4D Printing Based Piezoelectric Composite For Medical Applications
4D Printing Based Piezoelectric Composite For Medical Applications
MEDICAL APPLICATIONS
DANIEL GRINBERG1,2,3 ,SABRINA SIDDIQUE4 ,MINH-QUYEN LE1 ,RICHARD LIANG4 ,JEAN-
FABIEN CAPSAL1 PIERRE-JEAN COTTINET1
1
UNIVERSITÉ LYON, INSA-LYON, LGEF, EA682, VILLEURBANNE, F-69621, FRANCE
2
DEPARTMENT OF ADULT CARDIAC SURGERY, HOPITAL CARDIOLOGIQUE LOUIS PRADEL
– LYON MEDICAL SCHOOL-28, 69677, BRON CEDEX, FRANCE
3
DEPARTMENT OF CARDIOVASCULAR SURGERY, MOUNT SINAI HOSPITAL, NEW YORK
CITY, 10029, NEW YORK
4
HIGH-PERFORMANCE MATERIALS INSTITUTE (HPMI), FLORIDA STATE UNIVERSITY,
TALLAHASSEE, FLORIDA, 32310 CORRESPONDENCE TO: P.-J. COTTINET
Introduction
3D printing has long been used and discussed in different fields such as biomedical
devices, design, and rapid prototyping because of its ease of turning computer 3D files into
physical structures. However, most of such products are only conceptual prototypes rather than
functional products since these usually lack strength and functionality. In order to overcome such
weaknesses, a new technology known as 4D printing came into the research field. The main goal
of 4D printing is to make it possible for the self-assembling property of a 3D-printed object to
exposed on stimuli such as moisture, chemical reactions, heat, pressure, etc., and expect a
response. It can also be described as developed 3D printing with the addition of a time dimension
or the inclusion of time frame to such printing which makes it possible for the response to the
stimuli happen (Deshmukh,2020). Among the good candidates for this type of printing are smart
materials that can respond well to external stimuli. Although in the past complex structures are
difficult to be achieved, recent developments such as in electroactive composites, paved the way
for this complex functional systems to come in to use.
Piezoelectric(PZT) materials are one of the usually used electroactive materials. This has
the capacity to produce voltage or electrical charge in response to externally applied stress and
vice versa. Its properties are very much beneficial in the medical domain such as implant
technology. Take for example, increase of bone growth and reduction of bone resorption can be
achieved through selective electrical stimulation of such implants. This is usually fabricated
through a technique known as fused filament fabrication. Here, molten plastic is ejected by a
heated nozzle in thin layers put on top of one another placed on a print bed which later on leads
to the formation of the desired 3D printed product. Such shape is achieved by complimenting
movements of the nozzle and the print bed while the heated plastic is being extruded by the nozzle
(Weiner, 2020). As compared to the traditional methods of material-removal, this process results
to ease in creating complicated and ornate shapes with a wide range of densities and
compositions. Ceramic piezoelectric (PZT ceramic) materials have long been used in the
production of transducers but because of its need for high temperature in sintering, it is not
compatible with typical 3D printed materials with only about 150 to 250 °C of melting point. Aside
from this, PZT ceramic is also expensive and heavy weight. Another type of PZT is the
polyvinylidene fluoride (PVDF) which is beneficial and suitable in systems requiring small active
elements and mechanical flexibility. However, like the ceramic type, PVDF may also be hard to
be formed into complex 3D structures since it needs to be stretched during polymerization thus,
may make it hard for substrates to adhere to it.
In thus study, a new approach on the piezoelectric composites would be introduced in
order to overcome the aforementioned drawbacks and produce a lowcost and low weight material
that is adaptable to 3D printing. Specifically, a 3D-printed knee prosthesis would be the focus of
this study which was integrated with an active sensing element capable of determining the
mechanical strain on the prosthesis under a force applied. To support such aim, investigation of
the real time measurement of the piezoelectric coefficient versus the input force would be done.
Review
a. Property/Application
The main application discussed in the paper is in the medical field, specifically in
the production of knee prosthesis from 4D printing. Through different methods such as
Computerized Tomography scans, Magnetic Resonance Imaging , or translation of X-rays,
prostheses and implants could be made into any imagineable geometry presented in
different CAD formats and made into existence through 3D printing. Because of this this
type of printing have long been use din the healthcare sector in manufacturing both
standard and complex prosthetics and implants sometimes, only about a day. However,
such structures are considered as passive since they have limited level of intelligence not
capable of determining the lifetime of prostheses by measuring the mechanical
stress/strain as well as not having sensors and/or actuators that can provide information
regarding cell or bone growth. This is where 4D printing is needed. In order to validate the
composite’s feasibility based on 4D printing, the knee prosthesis produced in the study
where subjected to electro-mechanical characterization.
b. Experimental Design
The overall extrusion of the inorganic/organic composite filament was made possible
by solution casting of the commercially available thermoplastic Polyamide 11 (PA11) and
the piezoelectric material, in this case, Barium Titanate (BTO) particles. As seen in the
figure above, Polyamide 11 (PA11) dissolved in dimethyl acetyl amide at 150 °C is
combined with the required amount of BTO particles of about 10% volume fraction and
underwent ultrasound for a duration of 5 minutes. After washing with deionized water and
filtration, the solution was placed into an oven set to 150 °C to remove residues of the
solvent. At 220 °C, above the melting temperature of the polyamide, the films were then
hot pressed and loaded to the Laboratory Mixing Extruder(Dynisco,Inc.). At a constant
temperature of 200 °C, the acquired composites were then melted through the heaters
placed along the barrels and were mixed through rotating screws at 180 rpm. Through the
use of a die cutting machine, the molten polymer were cut at a 5 mm diameter cross
section subjected to a lower temperature of 130 °C. These are then fed to the 3D
printer(Ultimaker 3) after cutting the required length.
In order to assess the composites’ ferroelectric performance, an experimental test-
bench was used. Here, two electrodes were placed on both sides and circular samples of
20 mm diameter and 2mm thickness were set. Using a Kistler Amplifier Charge Meter
Type 5015A, the coefficient of piezoelectricity was determined.
It is also important to keep in mind that the development of the knee prosthesis in this
study followed the following clinical and technical requirements:
Knee implant systems are generally composed of a tibial and femoral component
which are both made of a metal alloy. These are then attached to the bone through acrylic
cement and an ultra-high-molecular-weight polyethyelene insert is also embedded
between them. On the other hand, as seen in Figure 4, four printed piezoelectric
transducers were used as the sensing system. These are placed in places where the two
condyles or part of the joint in the femoral component transmits the forces between tibia
(frontal bone below the knee) and femur (thigh bone). Universal electrochemical test frame
(Shimadzu AGS-X 10 N-10 kN) was then used to simulate the force applied by the femoral
component. Dewesoft acquisition card (SIRIUS-HD LV) was used to acquire the
piezoelectric response of the said printed structure while a load cell was used to determine
the applied compression force to the structure.
Results
Take note that the composite used is composed of BaTiO3 with 700 nm particle size and
10% volume fraction. In Figure 2(a), we can see that as the input electric field increases, the
normalized piezoelectric constant (𝑑33 /𝑑33𝑚𝑎𝑥 ) increases as well but at the critical value 𝐸𝐶 of 4
V/μm, we can see a sudden decrease of the constant. This is because this value is consistent
with ceramic’s coercive field since the composites for 30 mins, were poled at 4V/μm at 80 °C.
Thus, the piezoelectric constant becomes saturated at the maximum value beyond that level of
electric field. On the other hand, in figure 2(b), the relationship between the volume fraction of the
composite and the piezoelectric properties were determined. Here we can see that there is a
linear and direct proportion between the two. Figure 2(c) shows that relationship between the
piezoelectric voltage ( 𝑔33 ) of the composite and the volume fraction for different article sizes (100
nm, 300 nm, and 700 nm). We can see here that the 𝑔33 in composites with particle sizes greater
than 300nm are much greater than those with smaller particle sizes. Notable increase of 𝑔33 can
be observed 100 to 300 nm but there was not much of a difference from 300 nm to 700 nm.
Indeed, because higher particle sizes of ferroelectric materials favor homogeneity effects and
dispersion, higher piezoelectric properties of the composed were observed. Lastly, figure 2(d)
shows the developed sensor’s typical size in comparison to a human hand.
First and foremost, the explanation of results in the articles seems to have been
interchanged with one another thus, this explanation is from what I see on the figure based also
from the enumerated results in the article. Figure 5(a) displays the temporal evolution of the
piezoelectric charge and force and shows a perfectly in phase input compressive force and
resulting electrical signal. This means that piezoelectric behavior was properly reflected. In
figure(b), with different number of cycles starting from around 1000 times, both the charge
displacement and applied force were obtained based from the signals’ average amplitudes.
Figure 5(c) shows that mechanical excitation and electrical responses have linear dependences
and confirms that the electrochemical conversion is caused by the transported charge. Since the
samples were put under compressive mechanical stress, they become excited and produced
negative values for forces and piezoelectric charges. The slope between the force and charge
displacement as depicted in figure5(b) were then extracted to provide a much simpler figure of
the piezoelectric effect. As seen on figures 2(b) and 2(d), after roughly a huge number of cycles
at around 1000 to 50,000 cycles, the charge displacements attained have extremely small
variations (~ <1%) while the higher variation (~ <5%) of the piezoelectric coefficient were
observed might be because of some unavoidable fluctuations of measurements of forces.
Take note that in the above table, 𝐴𝑚 is the apparent contact surface between the sample
and the mechanical stress while 𝐴𝑠 is the sample’s active surface. Possible scenarios of the four
sensors are summarized in the above table. Here, the theoretical values for the ratio between
𝐴𝑚 and 𝐴𝑠 are 1,0.8,1.2 and 2 for sensors 1,2,3, and 4, respectively. The estimated values, on
the other hand, were calculated from the data obtained in Figure 5 and empirical measurement
of the theoretical electric displacement (D) and the applied force along the thickness direction
(𝐹3 ). In this table, we can see that the values for the real and estimated are not too far from each
other, meaning, an excellent reproducibility of the samples while still having the expected good
dispersion of the ferroelectric charges in the polyamide matrix could be observed.
Lastly, the overall performance of the knee prosthesis as perceived by the four sensors
were summarized in figure 6. As we can see here, figure 6(a) , shows that under the same applied
excitation of sinusoidal force, the temporal evolution of electrical responses of the four sensors
have quite close values between sensors 1 to 3 and sensor 4 is quite far. However, we can still
say that the four sensors were at the similar phase shifts thus all were in phase with the
mechanical excitation, a typical behavior of a piezoelectric material. Figure (b), on the other hand,
shows the variations of the electric charge through compression forces. Here, the attained slopes
from the curves for each sensor were seen to be proportional to the equation that the theoretical
electric displacement(D) is equal to the surface ratio(𝐴𝑠 /𝐴𝑚 ) multiplied to the applied force along
thickness direction ( 𝐹3 ). Thus, we can say that this excellent linearity could mean that the
proposed material, based on the sensors, can serve its purpose.
I do know about 3D printing specifically 3D printing pens. I also know about the abundance
of studies regarding biocomposites whose aim are to function as parts of the body yet made of
synthetic materials. However, honestly, the only four-dimensional things that I know are those in
cinemas. I was quite surprised by the fact that there is 4D printing which is quite useful in many
fields specially in medical application like in the formation of prostheses and in the aforementioned
biocomposites. I also realized that the implants that I’ve heard before were usually made of this
4D printing out of what are known as piezoelectric materials that can produce voltage or electrical
charge in response to externally applied stress and vice versa. I was also genuinely surprised by
the thought that prostheses such as those used in the knees need this ferroelectric and
mechanical response-stimuli interaction. I actually thought that prostheses just serve as
replacements for like broken bones and are manufactured in such a way that it can adapt to every
movement like how liquids take the shape and volume of its container. Lastly, I have realized that
although the usual structures made from 3D printing are not that functional and remains to just be
prototypes, with the use of 4D printing alongside proper selection of the materials to be used, we
can make continuous innovations out of these that can not only help those in biomedical field but
also because of its expected low cost, be of great help to those poor and handicapped or ill
persons who have a hard time tending their medical needs.
Conclusion/Recommendation
4D printing or the combination of the 3D printing mechanism and a response-stimuli
mechanism could be made possible through the use of smart materials. One of which is the
frequently used piezoelectric (PZT) ceramic, which is beneficial in the formation of medical
implants, and polyvinylidene fluoride (PVDF) which is beneficial and suitable in systems requiring
small active elements and mechanical flexibility. However, because of their limitations, a low cost
and reduce weight material that can adapt to the additive manufacturing process was introduced
in this study. The main focus here, is the production of a knee prosthesis equipped with 4 sensors
in order to keep track if the ferroelectric and mechanical stress response-stimuli relationship is
still working even in numerous amounts of cycles. Experimental results then showed that good
linearity and high sensitivity between the input mechanical excitation and resulting electrical
charge were accomplished, meaning, the produced prosthesis has high potential as a material
for smart sensing systems made from 4D. However, since the paper wasn’t able to show
experimental results of the compatibility of the material in a human body itself, it would be
important to have future research regarding this.
In terms of how the paper was written, I think it would be better to include more references
supporting the results of the experiments. It would also be of great help to mention how the results
were obtained since the experimental design part of the paper weren’t much given into detail. I
would also recommend future research on other ferroelectric and mechanical properties of
materials other than the aforementioned as well as in utilizing other materials other than
piezoelectric types in order to support the conclusion made in the paper.
References:
Deshmukh, Kalim (2020). 3D and 4D Printing of Polymer Nanocomposite Materials. Introduction
to 3D and 4D printing technology: State of the art and recent trends: 1–
24. doi:10.1016/B978-0-12-816805-9.00001-6
Grinberg,et al. (2018). 4D Printing Based Piezoelectric Composite for Medical Applications.
Journal of Polymer Science, Part B: Polymer Physics. DOI: 10.1002/polb.24763
Hatten. B. (2016). The Total Knee Replacement Prosthesis. Retrieved from https://www.
mykneeguide.com/the-knee/the-knee-prosthesis
“Lumen”.(n.d.). The Lower Limb. Retrieved from https://courses.lumenlearning.com/boundless-
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Weiner,H. (2020). Fused Filament Fabrication – Simply Explained. Retrieved from
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