i, v3_j, v3_k
endloop
endfacet

.
. (Add more facets)
.

endsolid name

Fig 2.2 - The Fabrication process of Stereolithography

7
 Generations of Stereolithography

Below is the structure of the STL (Binary) file format - Scanning with galvanometric mirrors, however, results
in light beam defocusing, as well as optical errors. To
UINT8[80] – Header
UINT32 – Number of triangles prevent these problems, an idea of using the X-Y
translation stage with a fixed centered light beam
foreach triangle instead of galvanometric mirrors was introduced. The
REAL32[3] – Normal vector centered laser point stays fixed on the resin during
REAL32[3] – Vertex 1 printing and the X-Y translation stage is intended to
REAL32[3] – Vertex 2 move either all the optical systems or the printing
REAL32[3] – Vertex 3 platform on which the object is printed. Fig 2.4 shows a
UINT16 – Attribute byte count system known as constrain-surface system. For this
end system, objects are produced below a transparent glass
window since the fixed light beam focuses on resin
2.3 Generations of the technology through the window and the vector tracing of each layer
Since Hull proposed modern stereolithography, it has is executed by motorized stages.
undergone four generations of technical advancement.
Using various technologies, researchers have built
different kinds of physical systems to improve
stereolithography efficiency. Benefiting from these
systems, we can use a variety of materials to print
sophisticated objects with several orders of magnitude
in size.

2.3.a Laser Stereolithography

Laser scanning stereolithography imprints a 3D object
as the first generation by scanning a directed laser beam
over the surface of the resin to cure the irradiated resin.
Some researchers used galvanometric mirrors to control
the laser beam moving in the X-Y direction to perform
the scanning, while a motorized stage is taken to adjust Fig 2.4 - Constrain-Surface System
the location for each layer.
The purpose of a transparent glass window is to push
the liquid resin to prevent the spreading of the fresh
resin to the already polymerized part of the object,
allowing the thickness of the layer to be well managed.
However, Polymerization through a glass window
creates a significant limitation of the constrain-surface
scheme, which is the resin's adhesion to the glass
window. Zissi et al. first described a scanning
stereolithography system with a free surface technique
in 1994 to address this problem, and Zhang et al. also
presented their high-resolution free-surface system in
Fig 2.3 - Laser scanning using Galvanometric mirrors 1998.

Keywords: Galvanometric mirrors

8
 Generations of Stereolithography

It differs from traditional stereolithography by

concentrating laser pulses of the femtosecond to a very
narrow spot where the resin is polymerized by
simultaneously absorbing two photons.

2.3.b Projection Stereolithography

By projecting mask patterns onto the resin surface, the
second generation stereolithography can print each
layer of objects concurrently with a single exposure. The
initial photomask ideal was suggested in the 1980s by
Fudim. Fudim created a device that, through masks and a
piece of flat material transparent to the radiation,
Fig 2.5 - Free-Surface System illuminates a curable resin with UV radiation. Then, in
the early 1990s, to create 3D models, Pomerantz
Like the constrain-surface system, motorized phases are implemented his photomask method. The working
often used to map the contour profile of each layer of process of his system can be concluded as:
artifacts in the free-surface system. In order to create a) Deposit a thin layer resin
artifacts above the printing platform, the fixed UV light b) Illuminate the resin through a xerographically
beam focuses on the resin surface and solidifies the created mask that has a single cross section
curable resin. The free-surface stereolithography c) Remove the uncured resin
method shows excellent capacity in the manufacture of d) Fill the regions vacated by the uncured resin
microstructures without adhesion problems. e) Cure the rest of the layer
Furthermore, two-photon polymerization (2PP), another f) Grind the surface to build a uniform layer
significant laser scanning technique, is regarded as a g) Repeat these steps until the object is completed.
special photopolymerization process. However, this kind of photomask system requires a great
number of masks and precise mask alignment, which
consume a lot of cost and time.

A solution to the listed drawbacks is to replace multiple

mask sets with a dynamic mask. Using a liquid crystal
display (LCD) as a dynamic mask, Bertsch et al.
developed a projection stereolithography device. Each
pixel of an LCD is a small cell that can be set by altering
the orientation of the molecules it contains to either its
transparent or its opaque state. In projection
stereolithography systems, the LCD can therefore be
used as a dynamic mask-generator. In order to improve
its performance, the LCD-based dynamic mask was
Fig 2.6 - Two-photon further studied in projection stereolithography by
polymerization (2PP) system researchers. Although the methodology of LCD
demonstrates great superiority over previous methods,
it has some inherent flaws.

9
 Generations of Stereolithography

The large pixel size, very low transmission in UV and C. Sun et al. introduced their DMD-based
poor contrast seriously limit the further development of stereolithography system in 2005. In their system, a UV
projection stereolithography systems. light source and a UV curable resin of 1,6-hexanediol
The digital micromirror device (DMD) developed by diacrylate (HDDA) were used for the fabrication of
Texas Instruments, which is widely used in video complex 3D microstructures with the smallest feature of
projection applications, has been adopted as a dynamic 0.6 µm. Fig 2.7 shows a typical top-down projection
mask for projection stereolithography. The DMD is in stereolithography system. Due to the high efficiency,
fact an array of up to several millions of mirrors that can which only depends on the layer thickness and the
be controlled independently to generate mask patterns. required exposure time, and the excellent property of
Table 2.1 below provides the comparison between LCD DMD, projection stereolithography using DMD as a
and DMD. The first stereolithography system using DMD dynamic mask has been widely used for micro
was reported by Bertsch et al. while a light source with manufacturing applications.
visible wavelengths was used in their system.

Table 2.1 - Comparison between LCD and DMD

LCD DMD

UV Compatibility No Yes
Modulation Efficiency 12.5% (transmission) 88% (reflection)
Pitch Size 26 μm x 24 μm 14 μm - 17 μm
Pixel Size 33 μm x 33 μm 13 μm - 16.2 μm
Filling Ratio 57% 91%
Contrast 100:1 350:1
Switching Speed 20 ms 20 μs

Fig 2.7 - The top-down projection stereolithography system

10
 Generations of Stereolithography

2.3.c Continuous Stereolithography light exposure area, Y. Chen et al. also presented their
To reduce time taken by cycles of steps, a continuous continuous stereolithography system. Differing from the
manufacturing process, CLIP, from layer to layer was passive resin feeding used in the CLIP technique, the
introduced. This converted the following 3 steps cycle to resin recoating in Y Chen’s system can be significantly
a single step cycle: accelerated by the side motion. It is therefore expected
a) To expose resin to UV light, that the printing speed of continuous stereolithography
b) The cured part needs to be mechanically moved would be further enhanced. The CLIP technique has
either to separate from the surface of resin vat quickly gained a lot of attention due to strong
(for bottom-up systems) or to lower into the competitive advantages, although it has only been a few
resin (for top-down systems) for resin renewal, years since it was first proposed.
c) Re-positioning
Since each step takes several seconds, the printing speed Some researchers have documented their various
is restricted to a few millimeters per hour. Continuous continuous stereolithographic approaches in addition to
Liquid Interface Process (CLIP) (See Fig 2.8), achieved CLIP. A thermal controlled continuous stereolithographic
by creating a persistent liquid interface (dead zone) with approach that uses a mobile liquid interface to decrease
an oxygen-permeable window below the UV image the adhesive forces between the window and the curing
projection plane, is devised to print objects without artifacts was stated by Chad A. Mirkin (Fig 2.9).
stops from layer to layer.

Fig 2.8 - Continuous Stereolithography process Fig 2.9 - HARP System

The photopolymerization between the window and the Since the mobile liquid interface (flowing immiscible
polymerizing part can be inhibited by the fluorinated oil) can reduce interfacial adhesion and
oxygen-containing dead zone, which enables the part to dissipate heat in the building field, high-area rapid
be continuously exposed when elevated. The latter two printing (HARP) can be achieved without thermal
phases that have existed in conventional limitations by rapid printing speeds. A dual-wavelength
stereolithography may therefore be omitted. The pieces CLIP method was demonstrated by Timothy F. Scott et al.
can be continuously drawn out of the resin at rates of (Fig 2.10), where one wavelength of light is used to
hundreds of millimeters per hour by using CLIP. By suppress polymerization while a second wavelength of
integrating a side motion along the X axis between the light initiates resin polymerization.
resin tank and the Z platform to actively feed resin to the

Keywords: CLIP

11
 Generations of Stereolithography

An inhibition region can be created between the window By the compensation between each beam, volumetric 3D
and the curing parts, eliminating adhesion and allowing geometries can be formed in a single exposure from the
continuous printing by varying the intensity of two light superimposed profile. Timothy F. Scott’s team further
sources. explored their dual-wavelength process to realize
volumetric 3D printing (Fig 2.12).

Fig 2.10 - Dual-wavelength irradiation System

Fig 2.11 - Dual-wavelength Volumetric

2.3.d Volumetric Stereolithography
Stereolithography
Distinguishing from previous stereolithography
processes that fabricate structures layer by layer,
By employing two perpendicular irradiation patterns at
volumetric stereolithography produces 3D objects with
blue and near-UV wavelengths to independently effect
the formation of 3D volumes as a unit operation.
either polymerization initiation or inhibition, the system
Inspired by holographic lithography, Maxim Shusteff et
allows the fabrication of objects by volumetric
al. first introduced volumetric 3D structures patterned
photopolymerization patterning in bulk resin. A
as a single operation into 3D printing. They designed a
promising volumetric additive manufacturing technique
volumetric stereolithography system (Fig 2.11) in which
realized by tomographic reconstruction was separately
the superposition of patterned optical fields from three
proposed by Hayden K. Taylor et al. in 2019 and Paul
orthogonal beams were projected into a photosensitive
Delrot et al. in 2020. The tomographic volumetric
resin.
stereolithography is based on the simultaneous
irradiation of an entire volume of photosensitive resin.
As shown in Fig 2.13, a cylindrical container of resin is
set into rotation while it is being irradiated from the side
with computed patterns of light. The light patterns
computed by a Radon transform, similarly to
tomography, are displayed in synchronization with the
rotational movement of the resin container. After the
resin has been illuminated from all angles by patterns, a
three-dimensional distribution of accumulated light
dose is created, causing the resin to locally reach its
Fig 2.11 - Volumetric Stereolithography gelation threshold, thus the desired objects can be
fabricated as a whole of volume (Fig 2.14).

Keywords: Holographic Lithography

12
 Generations of Stereolithography

Currently, the volumetric additive manufacturing has

shown the potential to produce complex parts with a
high throughout (>105 mm3 per hour) and a wide range
of materials. In the foreseeable future, volumetric
stereolithography is expected to be further developed in
many aspects, such as resolution, process and physical
system, and combined with various fields.

(a) (b)
Fig 2.13 - Concept of Tomographic Volumetric Stereolithography

Fig 2.13 - The printing process and a model printed by tomographic volumetric stereolithography

13
Chapter 3

Stereolithography Cure Process Modelling

In this chapter, a research paper “Stereolithography Cure

Process Modeling Using Acrylate Resin” is discussed
which is based on the work of Yanyan Tang, Clifford L.
Henderson, John Muzzy, David W. Rosen, a group of
Georgia Institute of Technology. A complex
stereolithography (SL) cure process model is presented
in this paper, which includes transient thermal and
chemical effects that influence the shape and properties
of the final component. Photopolymerization, mass
diffusion, and heat transfer are all included in the model.
Fig 3.1 - Single laser scanned cured shape
For a model compound system, material properties are
defined and a detailed kinetic model is parameterized. The shaded area is where temperature or concentrations
This chapter only presents a model of Stereolithography differ, and its size grows over time as heat conduction
by expressing the process kinetics and thermodynamics and/or molecular diffusion continue. The domain size is
in the form equations which are also validated by the chosen to ensure that atmospheric temperature and
group stated above. concentrations are preserved outside the rectangle at all
times.
3.1 Model Development
The laser travels in one direction and draws a single
vector scan line in the simplest case of complex laser
drawing patterns in SL apparatus. A parabolic cylinder is
the cured form of a single laser drawn line, as shown in
Fig 3.1, where the x axis is the laser drawing direction.
A rectangular domain in Cartesian coordinates (Fig 3.2)
was developed to simulate the resin cure behaviour
during the single-line drawing process, taking into
account the parabolic plane's repetition along the x axis
and its symmetry about the x-z plane.

Fig 3.2 - SL process modelling domain

14
 Stereolithography Cure Process Modelling

The two transport phenomena that occur in the SL cure Equations -

phase are mass transfer by diffusion and heat transfer by
[M] = [M]i t=0, 0≤y≤5wo, -2Cd≤z≤0 (4-a)
conduction. The energy balance, mass balance for the
monomer, and mass balance for polymeric radicals are ∂𝑇
=0 y=0, -2Cd ≤ z ≤ 0, t≥0 (4-b)
∂𝑦
all described in the equations below. ∂𝑇 z=0, 0 ≤ y ≤ 5wo, t≥0
∂𝑧
=0

= ℎ(𝑇0 − 𝑇) z=0, 0 ≤ y ≤ 5wo, t≥0

∂𝑇 (4-c)
𝑘 ∂𝑦

[P◦] = 0 t=0, 0≤y≤5wo, -2Cd≤z≤0 (4-d)

3.1.b Photopolymerization Kinetic Model

Below are the representation of polymerization
occurring during the curing process -

Here ρ, Cp, k and △Hp are density, specific heat capacity,

thermal conductivity and heat of polymerization,
respectively, of the monomer-polymer mixture at any
particular instant. Rp and Rt are rates of polymerization
and termination, respectively, at any instant during the
curing process. where PI represents photoinitiator, which decays to
generate primary radicals R•, M represents monomer,
3.1.a Boundary Conditions which reacts with radicals to create and elongate
Following conditions are expressed in mathematical polymer chains Pn•. These chain radicals Pn• could
format below. Here T0 in equation 3 is external combine with one another and terminate to become
temperature. dead polymer Mn, which is no longer reactive.
1. Initially the whole domain is filled with liquid This initiation, propagation and termination can be
monomer. expressed in following equations -
2. For the selected domain, there should be no
Ri = φiIa (5)
temperature gradients in vertical direction at
y=0 and horizontal direction at z=0. (6)
RP = kP[P•][M]
3. Convection heat transfer coefficient at horizontal
boundary z=0 is h.
RP = kt[P•]2 (7)
4. Initial radical or polymer concentration is zero

15
 Stereolithography Cure Process Modelling

where φi is the initiation quantum yield, Ia is the the rate constants when the reactions are not limited by
absorbed light intensity (mol/m3 -s), [P•] is the chain diffusion. Ap and At are temperature-independent
radical concentration, [M] is the monomer constants to be determined by fitting the experimental
concentration, and kp and kt are the propagation and data. The initial radical concentration is obtained by
termination rate constants, respectively. The integrating the rate of initiation:
dependence of kp and kt on temperature and free volume
−2.3ε𝐸
can be incorporated into following relations - [𝑃•]0 = φ𝑖𝑆0(1 − 𝑒 ) (10)

𝑘𝑃0 (8)
𝑘𝑃 = 𝐴𝑃(1/𝑓 − 1/𝑓𝑐𝑝)
where ε and S0 are the absorption coefficient and initial
1+𝑒 concentration of initiator, respectively, and E (mol/m2 )
is the exposure applied on the resin.
𝑘𝑡 0 (9)
𝑘𝑡 = 1 3.1.c Model Parameters
1+ 𝐴 (1/𝑓 − 1/𝑓 )
𝑡 𝑐𝑡
𝑅𝑟𝑑 𝑘𝑝 [𝑀] / 𝑘𝑡0 + 𝑒 The process and laser parameters were obtained from
where f is the fractional free volume, fcp and fct are an actual process in a SLA-250 machine and are shown
critical fractional free volume terms for propagation and below in Table 3.1. Liquid monomer used is E4PETeA
termination, respectively. Rrd is the reaction diffusion tetraacrylate with 2 wt% photoinitiator DMPA.
parameter. kp0 and kt0, dependent on temperature, are

Table 3.1 - Parameters used

Parameter Unit Data Range

Process Parameters Laser Scanning Velocity m/s 0.0272

Bath Temperature k 304.65
Heat Convection Coefficient W/m2-K 4.18

Laser Parameters Laser Power W 0.028

Wavelength nm 325
Beam Radius m 1.10E-04

Material Properties Thermal Conductivity W/m-K 0.2

Heat Capacity J/kg-K 1700
Heat of Polymerization J/mol 3.46E+05
Absorptivity (initiator) m3/mol-m 19.9
Initiation quantum yield
Diffusion coefficient (monomer) m2/s 1E-14 to 1E-08
Diffusion Coefficient (radical) m2/s 1E-14 to 1E-08
CTE (monomer) 1/K 0.00182
CTE (polymer) 1/K 0.00032
Glass transition temp (monomer) K 209.9
Glass transition temp (polymer) K 503.15
Density kg/m3 1175
Density (monomer) kg/m3 1128

16
 Density (polymer) kg/m3 1200

Stereolithography Cure Process Modelling

3.2 Material Characterization

3.2.a Specific Heat Capacity Below figures 3.3 and 3.4 are exported plots of heat
capacity signal for liquid E4PETeA monomer and its
A modulated differential scanning calorimeter (MDSC) cured polymer, respectively. Samples were weighed
option for DSC 2920 was used to measure the specific 12.09±0.03 mg using an analytical balance
heat capacity of the pure monomer and pure polymer.

Fig 3.3 - Cp-T plot for monomer

17
Keywords: MDSC, DSC
Stereolithography Cure Process Modelling

Fig 3.4 - Cp-T plot for polymer

The heat capacities were found to be functions of

temperature as follows: 𝐶𝑃 = 𝐶𝑃𝑀(1 − 𝑋) + 𝐶𝑃𝑃𝑋
● CPM = 5.6(T) + 218.6
● CPP = 9.1(T) - 1535.5 where X is the fraction of monomer converted.
where CPM is specific heat capacity of monomer and CPP is
specific heat capacity of polymer. And weighted average
specific heat capacity of monomer and cured polymer
can be expressed as -

18
 Stereolithography Cure Process Modelling

3.2.b Glass Transition Temperature

The glass transition temperatures of liquid E4PETeA Figures 3.7 and 3.8 illustrate the effect of heating rate on

monomer and its cured polymer are determined using a the Tg measurement. In the range of heating rates tested,

standard differential scanning calorimeter, DSC 2920. the measured Tg value increases linearly with the

The samples were weighed ~16mg for several heating heating rate. For Tg measurement, a heating rate within
rates: 5, 10, 15, 20 C/min. Figures 3.5 and 3.6 are the 10-20 o C/min is recommended. A lower heating rate
heat flow curves at 10C/min heating rate and leads to gradual material change and thus less obvious

demonstrate the glass transition of liquid monomer and glass transition.

cured polymer, respectively.

Fig 3.5 - Glass Transition temperature for monomer

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Keywords: Glass Transition Temperature
Stereolithography Cure Process Modelling

Fig 3.6 - Glass Transition of Cured polymer

Fig 3.7 - Heating Rate vs Tg Value of Monomer Fig 3.7 - Heating Rate vs Tg Value of Monomer

To eliminate the heating rate effect, the Tg values 3.8 to 0 C/min, -67.5 C and 215.2 C, are adopted for
obtained by extrapolating linear curves in Fig 3.7 and liquid monomer and cured polymer, respectively.

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 Stereolithography Cure Process Modelling

3.2.c Coefficient of Thermal Expansion

The coefficients of thermal expansion (CTE) of monomer
and cured polymer were determined by using an
ellipsometry technique to measure film thickness at
different temperatures. The linear CTE is defined as

where ∂𝐿/∂𝑇 is the slope of the film thickness versus

temperature plot, and L the average thickness over the
temperature range investigated. The variable angle
spectroscopic ellipsometer was used to determine the Fig 3.9 - Temperature vs Film Thickness for Polymer
film thickness at elevated (heating) or lowered (cooling)
temperatures. The fit for the first temperature scan (heating cycle) in
Fig 3.9 has a significantly higher slope than the second
scan (cooling cycle). This is probably due to the residual
unconverted monomer which has greater CTE entrapped
in the polymer matrix.
The films with a thickness greater than 1000 Å were
produced for the purpose of measurement. The thermal
fluctuation of the air above the film could cause a large
error in the thermal property quantification for films
with thickness less than 1000 Å.
The volumetric CTE can be obtained by the following
equation, assuming the bulk material is isotropic.

Fig 3.8 - Temperature vs Film Thickness for monomer

Before ellipsometric measurement, the film was heat where V is the volume of the material over the

treated to minimise the entrapped solvent to the point temperature range investigated.

that there was no solvent impact during the heating or

cooling stages. Fig 3.8 shows two L-T curves that almost
overlap each other.

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Keywords: Ellipsometer
Stereolithography Cure Process Modelling

3.2.d Density 3.2.f Heat of Polymerization

The density of the cured polymer was found to be 1200 The heat of polymerization was also calculated to be 650
3
kg/m at 35 C (column control temperature) by using a J/g from the theoretical enthalpy of 20.6 kcal/mol per
density gradient column. The temperature dependence acrylate double bond.
of density can be described as follows using the The isothermal standard DSC experiments performed on
volumetric CTE α : the model material show that the thermally initiated
polymerization doesn’t occur below 130 C. The DPC
experiments were performed at constant light intensity
(0.36 mW/cm2 ) for several different temperatures
below 130 C. The heat generated due to polymerization
Similarly, for the monomer density: was found to increase with temperature linearly.

where ρM(298 K) =1128 kg/m3

The density of the curing material system can be

expressed as:

where φM is the monomer volume fraction.

3.2.e Thermal Conductivity

The thermal conductivity of polymer can be calculated
Fig 3.9 - Temp vs heat generated by polymerization
using the following equation :

Additional standard DSC experiments were conducted at

elevated temperatures (till 350 C at a rate of 10 C/min)
for samples irradiated at 130 C. A small amount of
where ρ , CP , Lf , UR, Vm , and ν are density, specific heat residual heat was detected and added to give the
capacity, average free path length, Rao function, molar maximum total heat of 540 J/g generated at light
volume per structural unit and Poisson’s ratio of the intensity = 0.36 mW/cm2.
cured polymer, respectively.

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 Stereolithography Cure Process Modelling

3.2.g Absorption Coefficient The investigated system assumed to obey the Beer’s law,
The absorption coefficient of the photoinitiator, DMPA, the extinction coefficient spectra of the three solutions
was determined by using a UV-VIS spectrometer and of different concentrations overlap with one another.
Beer’s law. To obtain the absorption spectrum of DMPA
in its E4PETeA solution, spectral subtraction was
performed.

The 0.05, 0.1, 0.2 wt% DMPA in E4PETeA were used as

sample and pure E4PETeA monomer as reference in the
spectrometer. The absorption spectrum thus obtained is
the direct subtraction of the absorption of pure
monomer from that of solution. The subtraction factor
the reference absorption is multiplied by was taken as
1.0 due to the low concentrations investigated.
Fig 3.10 - Absorption Coefficient Spectrum of DMPA

3.3 Summary
In this chapter, the material thermal and physical properties are measured experimentally and verified by the
theoretical calculation and literature values for similar materials. These properties and relations can be used to carry a
computer based simulation of the process to produce a resulting surface and compare with a physical experiment.

Table 3.2 - Characterized Material Properties

Material Properties Data Range Unit

Thermal Conductivity 0.2 W/m-K

Heat Capacity 1700 J/kg-K
Heat of Polymerization 3.46E+05 J/mol
Absorptivity (initiator) 19.9 m3/mol-m
Initiation quantum yield 0.6
CTE (monomer) 0.00182 1/K
CTE (polymer) 0.00032 1/K
Glass transition temp (monomer) 209.9 K
Glass transition temp (polymer) 503.15 K
Heat Capacity (monomer) CPM = 5.6(T) + 218.6 J/kg-K
Heat Capacity (polymer) CPP = 9.1(T) - 1535.5 J/kg-K

Heat Capacity (curing system) CP = CPM(1-X) + CPPX J/kg-K

Density 1175 kg/m3
Density (monomer) 1128 kg/m3
Density (polymer) 1200 kg/m3

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Keywords: UV-VIS spectrometer

Chapter 4

Applications

With implementations in a variety of industries, SLA is a Medicine implementations, where patient-specific

very flexible process. For example, the aerospace and designs are often needed to accommodate individual
automotive industries will profit from rapid production anatomies, may also benefit greatly from AM. In order to
of high-performance materials. In addition, microfluidics determine the geometric requirements from which
and medicine are critical fields where SLA demonstrates equipment is then made, CT or MRI scans may be used.
tremendous potential and is already being successfully For example, craniofacial implants with porously
applied. From highly elastic silicones for soft robotics structured hydroxyapatite have been implanted in
applications to high-strength thermally post-curing patients with large bone defects. Since the 1970s, CAD
epoxy resins, completely polymeric materials structured modeling has been used in dentistry to produce crowns
by SLA can vary in their properties. For most polymeric that are used to cover a damaged tooth, and dentures
materials, their restricted thermo-mechanical stability that are temporary or fixed devices to replace missing
is, however, a concern. A possibility in SLA is the use of teeth. In order to speed up the process between the
filled resins to create metal or ceramic structures. In collection of geometrical data and the implantation of
addition, by using monomers as precursors, the system into the patient, several AM technologies,
polymer-derived ceramics can be produced which including SLA, can now be used. The manufacture of
contain the essential components to form ceramics upon hearing aids is a second application in healthcare, where
pyrolysis. For geometry, these techniques provide AM has become the norm. The production time of these
superior flexibility than casting or machining processes custom-made devices can be reduced from more than a
and can generate components for high-temperature week to less than a day by SLA while also enhancing
applications, such as in propulsion systems or as wear comfort.
thermal insulators.
4.1 Commercially Available SLA Systems
In the field of microfluidics, where small fluid volumes At present, many SLA printers are on the market,
need to be accurately manipulated by micro-sized varying in price and quality from amateur desktop
channels for applications such as inkjet print heads or applications to high-precision professional devices. In
Table 4.1, a brief overview of their specifications is given.
lab-on-a-chip technologies, SLA has recently been
The LCD-SLA is open to hobbyists only as a low-budget
extensively investigated. DLP-SLA displays superior 3D printer. However, the more common techniques such
resolution, smaller feature sizes, reduced surface as traditional laser-SLA and DLP-SLA have their low-cost
roughness, and faster processing times in this and low-resolution desktop editions for customers, but
application as compared to material extrusion and can also provide technical and industrial applications
jetting. It is fast and easy to combine channels with with high-end techniques. Although both CLIP and TPP
dimensions below 100 μm and valves, pumps, as well as are in higher price ranges, the former is designed to
produce larger parts extremely quickly, while the latter
multiplexers.
is used for the very slow manufacture of small parts with
sub-micron resolution.

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 Applications

Table 4.1 - Comparison of commercially available SLA systems

SLA - type Lateral Printing Speed Maximum Print Commercial Vendors
Resolution (μm) (mm/h) Size (mm)

Laser 60-140 14 27-750 3DSystems, Formlabs, XYZPrinting

TPP 0.400 - 100x100x3 Nanoscribe

DLP 33-120 25-150 45-230 EnvisionTEC, Kudo3D

CLIP 50-100 500 80-320 Carbon

LCD 50-100 20-60 55-160 SparkMaker, Photocentric

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Conclusions

● Stereolithography is an additive manufacturing technique that fabricates 3D objects by selectively solidifying

the resin through photopolymerization initiated by absorbing light energy. During the decades of development,
various kinds of processes as well as systems of stereolithography are demonstrated, and this paper
categorizes stereolithography processes or systems into four generations.
● The values and relations in chapter 3 can be used to conduct a simulation to generate surface characteristics
based on the laws mass conservation and energy conservation as discussed. And this model can be compared
with actual surfaces generated from a physical experiment.
● Applications and currently available stereolithography based printing machines are also discussed in this
paper. (Chapter 4)

References

A. Chapter 1 - Introduction:
a. Wikipedia
b. 3D HUBS

B. Chapter 2 - Generations of Stereolithography::

a. A Review of Stereolithography - Processes and Systems
b. Standard Tessellation Language (STL)
1. https://docs.fileformat.com/cad/stl/
2. https://www.fabbers.com/tech/STL_Format

C. Chapter 3 - Stereolithography Cure Process Modelling:

a. Yanyan Tang, Clifford L. H., John M., David W. Rosen - “Stereolithography cure process modelling”

D. Chapter 4 - Applications:
a. Christina Schmidleithner, Deepak M. Kalaskar: “Stereolithography”

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