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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.
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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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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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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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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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Light
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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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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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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.
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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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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 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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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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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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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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Conclusions
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References
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