Biomaterials Lab-3: PDMS preparation

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BE 2330 Lab 3a: Silicone Polymer Preparation and Modification.
Instron Tensile Test Demonstration

For this lab we will have 3 larger groups, so the assigned lab groups will need to combine
and work together.

Objectives:

1. Understand the operation of the Instron materials testing instrument in the tensile mode
as a means to characterize mechanical properties of stress, strain, and elastic modulus.
The TA will provide a demonstration. You should be able to run the instrument
independently next week to characterize the samples you prepare today.

2. Prepare polydimethylsiloxane (PDMS) using a commercial kit (Sylgard 184, Dow
Corning). Samples will be prepared at two cross-linking densities by varying the ratio of
polymer base (B) to in initiator (I). Please note that the initiator is used to initiate cross-
linking. It is not initiating polymerization of monomers into growing chains. Each of the
three groups will be assigned one of the following preparations:

a. B:I prepared at 10:1 mass ratio
b. B:I prepared at 20:1 mass ratio
c. B:I prepared at 20:1 mass ratio + 2% PDMS-PEO diblock copolymer

Prepare polydimethylsiloxane (PDMS) with 2% additive of a linear block copolymer
(PDMS-PEO), where PEO = poly(ethylene oxide), a hydrophilic polymer chain with the
formula: -(C-C-O)n-CH3. Please read about this biomedical polymer in the Temenoff text
and why it is widely used in biomedical applications.

While mixing the polymer and curing agent you will likely introduce air bubbles. These
bubbles will act as stress raisers, or weak links in the polymer samples that will lead to
early failure. Remove air bubbles by centrifuging at 5000 to 8000 RPM for 5-10 min.
Pour your polymer into the dog bone molds* (there are 33 molds, so prepare 11 samples
of each formulation (a, b, c). Cure the samples in the oven at 70C for at least 1 hr, then
carefully peel the polymer dog bones from the molds for measurement on the Instron.
Also prepare some polymer on glass slidesa thin coating across the top of the slide will
suffice. These samples will be used for surface analysis in subsequent labs. Any
remaining polymer mixture can be stored at -20C to prevent cross-linking and used at a
later time.

* Dog bone molds were prepared according to ASTM Report Standard Test Method for
Tensile Properties of Plastics D638 10. The ISO 37:2005(E) Report Rubber,
vulcanized or thermoplastic Determination of tensile stress-strain properties is followed
for Instron testing. We will review this ASTM Report when testing the samples.


Biomaterials Lab-3: PDMS preparation
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Materials:

1. Pipettes + tips (200, 1000) for adding
PDMS-b-PEO copolymer
2. 10 and 3 ml syringes for dispensing
base, initiator, PDMS-b-PEO
3. Analytical balances
4. Weigh boats
5. Stir sticks (or similar)
6. Gloves
7. KimWipes / paper towels
8. Sylgard 184 kit (PDMS base +
initiator)
9. PDMS-b-PEO 1200MW or similar
surfactant (Polysciences)
10. Vacuum chamber
11. Oven
12. Centrifuge (for 15 ml tubes)
13. 15 ml centrifuge tubes
14. Precision calipers for measuring
sample dimensions
15. Freezer (-20 C)

Details:

Form three groups. Each group will b three (a, b, c,) distinct PDMS samples. Each group
will prepare three dog bone samples from their PDMS.
While bubbles are being removed from the polymer mixtures, the TA will provide a
demonstration of how to operate the Instron using the Bluehill Sofware package in the
tensile mode.
Students will be permitted to test various samples during lab period to make sure they
understand the operation.
We will also review the data from the ZnO nanoparticle synthesis lab.


Polymer preparation:

For the 10:1 base to initiator preparation:

1) Put a piece of Al foil or Kimwipe on balance to protect from spills, tare the balance.
2) Add a weigh boat and tare the balance.
3) Remove the boat--let the balance read a negative value (this is boat weight). Replace the boat
on the balance and make sure it reads zero again.
4) Fill a 10cc syringe with Sylgard and dispense into the boat until 10 g is dispensed.
5) Add 1 g of initiator to the 10 g of base.
6) Remove boat from balance and gently stir polymer / initiator with a stir stick for 5 min and
avoid introducing too many bubbles. Pour the contents from the weigh boat into a 15 ml
centrifuge tube. (label tube with group name and B:I ratio).

For the 20:1 base to initiator ratio, double the preparation (20 mL total PDMS):
1) Follow steps 1 to 4; for step 5 prepare a 20:1 base to initiator ratio.
2) Remove boat from balance and gently stir polymer / initiator with a stir stick for 5 min and
avoid introducing bubbles. Pour 10 mL into a 30 ml centrifuge tube and label.

Biomaterials Lab-3: PDMS preparation
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For the 20:1 ratio that will have the copolymer (PDMS-b-PEO) additive:
1) Replace the weigh boat with the remaining 20:1 PDMS:Initiator (~10 ml or 10g) onto the
aluminum sheet on the balance. The balance should have read the negative weight of the weigh
boat before replacing the boat + polymer. If it did not, then add an empty weigh boat, tare,
remove the boat, then add your boat + polymer. Now you have the weight of just the polymer +
initiator.
2) By mass, add the PDMS-b-PEO surfactant to make a 2% by weight, remove from balance and
gently stir, again avoiding introducing bubbles
3) Degass the 20:1 samples.

Instron demonstration:
The TA will demonstrate how to operate the Instron while the samples are degassing. Use this
time to practice using the instrument.

PDMS dog bone preparation:

Make sure to have the mold next to the oven so as to not have to carry it across the lab and
risk the polymer spilling over the edges of the molds.

1) Pipette polymer into the molds (11 samples for each preparation a, b, c)fill only to the top
edge of the mold.
2) While dog bones are being prepared the remaining members of the groups can prepare PDMS
on glass slides for use in the surface analysis lab. Store any unused polymer (B+I) in the
centrifuge tubes at -20C.
3) Carefully transfer the plates and glass slides to the oven at 70C to cure for at least 1 h.
In lab 3b you will test the mechanical properties of the dog bone samples. In lab 3c you will
characterize the surface properties of the samples.


Dog-bone mold preparation:

The dog bones have been prepared according to ASTM and ISO standards. Both reports are
available on Canvas. To understand why we follow these standards, look over the abstract and
first page of the following journal article on the influence of dog-bone size on measurements for
thin polymer films: http://www.springerlink.com/content/wk353t8654554809/


Questions for Lab 3ab (Separate lab handouts are provided for Lab 3b, 3c):

1. Is PDMS prepared by chain or condensation polymerization?

2. Search the Internet to find the MSDS sheets for the base and initiator used in Sylgard
184. Are there any hazards with using this polymer? Could it be used as an implant
material or contact lens?

3. How does the shape of the dog bone influence the measurement of tensile properties?
Biomaterials Lab-3: PDMS preparation
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4. At what temperature did you cure the PDMS? What toxic product may be released if the
PDMS mixture is cured above 180 C in the presence of air?

5. The Instron provides force vs. displacement for a sample pulled in tension. How do you
convert this into stress vs. strain?

6. How does cross-head speed (rate of pulling sample) influence the shape of the stress vs.
strain graph for a polymer composed of entangled chains?

7. What is a load cell?

8. What is the maximum load capable with this model Instron? Where is the safety shutoff
in case of emergency?

9. Does increasing the cross-linking density of an elastomer increase or decrease the elastic
modulus?

10. Did the PDMS release cleanly from the molds? Did you observe any difference in release
and handleability of the PDMS containing the block copolymer?


Lab Reports:
This laboratory consists of three modules, over three weeks, and will be comprised of two
reports: 1) Report 1 is on the preparation and characterization of mechanical properties (Lab
3ab); 2) Report 2 is on the surface characterization and compressive properties.

Lab 3ab will be due in two weeks from the first module (i.e. one week after the samples are
tensile tested).

All the stress vs. strain data will be shared to provide statistical relevance. Each lab group must
plot their three polymer preparations (10:1, 20:1, 20:1+PEO) on a single graph to facilitate
comparison.

In a Table report the % elongation until failure and the tensile strength of each preparation.
Report the mean and standard deviation for these parameters based upon the shared lab data.
When reporting a mean, you must give the sample number (e.g. n = 7).









Biomaterials Lab-3: PDMS preparation
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Annex 1. PDMS polymerization (from: http://www.ims.ut.ee/~alar/microtech/Ch1_5/f)




Basic components of a curable PDMS elastomer (eg. Sylgard 184). Dimethylvinyl-terminated dimethyl
siloxane (1). Dimethyl methylhydrogen siloxane (2). Speiers catalyst (3).



Transition metal (M) catalyzed hydrosilylation reaction[30]. The catalytic cycle has two alternative routes;
both are beginning with the oxidative addition of hydrosilane ( (R)3-Si-H ), followed by migratory insertion
of the coordinated alkene either into the M-H bond (hydrometalation) or into the M-Si bond
(silylmetallation). The final step is a reductive elimination, which liberates the product and recycles the
catalyst.