Stereolithography

Joe McCullough Chris Hannigan

ENGR 371 Spring 2013 4-9-13

1. Introduction
Rapid-prototyping is a quickly growing method in manufacturing. One of the most relevant rapid-prototyping processes is stereolithography. Stereolithography is an additive process where layers are built upon each other. The procedure begins with a basin filled with photocurable resin, or photopolymer, and a platform that is slightly submerged within this. A blade swipes over the initial level to apply a fresh coat of resin and to make sure the layer is even. The stereolithographer then takes a CAD model as input and uses a laser to begin the first layer. The laser cures the resin using UV light to the desired shape of the current layer. The elevator lowers the platform to the next layers width, and the blade again swipes over it. As seen in figure 1, this process is continually repeated, building up the product layer by layer. When all layers of the product are complete, the platform is raised and the finished product is removed from the basin. Any support materials needed during solidification are removed. Sometimes it is necessary to further cure the product in order to reach complete solidification. This is done in post curing apparatuses such as an UV chamber or thermal oven.

Figure 1: Overview of stereolithography apparatus [14]

2. History
The term Stereolithography was coined by 3D Systems' president Chuck Hull, president of 3D Systems where the method was invented. Hull developed the concept of "three dimensional printing" in 1982, while vice president of engineering at UVP, Inc, a company specializing in applications of ultraviolet light technology. One such application was the development of UV coatings for the printing industry. Hull realized that the photopolymers used in the process were, in effect, thin films of plastic, and that overlapping successive layers could potentially yield three dimensional objects. Over the next two years these thoughts evolved into a system that could actually build parts, so he applied for a basic patent in 1984. The basic patent for the process was assigned to UVP in March, 1986, which officially began Stereolithography [8].

3. Computer-aided Design
Much like other rapid-prototyping production methods, stereolithography starts with a Computer-aided Design (CAD) model. The product to be made is first modeled to the desired dimensions on a computer and saved as a .stl file [9]. After the CAD model is completed, the CAD software mathematically slices the model into thin, horizontal cross sections using the .v (vector) and the .r (parameter) files [8,9]. These cross sections are sized depending on the desired cross sectional thickness, but generally are limited to the width of the laser being used; the smallest tolerance being 0.0125 mm [1]. The data is then sent to the stereolithographer where an image of each slice is produced [9]. The stereolithographer then builds the product from the bottom up, each defined layer at a time [11].

4. Photopolymer Materials
Stereolithography requires a liquid photopolymer that will cure when ultraviolet light is introduced. In order to obtain these results a liquid-acrylate polymer is used. This polymer consists of a liquid mixture of acrylic monomers, oligomers and photoinitiators.

4.1 Acrylic monomer

An acrylic monomer form polymers which are derived from acrylic acids. The acrylic properties often have moderate strength, good optical properties, and weather resistance. They are often transparent, generally resistant to chemicals, and have good electrical resistance [1]. Properties of the desired material largely depends on the mix and make up of monomers present in the liquid-acrylate polymer.

4.2 Oligomer

An oligomer is a molecule with few monomers. An oligomer is used in photopolymers to act as a polymer intermediate. These oligomers bind the acrylic monomers with the photoinitiators during the process of curing. The most common oligomer used has (meth)acrylate at the end. That is because it allows for it moisture permeability, weatherability and heat resistive properties. The amount of oligomers depends on the desired characteristics of the overall material. A preferred amount of oligomers present in the photocurable composition is 30 to 90 parts by mass based on 100 parts by mass of the sum of the amounts of the photocurable liquid (photoinitiator) and the acrylic monomer. Upon varied desirables, the oligomer and acrylate monomer can be exchanged [2].

4.3 Photoinitiator

The photoinitiators are the compounds that undergo the reaction upon absorbing light. The photoinitiator is often cationic so that a charge is transferred to the monomers which then become reactive, causing the photopolymer to cure. This transfer happens when exposed to UV light. The component of the photoinitiator which generates the reaction is the UV light absorber which is an organic, aromatic fused ring compound. The preferred UV light absorbers are anthracene, which is three fused benzene rings shown in Figure 2.1, and its derivatives [3]. Figure 2.2 shows the graphical peaks of the amount of UV light absorbed at certain wavelengths (nm). Anthracenes absorption peaks is at 375 nm while naphthalene peaks at 286 nm as seen in

Figure 2.3 [4]. Most Stereolithography machines utilizes lasers whose wavelength exceeds 286 nm (typically operating around 300-360) which would make Anthracene the most commonly used UV light absorber [3].

[4] Figure 2: UV light absorbers

[4] Figure 2.2: Graphical peak wavelengths of UV light absorbers

[4] Figure 2.3: Absorption peaks of UV light absorbers

4.4 Materials and Variation in Properties

When designing it is important to keep in mind the desirable properties of the product you are modeling. Important properties to consider, especially for functional prototypes, are the Tensile strength Elastic modulus and elongation at the break. Other important factors are its heat resistivity, chemical resistance and surface quality and appearance. The Table 1 shows the numerical properties of the Tensile strength at yield, the elastic modulus and the percent elongation at break as well as a brief description of other important properties of these different photopolymer materials.

Table 1
Name Tensile Strength at yield (MPa) 63 Elastic Modulus (MPa) 2590 Elongation at break (%) Description

Somos 7120a

2.3 4.1

Transparent amber; General purpose for prototyping. Transparent amber; Good chemical resistance; good fatigue properties; used for producing patterns in rubber molding Opaque Grey; stiff; impact resistant; water resistant; durable; used in automotive body parts; functional prototypes Transparent or white; similar mechanical properties to ABS; rapid tooling; tough; Impact resistant; High elongation at break; excellent surface quality Optically clear resin with ABS-like properties

Somos 9120a

32

1140 - 1550

15 - 25

Tusk Somos SolidGrey300

60 - 66

2970 - 3285

TuskXC2700T/ Tusk2700W/ WaterShead 11122 Water Clear Ultra WaterClear

47.1 - 53.6

2650 - 2880

11 - 20

56

2.9

6-9

55 - 56

2860 - 2900

6-9

Transparent; lower mechanical properties than WaterShed 11122; used for parts that require neutral transparency Opaque beige; good general-purpose material for rapid prototyping. White; good surface quality; good thermal properties; durable; used in high end finished models

DMX-SL 100

32

2200 - 2600

12 - 28

Protogen White

43.8

2310

16

Poly1500

30-32

1227 - 1462

15 - 25

Translucent; flexible; impact resistant; tough; durable; PP-like parts; used in snap fit assemblies. Grey; tough impact resistant; high elongation at break; excellent surface quality White; impact resistant; durable; tough; moisture resistance; thermal properties; used in function prototypes Off White; still; high temperature resistance; superior sidewall quality; brittle;

Xtreme

38 - 44

1790 - 1980

14 22

NeXt

41 - 43

2370 - 2490

8 - 10

NanoTool

61.7 - 78

11000 11400

.7 - 1

[1,16]

5. Blade
A key aspect of stereolithography is the swiping of the blade between layers as the product is being created. The blade is used to apply a fresh, even coat of resin to the previous layer before the next layer is solidified. Figure 3 shows the different phases of the blades recoating process. Part A shows the product after one layer has been solidified [10]. The cured layer is the same height as the surrounding resin. The elevator lowers to allow the resin to overflow it as seen in part B [10]. Excess polymer remains on the product while polymer sits uneven and concave downward due the attraction of the surrounding resin [10]. The elevator rises slightly causing there to be an excess of resin on the product as seen in part C [10]. Part D is the most critical part in order to either cause, or prevent inaccuracies depending if it is done correctly. It is in this step that the blade actually moves across the resin. The blade travels at a given velocity with a certain gap between the top of the part and the bottom of the blade; the gap width depending on the elevator height [10]. This swipe of the blade should remove unwanted resin as it passes and leave the desired layer thickness of polymer behind [10]. As shown in part E, the elevator lowers another step. This allows the product with its new layer of resin to be in position for the next layer to be cured [10]. This movement creates more lead time in order to allow the polymer to settle and become even again. This leads to F where the resin is once again stable and ready to be cured [10]. This process is repeated until the product is completed. This process is repeated over and over again which is a main contributor to inaccuracies. Layers can become too thick or thin, causing layers to not adhere or to over-cure [10].

It is important while using the blade to know the correct layer thickness to avoid inaccuracies. Layer thickness (T) can be calculated by using equation 1, where R is the reference measurement, or the width of the layer scanned first and L is the measurement of the scanned surface after the new coat of resin is applied [10]. Subtracting the resin layer from the initial layer gives the ideal layer thickness. Equation 1

. Figure 3: A-F demonstrates the blade sweeping process [10].

6. Stereolithography Curing process

The curing process works by exposing the specific resin to ultraviolet light (UV) laser beam radiation, which includes a localized polymerization process to solidify the liquid resin layer-by-layer to form manufactured parts directly from 3D computer data

6.1 Degree of cure

During the process of the resin being exposed to the UV radiation, the limitations of the laser yield a degree of curing. The degree of cure is a function of different parameters related to the resin composition or the manufacturing parameters.

The resin curing process depends on laser intensity and exposure time required to achieve cure depth. Equation 2 shows the how to find cure depth (Cd), where Ec is the critical laser exposure, Emax is the maximum radiation exposure for the liquid resin and Dp is the deep penetration [8,14] Equation 2

Emax can be found using the following equation using the laser power applied to the liquid resin (P1), the beam radius (W0) and the laser scanning speed (Vs). Equation 3 shows their relationship [8,14].

Equation 3 ( )

A fully cured, or even a near cured part, is not easy to obtain during the UV exposure process. The reason for this is that as the resin cures in a bullet shape due to the Gaussian energy distribution of the laser beam. The bullet shaped of the cured resin is the same diameter as the beam but tapers off into the over cure. This is illustrated in figure 4.1

Figure 4.1: Gaussian energy distribution of the UV laser which causes the bullet shape

The laser is not able to cure the entire resin because of the Gaussian effect of the laser beam that creates this parabolic shape of the over cure. Each successive line results in an inhomogeneous microstructure. A simple way to improve the degree of curability is to increase the laser power, slow the scanning speed or decrease the layer thickness [14]. By taking any of these measures, the producing time and cost production are increased. Figure 4.2 shows how uncured resin remains after a number of successive lines built upon layers.

Figure 3.2: Uncured resin within a layered block

6.2 Setting the wavelength of the laser

The most critical aspect is the selection of wavelength. The wavelength affects both the curing characteristics, which strongly dictate the mechanical properties of the structure, and the resolution of the structure, especially the curing depth. To obtain a specific wavelength, a small variety of lasers are used which can be seen in Table 2.

Table 2: Laser types along with their perspective wavelength and description. Laser type HeliumCadmium Argon ion [8,14] Wavelength (nm) ~324 331 - 364 Description Most commonly used; SLA-250 (250mm x230mm); 40mW; 4000 hour lifespan Specifically 351 and 364 nm; SLA-500 (500mm x500mm); 600mW; 4000 hour lifespan

Figure 4.3 illustrates the UV absorbance coefficient of the photoinitiator, benzoin ethyl ether, at different molar concentrations over varied wavelengths.

Figure 4.3: Absorbance coefficient of benzoin ethyl ether vs. wavelength at different molar concentrations [14].

The wavelength also affects the resolution of the structure. A low absorption rate creates a high resolution structure. High absorbance value regions are not advisable for curing thick structures as these can result in a non-uniform distribution of photo-energy throughout the thickness. For the example of benzoin ethyl ether, a wavelength of 364 nm would be chosen for a high resolution for any molar concentration [5].

7. Post Curing Process

Even though curing of the photocurable resin takes place initially with a laser, this first step doesnt completely cure the entire product being made. Generally speaking, parts built by stereolithography can only reach anywhere between 80%-96% degree of cure depending on the type of resin [14,15]. In order to reach 90%-100% solidification, a post curing process is necessary. The post curing process can result in either lower or higher strength of the final product depending on what type of resin is used. For example, the Accura SI40 resin increases its mechanical properties when undergoing a thermal post curing while SL7560 experiences decreases [13]. Post curing almost always results in shrinkage of the final product: refer to section 8. Minimum post curing is wanted if tight parameters and functionality are desired. There are several post curing options available, the most relevant being ultraviolet, microwave, and thermal post curing. Products taken directly from the stereolithographer prior to post curing are referred to as green. The normal post curing method used is placing the green product in a UV post curing apparatus for 90 minutes (time subject to change, 90 min based on using Accura SI40) [13]. The UV post curing apparatus is an ultraviolet chamber where the product is subjected to ultraviolet light at 300W [14]. Another less common post curing apparatus is the Toshiba microwave oven. The green product is placed in the oven and subjected to microwaves at a power level of 700W for four minutes [14]. The last more common post curing apparatus is a conventional oven. Inside, the green part undergoes isothermal treatment at 125 degrees C for 30 minutes [14]. Table 3 demonstrates the different energy levels needed per gram to complete solidification, and the hardness achieved by each apparatus. It can be conclude that the conventional thermal oven achieves the greatest overall hardness while using the least amount of energy (SOMOS 7110 resin, data subject to change depending on desired resin and parameters) [14].

Specimens

Top face
Enthalpy (J g1)

Top face
Hardness

Lateral face
Enthalpy (J g1) 42.4 0.4 38.4 0.4

Lateral face
Hardness

Bottom face
Enthalpy (J g1) 57.3 0.3 52.0 0.4

Bottom face
Hardness

Green Ultraviolet postcured Microwave postcured Thermal postcured at 125 C

4.7 0.4 3.7 0.3

83 2 83 1

79 1 79 1

77 2 77 2

2.7 0.5

84 2

32.5 0.6

80 2

41.4 0.5

79 2

2.6 0.3

84 1

12.2 0.3

82 1

16.8 0.3

82 1

Table 3: Cure enthalpy and Shore Durometer type D hardness for the SOMOS 7110 photosensitive resin specimens built with a 0.10 mm line hatch space and treated by different post-cure processes [14].

8. Accounting for Shrinkage

Even with all the positive aspects of stereolithography, it is not without its own faults. A main concern of stereolithography is its tendency to be more inaccurate than that of other conventional machining processes [1]. As previously discussed, products are formed through the use of photocurable resin cured using UV light. Unfortunately, these types of resin always undergo volumetric shrinkage while being cured; it is this shrinkage that accounts for the majority of inaccuracies in the final products dimensions [15]. This shrinkage is found to occur throughout all 3 phases of stereolithography. During the first phase, layers are formed on top of each other within the resin. As the platform lowers adding each additional layer on top of the previous one, forces build acting on the lower layers. The previously formed layers suffer compressive stress while the newest formed layer suffers tension stress [15]. This interaction as two layers are being formed allows for concave upward warpage within the plane of contact between the layers [15] As pressure builds on the lowermost layers, they tend to shrink or become slightly inaccurate (margin of inaccuracy increases as more layers are added).

After the product is formed and raised out of the resin, there is still the possibility for inaccuracies to occur. Some products are created with the use of support pieces. Supporters are thinner, perforated parts of a product that allow the resin to be cured completely on top of them only to be removed after the product is completed. As supporters are removed, residual stresses are released from the support and settle to a new equilibrium state of internal stresses within the final product [15]. This can cause fluctuations in the dimensional accuracy of the final product. Finally, after a piece is removed from the resin and stripped of its supporters, it undergoes the post curing process. Even though the UV light cures the product initially, it only can do so to about 96% of full solidification leaving residual liquid resin in the product [15]. The product is placed in an ultraviolet oven in order to completely solidify. While fully solidifying, the residual liquid resin leads to the solidification being uneven; thus the more liquid left within the product, the more deflection will occur from the desired dimensions causing shrinkage [15]. In general, the shrinkage caused by this post curing process can reach values of up to 8% by volume [14].

9. Costs
Stereolithography is not a cheap process. Generally speaking, a stereolithographer alone can cost as low as $100,000 to as high as $400,000 per unit [1]. The price increases depending on the capacity of the machine. The maximum capacity a stereolithographer can achieve is 19in. x 19in. x 24in.; the minimum being on the microscopic level (micro-stereolithography) with an accuracy as small as 1 micrometer [1]. The post curing apparatuses can also cost as much as $28,000 [12]. Not only are the machines expensive, but the photocurable polymer can run as much as $300 per gallon [1].

10. Time
The amount of time stereolithography takes can be viewed as both an advantage, and a disadvantage. One cycle of stereolithography can take a few hours to as long as a few days depending on the size of the desired product [1]. These times are ideal for quick prototyping, however, they would not be desired for mass production.

10.1 Time Equation

More specifically, the amount of time it takes to complete a build cycle for stereolithography can be broken down into two parts; the time it takes for each layer to be scanned by the laser, and the time needed for the recoating process between layers [9]. The laser scan time can be calculated by using equation 4

Equation 4 [ ] ( )

This equation is a combination of equations 2 and 3 stated in section 6 regarding the curing process, with the addition of a specified cure depth, . This gives the velocity necessary for a

laser to cure the resin to a specified depth [9]. Vs is then multiplied by the velocity factor of 0.685 (constant used by stereolithographer while calculating required scan velocity), and then transformed into step size and step period depending on the given range [9]. Next, the total scan distance, total jump distance, and total laser times are calculated by equation 5-7:

Equation 5-7:

[9] Finally, each layers recoating time is calculated by equation 8:

Equation 8: [9]

Where tPR and tPD represent the pre-dip and post-dip waiting time defined by the user; tN denotes the nth sweep period; tTR represents the time it takes for the platform to first lower to a defined dip position; and tdelay represents a hardware delay time[9]. The total amount of time it takes to create the finished product is then the sum over all layers [8].

11. Comparison to other Rapid Prototyping methods

11.1 3D Printing

3D printing is a diverse process where a print-head deposits an inorganic binder material onto a layer of polymer, ceramic, or metallic powder. A piston supporting the powder bed is lowered incrementally, with each step depositing another layer which is fused by the binder [1]. Since Stereolithography deals largely with photopolymers, 3D printers can make part from a wider variety of materials. Parts produced through 3D printing are often porous and may have less strength than parts produced from a stereolithographer. A 3D printer can be combined with sintering and metal infiltration to produce fully dense parts, however, that would increase the cost, material usage, and time [1].

11.2 Selective Laser Sintering

Selective laser sintering (SLS) is a process based on the sintering of nonmetallic or (less commonly) metallic powders selectively into an individual object. The bottom of the processing chamber is equipped with two cylinders. The first cylinder is a powder-feed, which rises incrementally to supply powder to the part-build cylinder through a roller mechanism. The second is a part-build cylinder which is lowered incrementally as the part is being formed. The part-build cylinder drops after each dimension is added by the laser sintering. Another layer of powder is distributed by the roller and the next layer is printed. A variety of materials can be used such as ABS, PVC, nylon, polyester, polystyrene, and epoxy [1]. Since SLS uses common polymers, the cost of material is often less expensive than the cost of photopolymers. The surface

finish of parts produced by SLS is often rough in comparison to parts produced by Stereolithographer.

11.3 Fused-deposition Modeling

The fused-deposition-modeling (FDM) process uses a gantry robot-controlled extruder which moves in two principle directions over a table, which can be raised and lowered as needed. A thermoplastic filament is extruded through the small orifice of a heated die. The initial layer is placed on a foam foundation by extruding the filament at a constant rate while the extruder head follows a predetermined path. When the first layer is complete, the table is lowered so that subsequent layer can be superimposed. If a filament layer needs to be constructed where no material exists underneath to support it, a less dense supports will be extruded separate from the desired material so that it can support the structure but also be removed easily after the part is complete. FDM dimensional accuracy can be as fine as .025mm as long as the filament can be extruded into the feature. A FDM part exhibits a stepped surface on oblique exterior planes which is not as common in stereolithography. A heated tool can be used to smooth the surface which can compromise the tolerances. FDM machines are a bit less expensive than stereolithography machines costing roughly $20,000 to $300,000 depending on the capability to produce certain part sizes and the types of materials that can be used [1].

12. Conclusion
Stereolithography remains the most commonly used rapid-prototyping method to this day. The use of photocurable resin to create a quick, complex prototype draws manufacturers to this process. Future developments are being researched to increase the spectrum of uses for stereolithography. Advancements are being made to decrease laser size and power consumption, while increasing its efficiency. Genetic algorithms are being tested to develop a better transition between CAD models and the parameters within the stereolithographer in order to further increase accuracy of dimensions. Biomedical applications are being looked at, as well as many other fields of study. The products of stereolithography are both expanding and shrinking for more functional purposes. Expect to see improvements in overall lead time, and functionality.

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