Post-Curing of Silicone Elastomers:
When is it Necessary?
William D. Inman, Jr.
Technical Service & Development
Silicone Elastomers
Dow Corning Corporation
About the Author
William Inman Jr.
Technical Service & Development
Science & Technology
Dow Corning Silicone Elastomers
William Inman has been employed with Dow Corning Corporation for more
than 20 years. He is currently an Application Engineer providing technical
product assistance for Dow Corning Silicone Elastomers. While Inman had
devoted his career to healthcare ― working in Bio-Analytical, Application
Engineering, Technical Service, and Sales Development ― he recently
expanded the industries he serves to include electronics, food and beverage, as
well as infant care, among others. He has significant experience in chemical
and physical characterization of materials, as well as product development,
manufacturing and extrusion of silicone elastomers used in medical devices.
Inman earned his bachelor’s degree from Saginaw Valley State University
in 2000.
ABSTRACT complex component parts. HCR is considerably higher
in viscosity and, as a result, does not flow as well
The process of post-curing silicone elastomer has been
ultimately making for simpler parts in similar molding
in practice since the inception of silicone rubber
processes. HCRs, due to their good green strength
materials. Some of the early silicone technology patents
(cohesive capability prior to cure) are much better suited
describe a secondary post cure cycle, mainly to improve
for extrusion applications. Extruded silicone tubing is
the physical characteristics of the material. In some
used for diverse applications ranging from fluid
instances, especially with the newer materials available
transport to electrical insulation (e.g., pacemaker leads).
today, this costly step can be removed from the overall
Silicone HCR can also be milled and molded or
scenario leading to cost savings, safety, and even
calendared into sheets.
environmental benefits.
Silicone elastomers are cured (or “vulcanized”) to turn
INTRODUCTION from thick liquids or semi-solid putties and pastes into
Post-curing, as the name describes, involves a secondary solids. The two most common curing processes are
cure of the silicone, typically in a hot air circulating oven peroxide initiated curing and platinum catalyzed curing.
at a given temperature for a certain amount of time. The Many, but not all, HCRs are cured with organic peroxide
process reduces toxic by-products from some peroxide- initiators, while LSRs typically are platinum-cured.
cured silicones and generally improves the physical
characteristics of both peroxide-cured and platinum- PEROXIDE-CURED SILICONE
cured silicones. The post curing of silicone elastomers is Initially, all silicone elastomers were cured with
a costly endeavor, adding time and money to the peroxide-based chemicals. This curing system is also
manufacturing process. While some original equipment called a free radical cure system or a high-temperature
manufacturers (OEMs) must post-cure their products to vulcanizing system because the peroxides generate free
meet certain regulatory requirements and safety radicals that decompose at high temperatures and initiate
standards, others may benefit from recent technology the cross-linking reaction.
advancements in silicone elastomers. Manufacturers
have searched for ways to eliminate the need to post- While silicone polymer materials have extremely low
cure materials after curing. This white paper details the concentrations of intrinsic siloxane volatiles, the process
advantages and disadvantages of post-curing, and of curing silicone with peroxide-based chemicals adds
highlights the situations where the process can be lower molecular weight organic by-products to the
completely eliminated. material. After curing, some of these by-products
remain. For example, when 2, 4-dichlorobenzoyl
SILICONE ELASTOMERS peroxide is used to cure silicone tubing, the main by-
In the 1800’s, researchers started making synthetic product 2, 4-dichlorobenzoic acid starts to accumulate at
silicones from elemental silicon combined with carbon. the surface of the tubing as a white powder (also called
Dr. Frederick Kipping spearheaded these development “bloom”). Post-curing helps remove the bloom and other
efforts, which eventually would lead to the by-products ― mainly dichlorobenzene and small
commercialization of silicone elastomers. Scientists at quantities of polychlorinated biphenyl (PCBs) ―
Corning Glass developed the first commercially used reducing levels to a parts-per-billion range.
silicone in the 1930’s. Since then, the material has been
used in multiple industries because of its many Post-curing means that the material is heated in an oven
advantages, such as resistance to heat and moisture, low at a given temperature for a certain amount of time.
volatility and inertness. While there are many variations in temperature and time,
the three most common combinations seem to be 2 hours
Today, the majority of silicone elastomers fall into two at 177°C, 2 hours at 200°C and 4 hours at 200°C.
main groups: liquid silicone rubber (LSRs) and high- Post-curing peroxide-cured silicone removes residue,
consistency silicone rubber (HCRs). LSRs, with their odor, and toxins; and improves the characteristics of the
inherent low viscosity, are easier to pump and can fill material. Post-curing is also necessary to prevent acidic-
intricate mold cavities making more geometrically catalyzed decomposition of the rubber.
PLATINUM-CURED SILICONE 2. Food and Beverage
Per 21 CFR 177.2600, silicone elastomer parts for
Platinum-based curing systems are sometimes called
food contact applications can meet regulatory
addition cure systems, because there is a silicone hydride
requirements either by formulation or extraction. If
polymer that adds across the double bond of a vinyl
the material doesn’t meet formulation specifications,
functional siloxane polymer in the presence of a
the parts need to meet extraction requirements. If a
platinum-based catalyst to create a cross-linking
manufacturer’s products cannot meet these
reaction. Platinum-based curing does not create any by-
requirements as molded and processed, post-curing
products, and component parts can theoretically be ready
becomes necessary.
for use straight out of the mold. However, when
platinum-based curing systems were invented, many
3. Health Care
manufacturers continued to post-cure their silicone
Because of the inherent risks and concomitant
elastomers since silicone elastomers had historically
regulatory requirements involved with the majority
been post-cured. They discovered that post-curing
of healthcare applications, healthcare original
platinum-based silicone can bring some advantages. In a
equipment manufacturers strive to ensure part to part
typical molding or extrusion application, curing
consistency in their molded articles. Post-curing is
continues to take place after the article is molded or the
often implemented because it can stabilize the
tubing is formed. This is because the material is cured
silicone to help standardize the end products.
sufficiently enough to be de-molded and inspected
before it has completely cured. Manufacturers take Post-curing is also used in the health care industry to
advantage of this phenomenon to be able to speed up the prepare samples prior to biocompatibility screening. The
overall productivity of the process. majority of biocompatibility requirements for silicone
elastomers are assessed based on testing of extracts of
The down side to this practice is that the material will
the cured material. As mentioned previously, when
continue its cure, until it attains full cure, as it ages. With
cured material is post cured, the lower molecular weight
this additional curing, changes can be observed in the
species in the material (volatile content) is reduced. By
physical properties of the materials; the hardness of the
decreasing the overall volatile content of the elastomer,
material will increase, ultimate tensile strength will
the concentration of volatile components in the extract is
typically improve and the elongation will drop. These
lowered as well; that may improve the odds of
changes can be important in specific applications, so this
successfully passing a biocompatibility test of the cured
effect needs to be well understood. To account for these
article’s extracts. Attention should be given to the use of
changes, a post cure is often implemented to drive the
a materials supplier’s biocompatibility data in this
elastomers cure to completion and stabilize the physical
regard. If the material supplier performed a post cure
characteristics of the material.
prior to biocompatibility testing of the material, then the
cured article or component should be post cured as well
Furthermore, volatile siloxane species remain in the
for the data to be considered relevant for the application.
cured silicone matrix of the particular component after
initial cure. Unlike some by-products of peroxide cure,
Post-curing of platinum-cured silicone also is carried out
these lower molecular weight volatile components are
in many industries to prepare silicone articles for
generally not considered particularly toxic; however
secondary bonding procedures. The low molecular
some industries must follow specific regulatory,
weight volatile fluids that remain after initial curing have
environmental and safety requirements which limit the
the potential to migrate to the surface of the component,
amounts of these volatile components that can be found
in effect acting as a release agent negatively impacting
in the cured component. Some examples are:
the ability to adhere the component to another substrate.
For example, if you are looking to bond a silicone
1. Infant Care and Automotive
balloon to an extruded silicone catheter shaft, any low-
These industries have to meet stringent volatile
molecular weight silicones that remain on the surface of
requirements. Post-curing is often necessary to
the shaft could act as a release, preventing good
remove or lower the overall volatile content in the
attachment between the balloon and the catheter shaft.
silicone article to achieve passing results for the
Post-curing both components will drive off the low-
respective testing.
molecular weight fluid and improve the overall adhesion use of scrubbers or other systems that recapture the
to the balloon. volatiles liberated during post-cure so they don’t end
up expelled into the environment.
COSTS OF POST-CURING SILICONE
IS POST-CURING NECESSARY?
Despite the many advantages of post-curing silicone
elastomer, manufacturers continue to look for ways to Depending on individual product and process
eliminate this step from silicone processing in order to circumstances, post cure may or may not be necessary.
cut the costs associated with it. Post-curing adds The majority of silicone suppliers (Dow Corning being
overhead to the manufacturing process in the following an exception) require some type of a post cure for their
ways: materials to achieve the physical property profile
described in the sales specification or data sheet.
1. Floor space:
Companies must allocate area on the manufacturing Because of the costs associated with post-curing, OEMs
floor for the ovens, carts, and trays to perform the should seriously question if the process step is necessary
task. for their application. In some instances, a higher degree
of variability in the cured article is acceptable if the
2. Ovens:
silicone meets minimum physical properties; in these
These ovens add additional costs to the capital
cases, post-curing might be adding unnecessary
budget.
processing time and costs. But even in industries where
3. Utilities: stable physical properties over time are required, such as
The electricity used to operate the ovens adds to a health care, new developments in materials offer
manufacturer’s expenses. promising alternatives to post-curing.
4. Equipment:
A current development aimed at providing more
Companies also must purchase equipment such as
physically stable as-molded articles and components is
timers, racks, and gloves to run a post-curing
the new Dow Corning® brand C6-7XX series of liquid
process.
silicone rubber materials. These recently introduced
5. People: LSRs from Dow Corning exhibit a physical profile that
While post-curing does not require high-skill labor, is essentially unaffected by the addition of a post-cure.
companies must either hire unskilled laborers whose
only job will be to post-cure silicone parts, or pay Figure 1: Shore A Durometer Comparison
skilled workers to do it as part of their job.
6. Time:
The time added to the manufacturing process while
the silicone parts are sitting in the oven during post-
curing delays usually creates a bottle neck in the
overall manufacturing flow of the cured article or
component. Depending on how it is defined, a
suitable post-cure typically will only take a few
hours; however, some companies post-cure their
silicone for days at lower temperatures, a process
that adds significant time to the manufacturing
process.
7. Safety: In Figure one, above, the hardness measured for various
While post-curing is a relatively safe process, high and low consistency silicone materials with
accidents can happen, perhaps with greater severity nominal 50 Shore A hardness are compared as molded,
due to the higher temperatures that can be used in and after a two- and four-hour post-cure at 177°C. The
the process. A burn injury could be not only painful new Dow Corning® C6-750 Liquid Silicone Rubber is
and disfiguring, but also quite disruptive and costly. the only material that shows no change in hardness after
In addition, certain regions in the world require the each post-cure cycle when compared against
Silastic® Q7-4850 BioMedical Grade Liquid Silicone CONCLUSION
Rubber, Dow Corning® C6-550 Liquid Silicone Rubber,
Post-curing of silicone rubber can easily become a
and Dow Corning® C6-150 Elastomer.
requirement when the material has been cured with
particular peroxide-based initiators such as
Figure 2: Tensile Strength Comparison
2, 4-dichlorobenzoyl peroxide, because it is an effective
way to remove the problematic by-products from the
vulcanization process. However, manufacturers that
post-cure platinum-cured silicone should evaluate if they
can eliminate the post-cure process step.
Innovative material suppliers are continuing to develop
new silicone elastomer technology that may enable
companies to eliminate the process of post-curing their
silicone parts, cutting time and costs from the
manufacturing process.
REFERENCES
In Figure 2, a comparison of ultimate tensile strength is K.L. Mittal, A. Pizzi (2009). Handbook of Sealant Technology. CRC
shown as molded and after the same two-and four-hour Press. p. 27. ISBN 0-8493-9162-8.
post cure that was described above. Again, the new
Dow Corning C6-750 Liquid Silicone Rubber is [Link]
essentially unchanged after post cure whereas the older
silicone materials exhibit a fair amount of variability in
the measured property.
Figure 3: Elongation Comparison
In the third and final figure, elongation is compared in
the same manner as previously described. As in each of
the previous figures, the new Dow Corning C6-750
Liquid Silicone Rubber remains essentially unchanged
after post cure whereas the older silicone materials
continue to exhibit a fair amount of variability in this
measured property as well.
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