Electronic Supplementary Information

Performance evaluation of Ce3+ doped flexible PVDF fibers for efficient

optical pressure sensors
C Hernandez1, Santosh K. Gupta2,3, Jose P. Zuniga2, Jorge Vidal4, Rene Galvan1, Misael
Martinez,1 Hector Guzman1, Lilian Chavez1, Yuanbing Mao5*, and Karen Lozano1*
1
Department of Mechanical Engineering, University of Texas Rio Grande Valley, Edinburg, TX
78539, United States of America
2
Department of Chemistry, University of Texas Rio Grande Valley, 1201 West University Drive,
Edinburg, Texas 78539, USA
3
Radiochemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai-400085
4
Department of Electrical Engineering, University of Texas Rio Grande Valley, Edinburg, TX
78539, United States of America
5
Department of Chemistry, Illinois Institute of Technology, 3105 South Dearborn Street, Chicago,
IL 60616, USA
*To whom correspondence should be addressed. ymao17@iit.edu, Tel.: +1-312-567-3815;
karen.lozano@utrgv.edu, +1-956-665-7020.

S1. Synthesis of undoped and CE doped PVDF fiber (CeN-PF and CeS-PF)
Polyvinylidene fluoride (PVDF) doped fibers were created using Forcespinning® technology.
Forcespinning® technology involves the creation of a polymer solution and the use centrifugal
forces to create nanofibers. The centrifugal forces release the polymer solutions and evaporates
transforming the solution from a viscous state into a solid one. The use of centrifugal spinning is
beneficial, since it does not require the use of a voltage input and has a high yield of fibers. The
use of a spinneret is a required attachment device of the Forcespinning® machine. Its function is
to hold the polymer solution, spin at high revolutions, and release the solution through its arms.
The arms contain 30 G needles. 3 mL syringes are used to input 1.5 mL of the solution into the
spinneret through 15 G needles. The machine could go up to speeds of 10,000 RPM. It also could
set a desired temperature and at times up to hours. The polymer solution contained 1.95 g of N,N-
Dimethylacetamide (≥99%, DMA), 1.95 g of acetone (≥99.5%), combined with the 1.1 g of PVDF
and 0.05 g of Cerium(III) Nitrate Hexahydrate (Ce(NO3)3•6H2O) or Ammonium Cerium (IV)
Sulfate Dihydrate (Ce(NH4)4(SO4)4•2H2O). The materials were homogenized by a magnetic stirrer

S1
on a hot plate at 75 Celsius for 1 hour. The rpms were set at ranges from 7000 to 8000 rpms for 8
mins, running for best results at ambient temperatures of 75 Fahrenheit and 45% humidity. The
fibers were gathered from the collectors, shown on Figure S1, by a 1”x1” aluminum collector
square.

Figure S1. ForceSpin technology for the synthesis of the Ce doped PVDF fiber.

S2. Instrumentation
The Zeiss Sigma VP scanning electron microscope (SEM) equipment was used to characterize the
diameter of the polymer fibers. When running an SEM characterization procedure, the polymeric
samples were sputtered with gold for 15 minutes to provide a better image. Five images were taken

S2
for each sample at 1 kV at magnifications from 200-5000X. Three-hundred counts of each sample
were obtained to analyze the average fiber diameter.
The use of Thermo Scientific K-Alpha x-ray photoelectron spectroscopy (XPS) equipment was
applied to verify the composition of the fibers. The fibers were split into small strands. The samples
and the raw powder materials were secured into the XPS testing surface via the use carbon tape.
The testing surface was inserted and pressurized into the vacuum chamber of the XPS. The XPS
software, Avantage, was employed to measure three distinct surface points of each specimen. A
survey and the required chemical elements of each sample were analyzed at 10 scans and at surface
scan spot of 300 microns at a time. The outer layer was scanned and etched at a rate of 0.07 nm
per scan.
Dynamic scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR) was
performed to identify the α and β polymer phases of the fiber samples. The DSC utilized was the
TA DSC Q-100. Aluminum hermetic pans were employed to run the DSC experiment. Each fiber
was measured to have a sample weight of 10 mg and then pressurized into a pan. A nitrogen
generator was used at 40 ml/min to control the cooling settings of the DSC.
The FTIR used on this project was the Bruker Vertex 70 series. A background test was first
performed to ensure the distinction between the reference and the test samples. The samples were
preloaded one at a time, and each absorbance test ran from 4000 to 400 cm-1.
The photoluminescence measurement was carried out using an Edinburgh Instruments FLS980
Fluorescence spectrometer. The instrument has the capability to record excitation/emission
spectrum and lifetime and is coupled with steady state and pulsed xenon lamp. The use of a
diamond anvil cell (DAC) was explored to induce the pressurized force on the fibers. The fibers
were pressurized up to a maximum pressure of ~63 GPa using a hydrostatic fluid such as
methanol:ethanol (4:1) solution. The fiber samples were doped with ruby. The ruby does not
interact with the luminescence of the fibers but used as pressure reference. CeN-PF/CeS-PF fiber
samples were placed between flat parallel faces of two diamond anvils (see Fig. S2) and subjected
to high pressure created by a force pushing one anvil diamond against the other. A prerequisite to
using the DAC for pressure generation is, that the anvil flats are parallel to each other and axially
aligned. Hydrostatic pressure is generated by pressing the anvil faces through a hole (200 µm
diameter) drilled at the center of the metal gaskets. A small sample (50 to 100 µm in linear Commented [KL1]: Check the highlighted section, I
changed the sentence but not sure if it makes sense, could
dimension and 50 µm thick) is placed in the chamber, along with a tiny fragment of Ruby for not read well how it was

S3
pressure calibration. The pressure generated in the DAC is measured by the Ruby fluorescence
technique.[1] The ruby fluorescent emission consists of two well defined peaks at wavelengths of
6942 Å (Rl line) and 6927 Å (R2 line).[2] The shift to higher wavelengths with increasing pressure
and the R1 shift has been calibrated against standard substances, to construct a pressure-scale. The
experimental set up showing light source from excitation side, DAC and light emission towards
detection side is also shown in Figure S3. DAC can be calibrated using an x-ray powder diffraction
method to measure the compression of NaCl and relating this to the measured shift in the
wavelength of the ruby R1-line.[3] The corresponding pressure was calculated from the
compression data utilizing an established equation of state for NaCl.

Figure S2. Essential components of diamond anvil Cell.

S4
 Figure S3. Experimental set up showing light source from excitation side , DAC and light
emission towards detection side
References.

[1] J.D. Barnett, S. Block, G.J. Piermarini, An Optical Fluorescence System for Quantitative Pressure
Measurement in the Diamond-Anvil Cell, Review of Scientific Instruments 44(1) (1973) 1-9.
[2] A. Jayaraman, The diamond anvil cell and high pressure research, Le Journal de Physique Colloques
45(C8) (1984) C8-355-C8-363.
[3] G. Piermarini, S. Block, The Diamond Anvil Pressure Cell, https://www.nist.gov/ (1972).

S5