CHAPTER 5

PHOTO POLYMER FOR RAPID PROTOTYING MACHINE

5.1 THE CHEMISTRY OF PHOTOPOLYMER

Sterolithography photopolymers for UV curing are generally formulated from

photo initiators and reactive liquid monomers. Some special photopolymers may

also contain fillers and other chemical modifiers. The photo initiator molecules, P,

mixed with the monomers, M, are exposed to an LA/ source of actinic photons

designated by hv. The photo initiators absorb some of the photons and yield an

excited photo initiator species [29], A small fraction of them are converted into

reactive initiator molecules, after undergoing various complex chemical energy

transformation steps. These molecules then react with monomer molecules to

form a polymerization initiating species. This is known as the chain initiation step.

Once activated, additional monomers continue to react during the chain

propagation step, until a chain inhibition process terminates the polymerization

reaction. If the reaction is sustained for a sufficient period, a high molecular

weight can be achieved. With difunctional monomers, having two reactive sites

per molecule, the polymerized material becomes highly viscous solid. However, if

the monomer molecules have three or more reactive chemical groups, then the

resulting polymer will be cross-linked [30], Cross-linking generates an insolvable

continuous network of molecules.

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Chapter 5 Photo polymer for rapid prototyping

5.1.1 Cross-linking

For SL, it is important for the polymers to be sufficiently cross linked that the

polymerized species must also posses sufficient green strength to remains

structurally intact, while the laser cured resin is exposed to various viscous forces

during the deep dipping and the recoating processes of SL.

As the laser cured SL photopolymer is post cured with additional UV radiation,

the reaction proceeds even further, increasing the degree of polymerization and

the cross-link density. The cross linking is formed by strong covalent bonds,

which connect the polymer chains to each other. The chemical bonds must first

break before molecular flow can be realized. Therefore, solidified SL

photopolymers do not melt upon heating as a result of their covalent chemical

cross-linking. They can, however, soften significantly upon heating and

eventually with thermally decompose at a very high temperature [31].

5.1.2 Acrylate chemistry

The first photopolymer system used for SL is based on acrylate chemistry, which

polymerizes via a free-radical mechanism. The photo speed of acrylate-based SL

photopolymers is quiet high. However, one of the drawbacks in terms of the

chemistry of free-radical polymerization is oxygen inhibition. This may result in

surfaces that are either not fully cured or are not quiet “tack-free”.

5.1.3 Cationic photo polymerization

The second type of chemistry used more recently in SL is cationic

photopolymerization. Cationically initiated SL photopolymers posses a number of

chemical advantage compared to photopolymers that are free-radically initiated.

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Chapter 5 Photo polymer for rapid prototyping

First, photo polymerization based on cationic reaction is not inhibited by ambient

oxygen, unlike acrylate-based system. However, cationic photopolymers

manifest a continued thermal curing following photo cure. However, cationic

photopolymers resins also have also some disadvantages. Bases and water,

including humidity, often inhibit the polymerization of cationic systems [32],

Another disadvantage of initial cationically curable SL resins is their slow photo

speed.

5.2 ADVANTAGES IN STEREOLITHOGRAPHY PHOTOPOLYMER SYSTEMS

5.2.1 Interdependence of machine and material

RP&M system accuracy is only one factor in building accurate parts. In SL for

example, no matter how accurately the laser beam may be positioned on the

liquid resin surface, if the photopolymers distort during or after laser photo curing,

the inherent machine pointing accuracy is compromised. SL photopolymers and

SLA systems are mutually dependent, and the performance limitations of either

component can result in inferior parts [33]. This interdependence of machine and

material doesn’t apply only to SL, but also to other RP&M systems. Each type of

RP system has its own set of strengths and weaknesses. Some of these may be

obvious, while other may not be apparent to the users. This makes it relatively

difficult to judge the quality of the parts that could be generated from a particular

combination of machine and its materials, simply by inspecting published

specifications such as the positioning accuracy of laser beams, elevator

translation, extruding heads, X-Y plotters, or jetting heads.

The resin behavior must be determined on a system capable of outstanding laser

pointing accuracy.

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Chapter 5 Photo polymer for rapid prototyping

5.2.2 Impact of polymers

The performance of the object generated from the SL process depends on the

availability of high-quality photopolymer system. The quality is characterized by

the resin dimensional proprieties, namely accuracy and dimensional stability, as

well as its physical and mechanical properties directly impact the user

applications. It is imperative that the dimensional accuracy and mechanical

properties actually achieved by the materials are compared with the required

tolerance and specifications appropriate for their needs.

The applications of SL parts depend strongly on the performance achieved by

the photopolymer systems [34], For example, with limited accuracy RP parts may

only be useful as concept models and for design visualization purposes.

Interference checks will not be appropriate where part accuracy is poor. With

inferior mechanical properities, direct functional testing using RP part is

impossible. Dimensional accuracy and mechanical properties cannot be

separated: rather they must be considered simultaneously for RP applications.

5.3 SELECTION OF RESIN

Stereolithography is based upon the solidification in layers of photosensitive

polymers are converted from liquid to solid, they shrink. While the prototype can

compensate for the overall dimensional shrinkage by adjusting build parameters,

shrinkage produces internal stresses that can cause curl and other distortion in a

SL part. The higher the shrinkage of a resin more is the distortion and warpage

will be observed in the final part [35, 36],

Swelling is another factor, which helps to determine the part accuracy. Once

solidified, most Stereolithography resins swell, as they remain immersed in the

5.4
Chapter 5 Photo polymer for rapid prototyping

uncured liquid resin for a longer duration. This means that longer the part

remains in the vat larger will be swelling [37], Moreover, swelling is more difficult

to compensate for because the bottom-most layers which are solidified first will

remain more time in the resin and swells more. Parts with thin vertical walls are

particularly affected.

Functional prototypes, those used to test design under conditions similar to

actual use, place the greatest demands on the physical properties of RP

materials [38], There is no RP material available in the market that can really

approximate the properties of substances like ABS, nylon, PVC or polycarbonate.

While some RP materials approach the tensile strength and modulus of

engineering plastics, they fall particularly short in properties of elongation and

impact resistance [39].

Process parts used as molds and pattern in secondary processes must be

accurate if they are to be used to create functional prototypes. They also must be

strong and durable enough to withstand the process in which they will be used.

Thermal expansion is very important in the case of shell investment casting. Most

SL material expands at a faster rate than the material from which the investment

casting shells are made [40], So, the shell cracks down on heating. This should

be considered. Another consideration in the selection of RP materials is long­

term stability. A problem with SL parts is that they tend to creep or deform over

time as internal stresses build up during fabrication gradually work themselves

out. Build speed is another important criterion. Build speed in SL is considered

by several material factors .The viscosity of a material determines how quickly

the recoating stage of the built process can take place. The less viscous material

will have quick flow. Toxicity is also an important property of any RP material.

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Chapter 5 Photo polymer for rapid prototyping

Some material possesses greater hazards than other and requires more carefully

handling. While toxicity might not disqualify a particular resin from use in a

specific application. Acrylates cause eye irritation. While some resins from Ciba-

Geigy and Dupont SOMOS are free from these substance.

The critical properties of the resin to be considered are:

• Resin/Hardener ratio

• Resin viscosity

• Hardener Viscosity

• Initial mixed Viscosity

• Working life

• Demand time

The critical cured properties to be considered are:

> Hardness

> Tensile strength

> Shrinkage

> Elongation

> Tear strength

> Notched izod impact

> Volume/Weight ratio

> Flexural rigidity

> Flame resistance

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Chapter 5 Photo polymer for rapid prototyping

5.4 OTHER RELEVANT PROPERTIES OF SL PHOTOPOLYMERS

5.4.1 Surface wetting

Surface wetting is also a very important property of epoxy resins. In SL, thin

layers of liquid resin are formed on top of cured resin. If the surface tension of the

liquid resin is much greater than the surface energy of the cured resin, then the

liquid will ball up, much like drops of water on the smooth surface of Teflon

coated frying pan. The equivalent problem that may arise on a SL building

surface is called dewetting. If dewetting occurs on the interior layers, dewetting

may lead to layer delamination, because the subsequent liquid layer requires

twice the original cure depth to achieve layer adhesion. If it occurs at the borders

dewetting often results in line separation, also referred to as “bird-nesting"

leading to parts that have fuzzy outside walls.

One of the most important parameters relevant to dewetting prevention is layer

thickness. The dewetting process happens mainly due to the difference between

the surface tension, and adhesive energies of the liquid, and laser-cured

surfaces. The surface of a nicely coated liquid layer can be break when the

surface energy difference between the liquid layers. Obviously, if the layer

thickness is large then the gravitationally induced pressure difference between

the liquid surface and the cured surface become correspondingly greater.

The next important parameter is the surface UV exposure level. The surface

tension of the cured SL resin surface depends on the degrees of cure. If

inappropriate exposure levels are used, excessive dewetting may occur for some

resin formulation.

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Chapter 5 Photo polymer for rapid prototyping

5.4.2 Swelling

Swelling is another important property. When SL resins are cured in the vat and

exposed to liquid resin for an excessive time interval during the building cycle in

a SLA, part dimension may increase due to the infusion monomers into the semi

cured green part.

For a given resin, swelling is primarily a function of the wetted liquid surface to

cured volume ratio, reduced degree of cure, and longer immersion time all results

in increased swelling. This becomes a measurable source of dimensional

inaccuracy if the resin swells excessively, especially when the parts are built with

a quasi-hollow internal structure.

5.5 POLYMERISATION

In general, there are two distinctly different types of polymerization, addition and

condensation; also called chain- growth and step-growth polymerizations

respectively. Chain-growth or addition polymerization may be illustrated by the

reaction of styrene with a free radical:

nCH2= CH +R > [CH2-CH n

Condensation or step-growth polymers are formed with the expulsion of a small

molecule for each unit added to the polymer chain, and the reaction proceeds in

a sequential fashion, former dimmer, timer, etc. for a polymer such as

polyethyleneterephthalate. This can be illustrated as follows:

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Chapter 5 Photo polymer for rapid prototyping

Overall:
O
i
i
i
CH3OC

hv
------------------------- ►

O O

C0CH2CH20------]- + CH3OH
Chapter 5 Photo polymer for rapid prototyping

A type of condensation polymerisation that gives a linear polymer (or a

“prepolymer” as commonly called) with reactive groups in chain ends, which may

be cured to give a network polymer, is the polycondensation of epoxy polymers.

The formation of an epoxy polymer may be illustrated by the reaction between 2,

2-bis (4-hydroxyphenyl) propane (I) (Bisphenol-A) and epichlorohydrin (II) to

initially form a prepolymer as follows:

CH3 O
Na0H/H20

H OH + CH2—CHCH2CI
hv

CH3 OH

H OCH2CHCH2CI

NaOH/H20
CHs OH

HO- OCH2CHCH2CI

CH3 O

HO- OH + CH2—CHCH2 + HCI

CH3

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Chapter 5 Photo polymer for rapid prototyping

This process may be repeated on either side to give a product that may be

represented as:

This process may be repeated on either side to give a product that may be

represented as

This is DiGlycidyl Ether of Bisphenol-A (DGEBA), where n represents the number

of times the repeating nit occurs in the prepolymer. If n is 0 or 1, the product is a

viscous liquid. If n is greater than 1 the product is a brittle solid. The relative

amounts of the reactants determine the value of n, a large excess of

epichlorohydrin favoring the formation of a liquid. Cross-linking or curing giving a

solid is illustrated with a general poly functional amine.

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Chapter 5 Photo polymer for rapid prototyping

—CH—CH2 CH2—CH
H^ ^ H
^ N—R—
H H

N—R—!

QH—CH2 CH2—CH-
OH OH
Some anhydrides such as phthalic anhydride (III) are also used for curing agents.

They react with free hydroxyl group on the chain, freeing a carboxylic acid group

to react either with hydroxyl or an epoxide group (III).

The photopolymer used for this rapid prototyping machine is DuPont SOMOS

7100. This photopolymer will be cured by UV (Argon Ion) laser beam at 351 nm

wave length.

5.6 SUMMARY

The chemistry of photopolymer used for stereolithography is briefed in this

chapter. Also the different properties of the photopolymers are indicated here.

The parameters to be considered for selecting suitable photopolymers for

stereolithography are discussed in this chapter.

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