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3D Printing and Viscosity

Purpose
1
To study how varying the parameters of a polymer solution apply to 3D printing.

Learning Objectives
To understand the importance of polymer properties, specifically viscosity, in the 3D printing applica-
tion of pharmaceuticals.

Investigate the effect of temperature and concentration on polymer solution viscosity.

Reconfigure a non-linear equation to determine the important parameters of an model.

Discussion

Students will study the correlation between temperature and concentration on the viscosity of a polymer solution.
In both solution or in the melt phase, polymer viscosity increases as temperature decreases. In solution, polymer
viscosity increases as concentration increases. Many methods of 3D printing take advantage of these relationships
to quickly create complex parts. In this lab, students will use a Brookfield Viscometer to measure the viscosity of
an aqueous polymer solution at different temperatures and use their data to calculate material-specific viscosity
constants. Additionally, students will measure the effect of concentration on polymer viscosity to understand the
relationship between molecular weight, viscosity and concentration. Ultimately, students will understand the
importance of polymer properties in a 3D printing application of personalized pharmaceuticals.

3D Printing is a powerful manufacturing process more correctly defined as Additive Manufacturing (AM).
In short, 3D printing adds layers of a material(s) to create a physical object from a digital file. This manufactur-
ing process represents a sustainable process as it significantly reduces material waste and energy usage. This is
contrasted to traditional processing that often uses subtractive manufacturing where the product development
process continuously cuts away material from a solid block producing significant waste.

When thinking of 3D printing, most people picture a fused filament fabrication (FFF) printer that resembles a
moving hot glue gun. However, there are many different methods of 3D printing, each with their own advantages
and disadvantages. Additionally, 3D printing utilizes a wide variety of materials including ceramics, metals, and
polymers. However, this experiment will focus only on polymers.

1 Professor Timothy Long and Dr. Emily Wilts contributed to the much of the discussion and suggested the general procedure used in this
laboratory experiment. Prof. Long and Dr. Wilts grants permission for use in the general chemistry laboratory manual.

Laboratory Manual Prepared by Catalyst Education, LLC for Virginia Polytechnic Institute and State University 3D.1
Department of Chemistry.
 3D Printing and Viscosity

Here are a few of the most popular methods of 3D printing utilizing polymers:

Fused Filament Fabrication (FFF) – Polymer filament is extruded through a heated nozzle, and then cools
and solidifies – the same principle as a hot-glue gun. The object is built from the bottom up, layer by layer. This
is the method used by most consumer 3D printers.
Advantages: Fast print times, easy setup, low-cost.

Stereolithography (SLA) – A UV light source is used to cure (polymerize) liquid resin into a solid polymer, in a
process called photopolymerization. When the layer has solidified, the part is lifted out of the pool of resin, and
the process is repeated. The object is built from the top down or the bottom-up. The light source can be a UV
laser that is scanned over the object, or a projected image which cures the entire layer at once.
Advantages: High-accuracy, fine features, smooth surface finish

Selective Laser Sintering (SLS) – Similar to stereolithography, but instead of photopolymerization, a high-
power laser is used to melt small solid particles (powders) of polymer (or other meltable material) together into
a solid shape layer by layer.
Advantages: High strength parts, complex shapes, can be used with metals.

Binder Jetting – A powder bed-based system that selectively deposits a binder (or polymer) onto the powder
bed, bonding these areas together to form a solid part one layer at a time. There are four essential steps. In the
first step a solid material or powder is deposited into a mold. In the second step, a carriage with an inkjet nozzle
deposits drops of a binding agent to bind the powder. In the final two steps the process is repeated and the final
product is cured to achieve the desired material properties.
Advantages: Lower-cost, allows for large and complex parts, excellent to produce small batch products.

In many 3D printing applications, understanding viscosity is critical to ensuring the product tolerances, surface
finish, and material properties. This experiment is based on a recent research study entitled “Comparison of
Linear and 4‑Arm Star Poly(vinyl pyrrolidone) for Aqueous Binder Jetting Additive Manufacturing of Personal-
ized Dosage Tablets”. The research provides comprehensive models and data supporting methods of predicting
jettability of varying polymer architectures in binder jet printing of personalized pharmaceuticals. The research
provided the relationships between polymer solution properties and jettability on a thermal printhead.

Laboratory Manual Prepared by Catalyst Education, LLC for Virginia Polytechnic Institute and State University 3D.2
Department of Chemistry.
 3D Printing and Viscosity

Linear poly(vinyl pyrrolidone) (PVP) has the chemical formula (C6 H9 NO)n and is de-
picted in Figure 3D.1, where the linear polymer backbone (C2 H3 ) is depicted inside the
parentheses, with n representing the number of monomer repeating units. PVP is a
common polymeric binder used in water-based binder jetting AM due to its biocompati-
bility, water-solubility, and high glass transition temperature. PVP is also used in contact
lens, drug delivery, skin-care products, hydrogels for wound care and other applications
deemed safe use in humans. PVP is synthesized using free radical polymerization of the
monomer N-vinyl pyrrolidone in the presence of an initiator.
Figure 3D.1:
Chemical structure Additive manufacturing of pharmaceutical tablets has the potential to provide patients
of Linear poly(vinyl
with personalized medication specific for their individual requirements. An estimated
pyrrolidone).
75−85% of side effects result from inaccurate dosing and pharmaceutical combinations
because of varying weights and metabolic rates of patients. To alleviate this problem, researchers utilized fuse
filament fabrication, binder jetting, and selective laser sintering 3D printing technologies to produce personalized
dosage tablets, which also transformed the tablet-making process into a more time- and cost-efficient process. The
focus of this experiment investigats binder jetting 3D printing.

Stable droplet formation in binder jetting systems significantly depends on binder solution properties such as
viscosity, surface tension, and density. In the research, investigators studied both linear and star-shape polymer
architecures to produce active pharmaceutical ingredient (API) tablets. No literature existed to compare the
polymer architecture of PVP on tablet formation. Star and graft polymers maintain lower solution viscosities
compared to linear analogues at the same molecular weight. The research demonstrated that the investigated
polymers represent strong candidates for future personalized dosage pharmaceuticals

During this laboratory experiment students will investigate the correlation between temperature and viscosity of
a linear PVP solution. Viscosity is a measure of a fluid’s resistance to flow and is a very important quantity in
certain types of 3D printing, which rely on the flow of liquid monomer or polymer to form the part being printed.
Viscosity is a subject of rheology, the study of the flow and deformation of matter (both solid and liquid). In the
cited research, as concentration increased the polymer chains exhibited a greater frictional force in solution and
began to interact, thus increasing the viscosity. As molecular weight increased, the polymer chains overlapped
and entangled, which also caused an increase in viscosity. In this laboratory experiment students will use a dilute
solution of 360,000 g/mol molecular weight linear PVP.

Viscosity is important in each of these 3D printing methods for different reasons. In the case of FFF 3D printing,
the heat of the nozzle must be carefully controlled so that the solid polymer filament will melt and be dispensed
at the right viscosity, after which, it will solidify when cooling. In binder jet printing viscosity controls the staple
drop formation which forces a drop to eject from the nozzle and bind the active pharmaceutical ingredients and
filler materials.

Laboratory Manual Prepared by Catalyst Education, LLC for Virginia Polytechnic Institute and State University 3D.3
Department of Chemistry.
 3D Printing and Viscosity

The viscosity of most materials decreases as temperature increases. In many simple polymer melts or polymer
solutions, viscosity can be described as a function of temperature using the Andrade equation. The Andrade
equation holds for many polymer solutions and polymer melts well above their glass transition temperatures.
The exponential Andrade equation is given in Equation 3D.1:

𝐵
𝜂 = 𝐴 ⋅ 𝑒𝑇 (Equation 3D.1)

The variables in the Andrade equation are defined as follows:

𝜂 – viscosity (mPa⋅s)
𝑇 – temperature (K)
𝐴 – material constant (mPa⋅s)
𝐵 – material constant (K)

With this equation, knowing the values of A and B for a particular liquid allows calculation of the viscosity at
any temperature under certain conditions. This holds for a polymer melt assuming the ploymer has not transi-
tioned back to a solid.To linearize this exponential equation, take the natural logarithm on both sides to obtain
Equation 3D.2 which can also be depicted as Equation 3D.4:

ln 𝜂 = ln (𝐴𝑒 𝐵/𝑇 ) (Equation 3D.2)

ln 𝜂 = ln 𝐴 + log 𝑒 𝐵/𝑇 (Equation 3D.3)

𝐵
ln 𝜂 = ln 𝐴 + (Equation 3D.4)
𝑇

Which, when rearranged, depicts a linear equation:

1
ln 𝜂 = 𝐵 ( ) + ln 𝐴 (Equation 3D.5)
𝑇

Therefore, if students plot ln 𝜂 versus 1/𝑇 the slope is 𝐵 and the 𝑦-intercept is log 𝐴.

In this lab, students measure the viscosity of 360,000 g/mol molecular weight linear PVP solutions at several
different temperatures using a Brookfield Viscometer and determine the constants A and B using the linearized
equation. Finally, the students will measure the viscosity of a 3% solutions of the PVP to further investigate the
effect of concentration on viscosity.

Laboratory Manual Prepared by Catalyst Education, LLC for Virginia Polytechnic Institute and State University 3D.4
Department of Chemistry.
 3D Printing and Viscosity

Experimental:

Equipment Chemicals
400 mL beaker clip Polymer solutions linear poly(vinyl
Hot plate Brookfield (3%) of 360,000 g/mol pyrrolidone)
Thermometer with viscometer

Safety Precautions
PVP Solutions of 3% Concentrations: Irritant

Procedure Summary:

Students will collect as many measurements of viscosity at different temperatures as possible in the allowed lab
period time for the 3% solution, with a minimum of at least 9 temperatures. Each student pair has three solutions
of the 3% 360,000 molecular weight PVP solutions.

• One solution is kept at room temperature at all times.

• One solution is initially cooled in an ice bath and subsequently allowed to warm. Measurements are
taken as the solutions increases in temperature after being removed from the ice bath.
• One solution is slowly heated on a hot plate and measurements are taken as the sample heats. The final
temperature should never exceed 60 °C.

Using the Brookfield Viscometer:

The viscometer can be raised and lowered using the quick-action lever on the back of the instrument. Take
extreme care not to touch the spindle, which is protected inside the spindle guard.

a. Attach the thermometer in the solution such that it is not touching the rotating spindle.

Take care not to let the thermometer touch the spindle during the measurement.

b. Check that the viscometer is raised so you can place the jar under the spindle without tilting it. Lower
the viscometer until the spindle is completely immersed in the solution.
c. Make sure the spindle speed is set to 100 RPM, and confirm the spindle is set to s61. These can be
changed by flipping the selector lever to the left or right, respectively, and using the dial.
d. Start the spindle and wait for approximately 1 minute while the measurement stabilizes.
e. Read the top measurement displayed on the viscometer and record the value in cPs. If the value fluc-
tuates slightly, record the average value.

Laboratory Manual Prepared by Catalyst Education, LLC for Virginia Polytechnic Institute and State University 3D.5
Department of Chemistry.
 3D Printing and Viscosity

f. Immediately afterwards, read the thermometer and record the current temperature of the solution in
°C.
g. Stop the spindle and wait for the spindle to completely come to a stop. Raise the spindle completely out
of the jar and let it drain for a moment before carefully removing the jar.
h. Place the rinse beaker directly under the spindle and use the rinse bottle with DI water to thoroughly
clean the spindle.
i. Leave the rinse beaker under the spindle to facilitate drying. Any polymer that dries on the spindle will
reduce the accuracy of your measurements.

Experimental:
Materials:

• Hot Plate
• Thermometer with clip
• 3% solution 360,000 g/mol linear poly(vinyl pyrrolidone
• Brookfield Viscometer

Procedure:
1. The jars of poly(vinyl pyrrolidone) (PVP) solutions have been prepared ahead of time. Each student pair has
three solution jars of the 3% PVP solution.

2. Attach a thermometer, with a clip, to the inside of the jar labeled “Room Temp”. The thermometer should
be submerged at least 3 inches into the 3% PVP solution. This jar will be kept at room temperature.

3. Place the jar of the 3% PVP labeled “Chilled” into an ice bath after attaching a thermometer, with a clip, to
the inside. The thermometer should be submerged at least 3 inches into the solution. Periodically, stir gently
with the thermometer to allow for uniform cooling.

4. Place the jar of the 3% PVP labeled “Heated” onto the hot plate and set to 60 °C after attaching a thermometer,
with a clip, to the inside of the jar. The thermometer should be submerged at least 3 inches into the solution.
Periodically, stir gently while making sure the thermometer does not come in contact with the stir bar.

Safety Precautions
Uncap the solution - never heat a closed vessel!
Do not allow the solution to heat above 60 °C

Laboratory Manual Prepared by Catalyst Education, LLC for Virginia Polytechnic Institute and State University 3D.6
Department of Chemistry.
 3D Printing and Viscosity

5. Using the special procedures directions and instructions for the Brookfield Viscometer located near the unit,
measure the viscosity of the room temperature 3% PVP solution.

6. Measure the viscosity of the heated 3% PVP solution using the same procedure.

7. Place the heated 3% PVP solution back on the hot plate and measure the viscosity periodically, as it warms.
Be sure to use the Kevlar gloves if the jar becomes too hot to safely handle.

8. Measure the viscosity of the cooled 3% PVP solution using the same procedure. Place the cooled 3% PVP
solution on the lab bench and measure the viscosity periodically, as it warms.

Do not discard any of the PVP solutions!

• Checklist
 I understand that the deadline for the three round robin experiments is only one week and there
would be no further extension.
 I understand that I need to submit the written report in modules on Canvas

Laboratory Manual Prepared by Catalyst Education, LLC for Virginia Polytechnic Institute and State University 3D.7
Department of Chemistry.