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Joe Strauss
President, HJE Company, Inc.
Queensbury, New York, USA

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Gary Dawson
President, Gary Dawson Designs
Eugene, Oregon, USA

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Direct Casting
Photopolymer Resin Models

Introduction
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Prior Research

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We are making minimal attempt here to tie our current study directly into
prior research presented at the Santa Fe Symposium. However, we find some
information in each of the following studies that is useful to our current
examination.

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Photopolymers are not new and have been in some form of prototyping service
for at least a couple of decades. And historically, photopolymers have not enjoyed
a reputation of acceptable direct casting, and prior studies published with the
proceedings of the Santa Fe Symposium attest to this fact. With a proliferation
of rapid prototyping systems evolving into the jewelry industry at prices much
more accessible to smaller shops, direct casting of cured photopolymer resins has
become an issue of even higher importance. This paper outlines our process for
optimizing a technique for direct casting a specific photopolymer. Using practical
casting tests with photomacrographic documentation and materials analysis, we
feel that we have achieved the goal of this project.

In Teresa Frys, A Study of the Effects of CAD/CAM-Derived Materials in


the Casting of Platinum Alloys (2008 Symposium), we find that although
photopolymers seem to leave the highest concentration of ash residue compared
to other model mediums, there can be substantial differences in the ash residue
between different polymers and also that there is some difference in the residue
depending on exposure to air.

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In Alan S. (Andy) Andrews study, The Quest for the Perfect RP Burnout (2011
Symposium), we find that investment and how its processed can make vast
improvements in investment toughness, which can improve the resultant casting
detail considerably. This study also emphasizes that the integrity of the mold
body is critical for casting success with photopolymers.

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In his study, Quality Excellence in the Direct Casting of RP Resins: Reality


or Fiction? (2011 Symposium), Marco Actis Grande further demonstrates
that investment processing demonstrably affects casting results. In this study,
superior castings seem to be produced by relatively freshly printed resins, with
some observable degradation in castings produced by older resin models.
Interestingly, this is in contrast to some of the conclusions of this current
examination.

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Background
Our first experience with any photopolymer resin casting came when I (Dawson)
did some casting tests for an RP technology manufacturer. The tests were simple
burnout and casting tests and not extensive. The manufacturer supplied a sample
of the resin with no explanation of its material character or history. The results of
that test seemed to indicate that the material was compatible with direct casting
and my procedure and summary were as follows
Scope:
This project was designed as a preliminary test of burnout characteristics of the resin
used in the B9C RP-DLP system.
Three sections of cured resin were chosen for their texture in hopes of evaluating possible
ash residue and potential problems created by thermal expansion characteristics of
the resin during ramp-up within the burnout cycle. One piece of textured resin was
invested in each of two flasks using Ransom & Randolph Ultra-Vest. Instructions
supplied with the investment were followed for mixing and burnout. One section of
cured resin was placed directly on the kiln floor for the purpose of direct observation
of ash residue. The kiln was observed at the end of the burnout cycle and both flasks
were cast in Sterling Silver using a horizontal centrifugal casting machine. Melt
was accomplished by Hydrogen-Oxygen flame. If the kiln floor piece had displayed
any amount of ash residue and/or the first casting showed any signs of residue
contamination, I had planned to use a protocol established by another researcher
of using compressed air to clear the mold cavity prior to casting the second flask.
However, based on my observation of the kiln floor and the first flask casting results,
I felt no need to use this protocol.
Conclusions:
Upon completion of burnout, the kiln floor where the single piece of cured resin
was placed was observed to have no ash residue.
Both flasks containing cured resin cast normally and seemed to have normal
resolution of cast surfaces in all cases which led to an initial indication of no
interior mold degradation due to thermal expansion of the resin during
ramp-up in the burnout cycle.
Photos:

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Procedure:

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Figure 3 Interior of kiln prior


to initiation of burnout

Figure 4 Interior of kiln after


burnout cycle complete

Figure 5 Cast pieces after pickle,


prior to magnetic pin tumbling

Figure 6 Cast pieces after


magnetic pin tumbling

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Figure 2 Texture on sprued resin

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Figure 1 Texture on sprued resin

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At some point after test casting this resin, I came into possession of one of the
machines using this resin and soon found that the direct casting results I was
getting were not at all comparable with what I had achieved with the initial
casting tests. They were, in fact, not acceptable. This was beguiling in that I was, at
that time, attempting to integrate RP technology into my own studio production.
When the supplier of this resin assured me that I was printing with the same resin
formula that he had initially shipped to me, I began to look for reasons why my
results varied so much from my initial testing.1

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Beyond Initial Testing

Figure 7 Typical casting results of freshly printed resin

Investment
The first diversion from our standard casting procedure was to obtain an
investment formulated for casting polymer resins. This new (for my process)
investment gave me slightly better results but did not demonstrate enough
improvement to be considered a solution to the problem. Since some improvement
was noted, however, all further testing done for this paper was accomplished with
investment formulated for polymer casting.

Post-Print Processing
Taking a hint from vague leads from the supplier of this particular resin,1 we
soon focused on post-print processes for resin models as the only real direction to
follow. The differences between freshly printed polymer and the original samples
I had cast were seemingly few, other than that the original sample had sat for
some time in a sunlit window. Not only was I casting very soon after printing, the
nearly perpetual overcast sky of mid-winter Oregon where I live does not avail
itself to much direct sunlight. This single difference can be seen to break down
into three distinct parts: time, heat, and light.

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At this stage of our investigation, my timeframe from print to casting varied from
only several hours to a couple of weeks, and the casting results I was getting
from these different lapse times didnt seem to alter the outcome. Perhaps the
most extreme example of a time-frame anecdote came later in our investigation
when a friend sent me a picture of a casting from a print I had done for him. This
model had rested on his workbench for an extended period, about two months, at
ambient temperature and under shop lighting only, and was as bad as my freshly
printed examples. He sent me this photo of the casting with the simple phrase
What Happened? as the message body.

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Time

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Figure 8 Casting done about two months after printingno post-print curing

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Anecdotal though it is, this seems to indicate strongly that time alone isnt enough
to successfully prepare this resin for casting. It seems that for all reasonable time
frames after printing, casting results are still not acceptable for production, and
we shifted our immediate focus to the other areas of investigation.

Heat

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We had a surprise during our analytical testing in a discovery that heat alone
seems to facilitate the continued polymerization of freshly printed resin. This will
be further explained in the following section. We did not attempt to optimize
a heat curing process for this resin, but the parameters followed during the
following casting tests were a ramp of 2.2C (4F) to a hold temperature of 175C
(347F) with a half-hour hold.

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Consultation with Dr. Richard Chartoff, Director of the Polymer Characterization


Facility at the University of Oregons CAMCOR (Center for Advanced Materials
Characterization in Oregon),2 indicated that most photopolymers in use for rapid
prototyping do not fully cure in the print process, and additional light exposure
may be helpful. Our casting results seem to confirm this and will be demonstrated
later in this paper.

Analytical Testing of Resin Burnout


The activity of a polymer during heating is typically quantified by DSC/DTA
(Differential Scanning Calorimetry/Differential Thermal Analysis) and TGA
(Thermal Gravimetric Analysis), which have been described elsewhere.3 DSC/
DTA is capable of monitoring phase changes and chemical reactions in the
material while the weight change of the sample may be monitored by TGA.
For example, Figure 9 is a DSC of a typical photopolymer. The lowest (green)
curve is that for the fresh as-printed piece. This green material contains cured
resin and uncured resin. There is a very prominent endotherm (reaction absorbing
heat) starting about 200C (392F). This reaction is the polymerization reaction of
the raw resin that was not cured by the initial exposure to UV. The middle curve is
for a part that was post-cured for one hour. There is a less prominent endotherm,
indicating that there is less uncured resin in the one-hour post-cured material. The
top curve is for the same material after a 24-hour post cure. There is no endotherm
between 200C and 300C (392F and 572F), which implies that there was no
reactable material remaining in this well-cured material.

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Light

Figure 9 Composite DSC plot of a typical photopolymer2

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Figure 10 is a TGA plot of an epolene part burned out in air. The plot shows
the percent weight loss as a function of temperature. No significant weight loss
occurs until about 340C (644F) and then weight loss occurs relatively rapidly.
The weight loss event is essentially over by 475C (887F). Since the curve is
monotonically decreasing, this implies that the polymer is made of one component
and the weight loss is governed by one mechanism (oxidation).

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Figure 10 Percent weight loss vs. temperature (epolene in air)


Based on observations that casting defects arise from using photopolymer
patterns that are not completely cured, it was hypothesized that something
remained in the investment after burning out the incompletely cured resin versus
that of a completely cured resin. This residue acted as a contaminant that either
reacted with the melt or the investment to cause the resultant surface defects in
the final cast part.

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In the current investigation it was thought that TGA is a more appropriate test
as the goal is to quantify the burnout behavior of the resin and detect the residue
remaining after the burnout. TGA measures the weight of the sample as a function
of temperature and time. If a residue remains, then its mass may be detectable.

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The TGA testing entailed a heating rate of 2.2C/min (4F/min), which is a


recommended rate for printed resins in flowing air.5 TGA plots were made for
freshly printed resins, fully cured resins, and raw resin (liquid, no curing). Figure
11 is a composite plot of these three tests. From a first observation, the burnout
behavior and percentage of residue for the fresh and cured resins are essentially
identical as the plots overlap substantially. For these two samples, the weight loss

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A macro-TGA was used in this current study. While most TGA use samples in the
50-100 milligram size, the macro-TGA has the capability to measure samples of up
to 50 grams with 0.1 milligram resolution.4

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begins about 230C (446F). The slope of the curve changes around 400C (752F),
which could indicate a change in weight loss mechanism (i.e., volatilization to
oxidation). The slope of the curve changes again around 440C (824F), which may
indicate a dominance of the oxidation mechanism.

Figure 11 Percent weight change vs. temperature for photopolymer


The burnout behavior of the raw resin differs significantly. First, there is a rapid
weight loss between 100 and 150C (212 and 302F). This is followed by a very
shallow profile (low or no weight loss) to about 350C (662F), where it joins
up with the other two plots and behaves essentially the same throughout the
remaining burnout.
The rapid weight loss that initiates at 100C is most likely volatilization of a
singular component. Most photopolymers have two to three components: 1) the
base monomer/oligomer that constitutes the majority of the resin, 2) an optional
additive to modify the raw resin or cured resin properties, and 3) an initiator,
which absorbs the light energy to become active and enable polymerization and
crosslinking of the other components. The amount of weight loss in this initial
period is about 10%, which is consistent with typical amounts of additives used in
photopolymers.6 The absence of this portion of the curve in the other plots (fresh,
cured) is an indication that this material is polymerized in the curing process and
is no longer volatile in this temperature range.
The raw resin plot joins and follows the other curves above 350C. In a related test,
the raw resin was heated to 280C (536F) only. The material remaining after this
heat treatment was a solid. This is an indication that the material cures with heat
alone. Once solid, the remaining burnout behavior mimics the cured polymer.
It was thought that the freshly printed resin would display some TGA
characteristics of the raw resin such as the low-temperature weight loss. In the

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In all of the TGA burnout emulations there was some residue remaining, generally
between 1 and 3% of the initial weight. The hypothesis is based on the presence of
some remaining material so this may be contributing evidence. However, it also
points out that it may be the makeup of the remaining material is as important as
the presence of remaining material. Characterization of the remaining material is,
unfortunately, outside the scope of this present study.

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incompletely cured resin, there exists some raw resin within the cured matrix,
i.e., the cured matrix is like a sponge and the uncured resin is a liquid within the
matrix. The TGA curve does not show this; however, closer examination of the
TGA data shows that the onset temperature for weight loss for the cured resin is
about 230C (446F) while the onset temperature for the fresh resin is about 170C
(338F). This is a significant difference, and while it doesnt exactly coincide with
the onset temperature of about 100C for the raw resin, it could be a result of the
presence of uncured components.

It should be noted that these TGA tests are not exactly the same as performing
a burnout of the resin in the investment. The investment will shroud the pattern
and the burnout will be oxygen-lean. This will certainly change the kinetics of the
burnout. This current series of TGA tests are still valid as a method to determine
basic differences between as-printed, fully cured, and raw resin.

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Observations of Casts Made with Incompletely


Cured Resin Patterns and Comparisons with Fully
Cured Resin Patterns

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Numerous parts have been made and subsequently cured and compared
with not fully cured patterns. The castings made using patterns that are not
fully cured are consistent in that their surface quality is poor. Figure 12 shows
castings made side-by-side with cured and not fully cured resins. This is strong
evidence that it is the uncured resin causing the defects and not some other
processing parameter or quality issue.

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Figure 12 Comparison of cast resin models

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Figure 13 Closer view of comparison casting


If one had to conject the cause of these defects without knowing the link to
uncured resin, two plausible causes may be 1) the investment is breaking down
(surface positive)5 and 2) the defect is caused by gas evolution at the surface of the
casting (surface negative).7
Tyler Teague notes that acids can break down investments or even prevent them
from setting. To investigate the effect of the resins on the investment itself, large
flat resins were printed, one cured and the other not, invested side-by-side, and
then burned out. (The large flat surface allows one to see any effects more clearly.)
Figure 14 shows the results of this experiment. It is clear that the uncured resin
caused the investment surface to break down. This would certainly result in
the rough surface-positive defect that has been noted. (The investment debris is
thought to be floated away rather than relocated to cause surface-negative defects
as the surface-negative defects are smooth.)

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Figure 13 is a closer view of one of the trees depicted in Figure 12. Close
examination shows that there are two distinct types of surface defects: 1) surface
positive (defect sticks out above the intended surface) and 2) surface negative
(defect extends into the part). The surface-positive defects are rough while the
surface-negative indications are relatively smoother. This may indicate that there
are two defect-causing mechanisms resulting from using non-fully cured resins.

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Figure 14 Close view of flat, dense resin burnout comparison

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To test the hypothesis that the surface-negative defects are caused by oxygen
derived from the melt, castings were made from resins both incompletely cured
and fully cured but cast in a closed system in a low-oxygen activity (see Figure
15). The resulting castings, specifically those of the uncured sample, while not
perfect had far fewer surface-negative defects than those made with sterling silver
melted in an open atmosphere with an oxygen-hydrogen torch. This indicates that
the defects are associated with dissolved oxygen.

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Stewart Grice noted that the gas evolution that could cause the surface-negative
defect may come from the melt or the investment. If the melt has an appreciable
amount of dissolved gas (typically oxygen), then the presence of a reducing agent
in the investment may induce the dissolved oxygen to combine and form carbon
dioxide, which would form a bubble and an attendant smooth surface-negative
defect.

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Could this investment breakdown be caused by acid and, more importantly, is


this acid from the uncured resin? There are numerous types of photopolymers
and most of the ones sold for rapid prototyping are proprietary so little is known
about their type and composition. However, many photopolymers contain acidic
components that are consumed upon polymerization (curing),6 that is, the raw
polymer can be acidic and the cured polymer would be neutral. To test this, a
quantity of raw resin was mixed with water and then the solution was subjected
to a simple litmus paper test. The litmus test showed that the addition of the
resin caused the PH of the water to decrease by approximately one point (from
neutral 7 to acidic 6)an increase in acidity. This establishes that this particular
resin has acidic character when not cured. Curing essentially removes the acidic
component. Thus, a very plausible mechanism for the investment breakdown is
an acidic reaction from acid in the uncured resin.

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One of the mechanisms for polymerizing the resin is that a carbon double bond in
the resin molecule is broken and polymerization takes place at this site. The new
bonds at this site are single-bond carbon bonds. Carbon double bonds are stronger
than single bonds and polymers containing carbon double bond are more difficult
to burn and may leave carbonaceous material as a burn product.8 The presence of
this carbonaceous material could conceivably react with dissolved oxygen in the
melt to form the surface-negative defects that are observed.
In summary, it is known that the use of uncured resins produce surface defects
in silver castings. TGA burnout tests confirm different burnout characteristics for
cured, uncured, and raw resin, and it can be implied that raw resin remains in
uncured patterns. It was shown that this particular uncured resin contains acidic
components, which react with the investment to produce surface-positive defects.
It is also plausible that carbonaceous material remains in the investment to react
with dissolved oxygen in the melt to form surface-negative defects.

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Figure 15 Castings of cured and uncured resin models in inert atmosphere

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Linus Drogs
Stewart Grice
Tyler Teague
Richard Chartoff
Douglass Neckers
Michael Joyce

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Acknowledgments

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This paper only begins the process of optimizing this specific resin to our casting
operations. Further study could include discovering sources of the various
mechanisms at play, both chemical and physical, that affect successful casting
of the resin. Further optimization of heat and light curing processes with regard
to lumens, temperatures, times and cycles would be helpful for a more simple
application of this photopolymer to our needs as manufacturers.

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Further Study

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Freshly printed photopolymer resin is not fully polymerized.


Uncured photopolymer resin does not cast with acceptable surface characteristics.
There seem to be two mechanisms that work together to degrade surface
characteristics when casting freshly printed resin, creating both surface-positive and surface-negative defects.
Post-print curing by both light and heat seem to effectively cure resin models
and prepare them for successful casting in sterling silver.
We believe this particular photopolymer resin will provide acceptable casting results with little process modification for most contemporary casting
operations, provided it is handled properly after the print process.
We suspect that until photopolymers become more prevalent in the jewelry
industry and take up additional photopolymer market share, we will continue to experience varied results with different photopolymers. If use within
jewelry industry accumulates to a level that becomes important to the polymer industry, their technology may begin to adapt to our needs and we may
then see more consistent results.
Until or unless that happens, jewelry manufactures will need to test various
resin formulas for suitability in our industry and make modifications to our
process to accommodate some resins.

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Conclusions

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1. Michael Joyce, founder, B9Creations LLC, private communications (2012).


2. Richard Chartoff, Polymer Characterization Facility at the University of
Oregons CAMCOR facility, private communication (February 2013).
3. M.A. Grande, I. Forno, U. Klotz, Quality Excellence in the Direct Casting of
RP Resins: Reality or Fiction? The Santa Fe Symposium on Jewelry Manufacturing
Technology 2011, ed. Eddie Bell (Albuquerque: Met-Chem Research, 2011).
4. J.A. Grohowski, J.T. Strauss, Effect of Atmosphere Type on Thermal
Debinding Behavior, International Conference on Powder Metallurgy &
Particulate Materials, (New York, N.Y: May 30-June 3, 2000).
5. J. T. Teague, Jett Research, Johnson City, TN, private communication
(March 2013).
6. BASF product literature, High lights! Radiation curing with resins and
photoinitiators for industrial coatings and graphic arts, #EDC 4511
(Ludwigshafen, Germany: BASF SE), www.basf.com/resins.
7. S. Grice, Hoover & Strong, Richmond, VA, private communication (March
2013).
8. J. Darab, Magnesium Elektron Limited Chemicals, Flemington, NJ, private
communication (March 2013).

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References

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