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Global J. Environ. Sci. Manage., 1(3): 189-198, Summer 2015
INTRODUCTION
A paramount requirement of effective analytical
techniques and methods is that they are capable of
detecting desired concentrations (Seaton et al.,
2009). In the case of carbon nanotubes (CNTs), the
technique must be capable of identifying
concentrations at or below the 1µg/m3
recommended
occupational (airborne concentration) exposure limit
(NIOSH, 2013) required to prevent the array of
adverse health effects that are reasonably
attributable to exposure. The technique must also
differentiate nanoparticles of interest from naturally
occurring or anthropogenic nanoparticles that may
originate from dust storms, fires, vehicle exhausts,
indoor pollution, cigarette smoke, and consumer
Deposition of carbon nanotubes in commonly used sample filter media
1
*B.D. Smith; 2
S.B.H. Bach
1
Department of Civil Engineering, University of Texas at San Antonio, One UTSA Circle, San Antonio, Texas
78249, USA.
2
Department of Chemistry, University of Texas at San Antonio, One UTSA Circle, San Antonio,
Texas 78249, USA.
ABSTRACT: There is no single standard technique or methodology to characterize the size, structure, number, and
chemical composition of airborne carbon nanotubes. Existing analytical instruments and analytical techniques for
evaluating nanoparticle concentrations cannot simultaneously provide morphology, state of agglomeration, surface
area, mass, size distribution and chemical composition data critical to making occupational health assessments. This
research utilized scanning electron microscopy and thermogravimetric analysis to assess the morphology and mass of
carbon nanotubes collected using various commercial sample filters. It illustrated carbon nanotube agglomeration,
deposition and distribution in commonly used sample filter media. It also illustrated that a sufficient mass for carbon
nanotube analysis by thermogravimetric analysis is uncommon under most current research and production uses of
carbon nanotubes. Individual carbon nanotubes were found to readily agglomerate with diameters ranging from 1 – 63
µm. They were collected at the face of or within the filter. They were not evenly distributed across the face of the
filters.
Keywords: Agglomerates, Carbon nanotubes (CNTs), Filter deposition, Particulate sample filters, Scanning electron
microscopy (SEM), Thermogravimetric analysis (TGA)
Global J. Environ. Sci. Manage., 1(3):189-198, Summer 2015
ISSN 2383 - 3572
*Corresponding Author Email: bioenvengineer@aol.com
Tel.: +1 210-602-2784; Fax: +1 210-602-2784
Note. This manuscript was submitted on March 27, 2015;
approved on May 7, 2015; published online on June 1, 2015.
Discussion period open until October 1, 2015; discussion can
be performed online on the Website “Show article” section
for this article. This paper is part of the Global Journal of
Environmental Science and Management (GJESM).
Received 27 March 2015; revised 27 April 2015; accepted 7 May 2015; available online 1 June 2015
products (Lam et al., 2006; Buzea, et al., 2007; Sass
et al., 2008).
A nanotube is a nanometer-scale tube like structure
with different material composition (Bernholc et al.,
1997) that includes carbon nanotubes, inorganic
nanotubes that are often composed of metal oxides
(Ahmadi et al., 2011; Beheshtian et al., 2012; Lam et
al., 2004) and DNA nanotubes. The application of
nanotubes is in the midst of an explosive growth which
is due primarily to their unique chemical and physical
properties. These properties are said to promise new
inventions, new products and new contributions to
human knowledge (Remskar, 2004).
Carbon nanotubes (CNTs) are considered a new form
of pure carbon that can be visualized as rolled hexagonal
carbon networks that are capped by pentagonal carbon
rings (Terrones, 2003). The simplest nanotubes are a
single layer of carbon atoms arranged in a cylinder
(single-walledcarbon nanotubes). They may also
consist of multiple concentric tubes (multi-walled
carbonnanotubes) with diameters up to 20 nm and
Global J. Environ. Sci. Manage., 1(3): 189-198, Summer 2015B.D. Smith; S.B.H. Bach
lengthsgreater than1 mm(Fairbrother,2008). Theyhave
been produced with length-to-diameter rations of up to
132,000,000 to 1. CNTs are verystrong (about 100 times
stronger than steel), very light (one-sixth the weight of
steel), and 10 times more conductive than copper
(Ebbesen et al., 1996; Elcock, 2007). CNTs have been
reported as having a negative charge (Cheng, 2006) and
can be either metallic or a semiconductor (Che et al.,
2000). They also tend to self-agglomerate (Grzelczak et
al., 2010) and easily fragment (Froeshke et al., 2002).
Each ofthese properties must be taken into consideration
during analytical method and technique development
processes.
NIOSH’s Current Intelligence Bulletin, Occupational
Exposures to Carbon Nanotubes and Nanofibers
(NIOSH, 2013) recommends occupational exposures to
all types of CNT may be quantified by NIOSH Method
5040, Elemental Carbon (Diesel Particulate). It also
recommends using a mass-based airborne concentration
measurement for monitoring workplace exposures to all
types ofCNT, and using additional analytical techniques
to help to better characterize exposures to CNTs such as
transmission electron microscopy equipped with x-ray
energy dispersive spectroscopy. The NIOSHAnalytical
Method 5040 was developed in 1996 for use in the
evaluation of occupational exposures to diesel
particulates and may be prone to errors while attempting
to measure airborne carbon nanotubes.
NIOSH Method 5404,served as a reference point
for this research and the development of a method for
the collection, measurements and analysis of CNTs
because diesel particulates are typically less than 1
micron in diameter. Diesel particles are also generally
expected to be equally distributed across the face of
the sample (NIOSH, 1996).
Of importance in filter sampling is filter particle
loading. This depends on the structure and composition
of the fiber (packing density, fiber diameter, thickness),
operating conditions (filtration velocity, temperature),
and the density, particle size, and distribution
characteristics of the filtered aerosol (Contal et al.,
2005).The most important mechanisms causing particle
deposition in fibrous filters are diffusion, interception,
and inertial impaction (Lee and Byh,1982). Electrostatic
forces and gravitational settling may also contribute to
particle collection in afibrous medium.However,particle
collection is not uniformly distributed over the surface
and thickness ofa filter (Thomas et al., 2001). The effect
of particle loading is an initial increase of the filter
performance. In the beginning, particles deposit in the
depth of filters (Thomas et al., 2001) with surface layers
eventually becoming more loaded than depth layers.
However,aftersometime,adecreaseinparticlecollection
efficiencywillresultwithapointwhereparticlecollection
will no longer be efficient. Recognizing when this
transition is beginning to take place is an important part
of particle collection activities.
The filters used in this research were selected
because of their properties or because of their previous
applications in quantifying occupational exposures to
airborne contaminants: glass fiber (heat resistance, high
collection efficiency), mixed cellulose esters (asbestos,
metals), polycarbonate (cellulose insulation) and
polyvinyl chloride (particulate matter). While each filter
selected offers specific advantages with their use, their
use can include disadvantages that may include
potential overloading, static electricity, sampling
interferences and physical damage problems that must
be accounted for during use.
MATERIALS AND METHODS
Materials
Multi-walled carbon nanotubes were selected for
this research. These CNTs were produced by chemical
vapor deposition and purchased from Nanolab, Inc. of
Waltham, MA. They were reported to be 15 +/- 5 nm in
diameter, 1 – 5 µm in length, and > 95% purity. The
sample filters selected were Millipore glass fiber (Lot
#RODA25758), SKC mixed cellulose ester (Lot #8459-
7D9pask-190), SKC polycarbonate (Lot # 10271-
7dapask-278) and SKC polyvinyl chloride
(Lot # T91021) and a SKC incorporated 37 mm, 3-piece
air sampling cassettes were also used.
An Aldrich 250 ml two-neck round bottom flask
(part # Z516872) was selected to serve as the test
chamber.An air moving pump (Zefon product # Zefon
Z-lite) was used to draw air through the test chamber.
A Bjornax smoke pen was used to assess mixing within
the chamber. CNT and filter analyses was
accomplished with a JOEL JSM-6510 scanning electron
microscope (SEM), X-ray energy-dispersive X-ray
spectroscopy (EDS) and a Shimadzu TGA-50
thermogravimetric analyzer (TGA). Tygon tubing was
used to connect the sampling cassette to the pump.
Methods
To evaluateCNT mixing within the chamber, a smoke
pen (part # S221, manufactured by Bjornax) was used
to generate smoke particulates to be drawn into the
190
Global J. Environ. Sci. Manage., 1(3): 189-198, Summer 2015
test chamber and through the testchamber assembly.
This was accomplished without a filter in the assembly.
Prior to assessing CNT deposition in sample filters at
low and high volume air collection rates, and at short
and long collection times, baseline data on the carbon
nanotubes and sample filters had to be establish.
To establish the carbon nanotube baseline data, and
verifythe manufacturer’sdata, asampleoftheCNTs were
spread with a spatula across the face of mounting tape
for visualization under the SEM. Additionally, 5 mg of
CNT were also analyzed using TGA. To establish the
baselinedataforeachfilter,thefilterswerecutinto squares
with a sample of each visualized under SEM and
approximately 5 mg of the cuttings analyzed using TGA.
The test chamber assembly, consisting of the test
chamber, air sampling cassette, and air moving pump
(Zefon product # Zefon Z-lite) were assembled in the
order as indicated in Fig. 1, rinsed twice with acetone,
and allowed to air dry.
After allowing the test chamber to dry, the top cover
and inner ring of the 37 mm filter cassette were removed
from the cassette body (these were not used during
the experiment) and the experimental filter was then
inserted into the lower ring. The lower ring was then
attached to the test chamber using duct tape. The
assembly was configured so that there were no
obstructions between the air drawn into the test
chamber and the experimental filters. CNTs were then
introduced into the chamber as indicated in Table 1.
With the pump on, room air entered chamber where it
would mix with the test CNTs introduced into the
Air flow
Test chamber Test filters Air moving pump
Fig. 1: Test chamber assembly set up
2 lpm for 71 minutes
4 lpm for 71 minutes
2 lpm for 35 minutes
4 lpm for 35 minutes
CNTs introduced
into system
200 mg
200 mg
200 mg
200 mg
1st
batch CNT
Introduction
Start of test
Start of test
Start of test
Start of test
2nd
batch CNT
Introduction
23 minutes into test
23 minutes into test
11 minutes into test
11 minutes into test
3rd
batch CNT
Introduction
46 minutes into test
46 minutes into test
23 minutes into test
23 minutes into test
Table 1: Experimental filters tests
191
chamber, was drawn through the filter into the tubing,
and exhaust through the pump.
At the end of each run, the filter was removed from
the assembly. It was then cut into 6 mm squares for
analysis by SEM and EDS as indicated in Table 2.
The entire surface of the mounted squares was
viewed in a left to right, top to bottom pattern. The
visual and SEM observations of each filter square and
an estimate of the number of agglomerates (Froeschke
et al., 2003) and the sizes of each were recorded.
Photographs were also taken for illustrative purposes.
EDS scans were then taken of each sample filter.
RESULTS AND DISCUSSION
The smoke pen test resulted with what appeared to
be complete mixing in the text chamber. Upon assuring
the test chamber would enable the complete mixing of
the CNTs introduced within it, the focus then shifted
to the CNTs themselves. Figs. 2, 3 and 4 depict SEM
images of CNTs spread across the face of mounting
tape, the accumulation of several agglomerations
within a sample filter, and an indication of the large
numbers of CNTs within a single agglomerate.
The TGA traces of the CNTs and sample filters are
presented in Fig. 5.
The Y axis presents the sample mass (in mg) in the
crucibleand the X axis presents the temperature in 0
C
ranges of the TGA during the sample run. The colored
lines (traces) indicate the mass of the sample in crucible
at the start and end of the sample run for the CNTs and
test filters.
The SEM images of the CNT laden glass fiber (GF)
filter are presented in Figs. 6 and 7.
Fig. 6 is the GF filter upon removal from the test
chamber. It is readily observable that equal particulate
deposition has not taken place on the face of the filter.
As particles tend to deposit only by touching and
sticking to a capillarywall orother immobilized particles
(Elmoe et al., 2009), significant shading at the edges of
the filter is visible. The SEM (13000X magnification)
Global J. Environ. Sci. Manage., 1(3): 189-198, Summer 2015Deposition of carbon nanotubes
analysis of the CNT agglomerates within the filter is
presented in Fig. 7. The blue box in Fig. 6 indicates
where the sample square was taken from the filter.
The CNT agglomerates ranged from 1– 63 µm in
diameter. The GF filter was the preferred of all the
experimental filters to work with because its strength
made it easy to handle and cut and it did not stick to
other objects.
The SEM images of the CNT laden mixed cellulose
ester (MCE) filter are presented in Figs. 8 and 9.
Fig. 8 is the MCE filter upon removal from the test
chamber. An uneven particulate deposition is
observable across the face of the filter. Shading at the
edges of the filter is visible. The blue box in Fig. 8
indicates where the sample square was taken from the
filter. The SEM (2700X magnification) analysis is of
the CNT agglomerates (Fig. 9) within the bed of the
filter. The CNT agglomerates ranged from 1– 63 µm in
diameter. The MCE filter was moderately difficult to
work with as it had a tendency to stick to most object
used during its handling.
The SEM images of the CNT laden polycarbonate
(PC) filter are presented in Figs. 10 and 11.
Fig. 11 is the PC filter upon removal from the test
chamber. Almost no particulate deposition is visible
across the face of the filter. Shading at the edges of the
filter is visible. The blue box in Fig. 6 indicates where
the sample square was taken from the filter. The SEM
(4000X magnification)analysisof the CNT agglomerates
on the filter face is presented in Fig. 11. The CNT
agglomerates ranged from 1– 63 µm in diameter. The
polycarbonate filter was enormously difficult to handle
because it had a tendency to “roll-up” and stick to
most objects used during its handling.
The SEM images ofthe CNT laden polyvinyl chloride
(PVC) filter are presented in Figs. 12 and 13.
Fig. 12 is the PVC filter upon removal from the test
chamber. An uneven particulate deposition is
observable across the face of the filter; with more
caking at the face than the other experimental filters.
Light to moderate shading at the edges of the filter is
visible. The blue box in Fig. 6 indicates where the
Filter
Glass fiber - Blank
Glass fiber- Single filter
Mixed cellulose ester - Blank
Mixed cellulose ester - Single filter
Polycarbonate - Blank
Polycarbonate - Single filter
Polyvinyl chloride - Blank
Polyvinyl chloride - Single filter
Manufacturer and lot number
MilliporeLot # RODA25758
MilliporeLot # RODA25758
SKCLot # 8459-7D9PASK-190
SKCLot # 8459-7D9PASK-190
SKCLot #10271-7DAPASK-278
SKCLot #10271-7DAPASK-278
SKCLot # T91021
SKCLot # T91021
Diameter
37 mm
37 mm
25 mm
25 mm
25 mm
25 mm
37 mm
37 mm
SEM filter squares
4
32
4
16
4
16
4
32
Table 2: Filters analyzed by scanning electron microscopy andenergy-dispersive X-rayspectroscopy
Fig. 2: CNT agglomerates on carbon
adhesive tabs
Fig. 3: CNT agglomerates on the face of
a glass fiber filter
Fig. 4: Tightly agglomerated CNTs
192
Global J. Environ. Sci. Manage., 1(3): 189-198, Summer 2015
Fig. 5: CNT sample and test filters TGA traces
Fig. 6: GF filter upon removal from test chamber Fig.7: SEM analysis of particles within depth of GF filter
Fig. 8: MCE filter upon removal from test chamber Fig. 9: SEM analysis of particles within depth of MCE filter
Tempetature 0
C
Mass(mg)
193
Global J. Environ. Sci. Manage., 1(3): 189-198, Summer 2015B.D. Smith; S.B.H. Bach
sample square was taken from the filter. The SEM
(1300X magnification) analysis of the CNT agglomerates
within the filter is presented in Fig. 13. The CNT
agglomerates ranged from 1– 63 µm in diameter. The
filter tendency to stick to objects make it difficult to
work with.
Figs. 14, 15, 16 and17 present the EDS scans of the
CNT laden filters.
The filter spectra presented in Figs. 14, 15, 16 and 17
were collected from the highest, a medium and the lowest
areas of deposits on the test filters. As the SEM and
EDS operate in tandem, the spectra were obtained after
the SEM analysis. EDS is capable of providing spectra
data for any element with an atomic number above six
(carbon). Identified elements were then classified
according to their probable source and are listed
accordingly. In the obtained spectra, there was no
observation of elements that did not originate from the
CNT synthesis, filter manufacturing, sample collection
apparatus, or analytical support materials in any of the
samples.
The smoke pen particles average about 1micron in
diameter (Van Zant, 2000). However, the large quantity
generated by the pen enabled the smoke stream to be
seen with the unaided eye. Because of this, it was
possible to visualize what appeared to be complete
mixing of the particles in the test chamber.
The SEM, EDS and TGA of the stock CNT
validated the manufacturer’s listed properties in terms
of the physical properties and the percent CNT purity.
The observed impurities that were listed at 5% by the
manufacturer were believed to be amorphous carbon
and trace metals since CNT batches typically contain
other carbonaceous and transition metal particles
(Oswald et al., 2005). The EDS scans ofthe CNT laden
samples seemed to verify this.
TheSEMvisualizationofCNTagglomerationinFigs.
2, 3 and 4 highlight the literature references that the
normaltendencyofCNTs is to agglomerate(Curtzwiler,
2008). It also answers the question as to why, unlike
asbestos, determining a number of CNTs per a given air
volume would prove nothing more than an impossible
Fig. 12: PVC filter upon removal from test chamber Fig. 13: SEM analysis of particles within depth of PVC filter
Fig. 10: PC filter upon removal from test chamber Fig. 11: SEM analysis of particles on the surface of PC filter
194
Global J. Environ. Sci. Manage., 1(3): 189-198, Summer 2015
Manufacturing catalysts:
iron, molybdenum
Support materials:
aluminum, manganese,
silica
Filter: carbon, nitrogen,
oxygen
SEM specimen mounts and
mounting tape: aluminum,
carbon
A
B
C
B
C
A
Manufacturing catalysts:
iron, molybdenum
Support materials:
aluminum, manganese,
silica
Filter: carbon, oxygen,
sodium, silicon, barium,
fluorine, potassium, zinc,
magnesium
SEM specimen mounts and
mounting tape: aluminum,
carbon
A
B
C
AA
A
C
B
Fig. 14: Glass fiber filter spectra
Fig. 15: Mixed cellulose ester filter spectra
Manufacturing catalysts:
iron, molybdenum
Support materials:
aluminum, manganese,
silica
Filter: carbon, oxygen,
sodium, silicon, barium,
fluorine, potassium, zinc,
magnesium
SEM specimen mounts and
mounting tape: aluminum,
carbon
Manufacturing catalysts:
iron, molybdenum
Support materials: aluminum,
manganese, silica
Filter: carbon, nitrogen,
oxygen
SEM specimen mounts and
mounting tape: aluminum,
carbon
195
Full scale counts: 7790 Base(3)-pt1 Cursor: 4.500 keV
105 Counts
Full scale counts: 46791 Base(2)-pt1 Cursor: 4.500 keV
121 Counts
Full scale counts: 49743 Base(4)-pt1 Cursor: 4.500 keV
141 Counts
Full scale counts: 339 Base(10)-pt1 Cursor: 4.500 keV
0 Counts
Full scale counts: 2643 Base(9)-pt2 Cursor: 4.500 keV
4 Counts
Full scale counts: 3614 Base(8)-pt2 Cursor: 4.500 keV
3 Counts
Global J. Environ. Sci. Manage., 1(3): 189-198, Summer 2015Deposition of carbon nanotubes
Manufacturing catalysts:
iron, molybdenum
Support materials:
aluminum, manganese,
silica
Filter: carbon
SEM specimen mounts and
mounting tape: aluminum,
carbon
A
B
C
A
B
C
Fig. 16: Polycarbonate filter spectra
analytical data point to obtain because, as seen in Fig. 4,
the CNTs areso tightly agglomerated thatit is impossible
to tell where one CNT stops and the other starts.
A challenge related to utilizing the TGA for the
analysis of carbon nanotube exposed air sample filters
is the 10 mg mass limit for samples placed into the TGA
sample crucible. Because of the mass of the filters (GFF
= 53.7 - 54.5 mg, MCE= 20 - 21.7 mg, PC = 3.4-4.8 mg,
and PVC = 15.6 - 16.1 mg), all (with the exception of the
polycarbonate filter) must be cut prior to placement
into the TGA sample crucible. These cuts could require
8 – 20 samples per filter and may cause significant
carbon nanotube sample loss resulting from the
handling and cutting of the filter.
With regard to theTGAshown datain Fig. 5, thetraces
indicates that CNT mass loss beginsat approximately420
0
C and concludesatapproximately580 0
C. Theglass fiber
filter,shows no mass loss through 10000
C, the upper limit
oftheTGA.Theremainingthreesamples,themixedcellulose
ester filter, the polycarbonate filter, and the polyvinyl
chloride filter, illustrate mass losses that either begin or
conclude within the CNT loss ranges, thereby making it
impossible to define what portion of sample in those
temperature ranges were CNTs and what portion of the
sample in those ranges were the particular filter. Because
of this, those three filters were not suitable for CNT
collectionactivities. The data is summarized in Table3.
Increasing the flow rate or sample time had almost
no bearing on the collection or deposition of CNTs
using the glass fiber filters. Likewise, no difference was
observed with the other three filters under the same
parameters. Decreasing the flow rate or sample time
decreased the volume of CNTs collected by the glass
fiber filters and again made no difference whatsoever
with the other three filters.
As indicated previously, EDS can be used to identify
non-carbon sample constituents and may help
differentiate CNTs from other possible elemental
carbon containing particles such as diesel soot or
carbon black or contaminants. Using the EDS point
and shoot mechanism, the elements listed in Figs. 14,
15, 16 and 17 are those anticipated to be found in each
of the CNT exposed filters.
Manufacturing catalysts:
iron, molybdenum
Support materials:
aluminum, manganese,
silica
Filter: carbon
SEM specimen mounts
and mounting tape:
aluminum, carbon
196
Full scale counts: 2314 Base(8)-pt1 Cursor: 4.500 keV
0 Counts
Full scale counts: 3479 Base(7)-pt1 Cursor: 4.500 keV
0 Counts
Full scale counts: 2936 Base(1)-pt1 Cursor: 4.500 keV
0 Counts
Global J. Environ. Sci. Manage., 1(3): 189-198, Summer 2015
CONCLUSION
This research project illustrated that CNTs are not
evenly distributed across the face of air sampling filters
during sample collection events. It bears mentioning
that, since CNT disposition across the sample filter is
not uniform, the filter portion selected for analysis
when following the NIOSH analytical method may
significantly underestimate or overstate the true sample
concentration. Consequently, analysis of the entire
sample filter will generally be required to obtain an
accurate CNT mass. It is for these reasons that the
deposition of CNT on commonly used sample filter
media is important data.
A second point that needs to be made regarding
airborne carbon nanotubes is given their current use,
it is unlikely that in most cases a sufficient mass of
CNTs for thermogravimetric analysis. Therefore, it
remains important that the analysis of airborne carbon
nanotubes be accomplished by two methods in tandem,
one that estimates the mass of the CNTs and one that
enables the visualization of the number of particles,
their shapes, sizes and states of agglomeration.
olycarbonate filter spectra
Manufacturing catalysts:
iron, molybdenum
Support materials:
aluminum, manganese,
silica
Filter: carbon
SEM specimen mounts and
mounting tape: aluminum,
carbon
A
B
A
C
C
B
Fig. 17: Polyvinyl chloride filter spectra
Manufacturing catalysts:
iron, molybdenum
Support materials:
aluminum, manganese,
silica
Filter: carbon
SEM specimen mounts
and mounting tape:
aluminum, carbon
197
Full scale counts: 2605 Base(15)-pt1 Cursor: 4.500 keV
21 Counts
Full scale counts: 7770 Base(14)-pt1 Cursor: 4.500 keV
22 Counts
Full scale counts: 2742 Base(10)-pt1 Cursor: 4.500 keV
31 Counts
Sample Beginning of sample
degradation (0
C)
End of sample
degradation (0
C)
Maximum TGA
temperature setting (0
C)
CNT 420 580 1000
GF n/a n/a 1000
MCE 100 500 1000
PC 380 550 1000
PVC 200 550 1000
Table 3: Thermogravimetricanalysis of CNTs and sample filters
Global J. Environ. Sci. Manage., 1(3): 189-198, Summer 2015B.D. Smith; S.B.H. Bach
CONFLICTOFINTEREST
The authors declare that there is no conflict
ofinterests regarding the publication of this manuscript.
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AUTHOR (S) BIOSKETCHES
Smith, B.D., Ph.D. Candidate, Department of Civil Engineering, University of Texas at San Antonio, One UTSA Circle, San Antonio, Texas
78249, USA. Email: bioenvengineer@aol.com
Bach, S.G.H., Ph.D., Associate Professor; Department of Chemistry, University of Texas at San Antonio, One UTSA Circle, San Antonio,
Texas 78249, USA. Email: stephan.bach@utsa.edu
How to cite this article: (Harvard style)
Smith, B.D.; Bach, S.B.H., (2015). Deposition of carbon nanotubes in commonly used sample filter media, Global J. Environ. Sci.
Manage., 1(2): 189-198.
198

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Deposition of carbon nanotubes in commonly used sample filter media

  • 1. Global J. Environ. Sci. Manage., 1(3): 189-198, Summer 2015 INTRODUCTION A paramount requirement of effective analytical techniques and methods is that they are capable of detecting desired concentrations (Seaton et al., 2009). In the case of carbon nanotubes (CNTs), the technique must be capable of identifying concentrations at or below the 1µg/m3 recommended occupational (airborne concentration) exposure limit (NIOSH, 2013) required to prevent the array of adverse health effects that are reasonably attributable to exposure. The technique must also differentiate nanoparticles of interest from naturally occurring or anthropogenic nanoparticles that may originate from dust storms, fires, vehicle exhausts, indoor pollution, cigarette smoke, and consumer Deposition of carbon nanotubes in commonly used sample filter media 1 *B.D. Smith; 2 S.B.H. Bach 1 Department of Civil Engineering, University of Texas at San Antonio, One UTSA Circle, San Antonio, Texas 78249, USA. 2 Department of Chemistry, University of Texas at San Antonio, One UTSA Circle, San Antonio, Texas 78249, USA. ABSTRACT: There is no single standard technique or methodology to characterize the size, structure, number, and chemical composition of airborne carbon nanotubes. Existing analytical instruments and analytical techniques for evaluating nanoparticle concentrations cannot simultaneously provide morphology, state of agglomeration, surface area, mass, size distribution and chemical composition data critical to making occupational health assessments. This research utilized scanning electron microscopy and thermogravimetric analysis to assess the morphology and mass of carbon nanotubes collected using various commercial sample filters. It illustrated carbon nanotube agglomeration, deposition and distribution in commonly used sample filter media. It also illustrated that a sufficient mass for carbon nanotube analysis by thermogravimetric analysis is uncommon under most current research and production uses of carbon nanotubes. Individual carbon nanotubes were found to readily agglomerate with diameters ranging from 1 – 63 µm. They were collected at the face of or within the filter. They were not evenly distributed across the face of the filters. Keywords: Agglomerates, Carbon nanotubes (CNTs), Filter deposition, Particulate sample filters, Scanning electron microscopy (SEM), Thermogravimetric analysis (TGA) Global J. Environ. Sci. Manage., 1(3):189-198, Summer 2015 ISSN 2383 - 3572 *Corresponding Author Email: bioenvengineer@aol.com Tel.: +1 210-602-2784; Fax: +1 210-602-2784 Note. This manuscript was submitted on March 27, 2015; approved on May 7, 2015; published online on June 1, 2015. Discussion period open until October 1, 2015; discussion can be performed online on the Website “Show article” section for this article. This paper is part of the Global Journal of Environmental Science and Management (GJESM). Received 27 March 2015; revised 27 April 2015; accepted 7 May 2015; available online 1 June 2015 products (Lam et al., 2006; Buzea, et al., 2007; Sass et al., 2008). A nanotube is a nanometer-scale tube like structure with different material composition (Bernholc et al., 1997) that includes carbon nanotubes, inorganic nanotubes that are often composed of metal oxides (Ahmadi et al., 2011; Beheshtian et al., 2012; Lam et al., 2004) and DNA nanotubes. The application of nanotubes is in the midst of an explosive growth which is due primarily to their unique chemical and physical properties. These properties are said to promise new inventions, new products and new contributions to human knowledge (Remskar, 2004). Carbon nanotubes (CNTs) are considered a new form of pure carbon that can be visualized as rolled hexagonal carbon networks that are capped by pentagonal carbon rings (Terrones, 2003). The simplest nanotubes are a single layer of carbon atoms arranged in a cylinder (single-walledcarbon nanotubes). They may also consist of multiple concentric tubes (multi-walled carbonnanotubes) with diameters up to 20 nm and
  • 2. Global J. Environ. Sci. Manage., 1(3): 189-198, Summer 2015B.D. Smith; S.B.H. Bach lengthsgreater than1 mm(Fairbrother,2008). Theyhave been produced with length-to-diameter rations of up to 132,000,000 to 1. CNTs are verystrong (about 100 times stronger than steel), very light (one-sixth the weight of steel), and 10 times more conductive than copper (Ebbesen et al., 1996; Elcock, 2007). CNTs have been reported as having a negative charge (Cheng, 2006) and can be either metallic or a semiconductor (Che et al., 2000). They also tend to self-agglomerate (Grzelczak et al., 2010) and easily fragment (Froeshke et al., 2002). Each ofthese properties must be taken into consideration during analytical method and technique development processes. NIOSH’s Current Intelligence Bulletin, Occupational Exposures to Carbon Nanotubes and Nanofibers (NIOSH, 2013) recommends occupational exposures to all types of CNT may be quantified by NIOSH Method 5040, Elemental Carbon (Diesel Particulate). It also recommends using a mass-based airborne concentration measurement for monitoring workplace exposures to all types ofCNT, and using additional analytical techniques to help to better characterize exposures to CNTs such as transmission electron microscopy equipped with x-ray energy dispersive spectroscopy. The NIOSHAnalytical Method 5040 was developed in 1996 for use in the evaluation of occupational exposures to diesel particulates and may be prone to errors while attempting to measure airborne carbon nanotubes. NIOSH Method 5404,served as a reference point for this research and the development of a method for the collection, measurements and analysis of CNTs because diesel particulates are typically less than 1 micron in diameter. Diesel particles are also generally expected to be equally distributed across the face of the sample (NIOSH, 1996). Of importance in filter sampling is filter particle loading. This depends on the structure and composition of the fiber (packing density, fiber diameter, thickness), operating conditions (filtration velocity, temperature), and the density, particle size, and distribution characteristics of the filtered aerosol (Contal et al., 2005).The most important mechanisms causing particle deposition in fibrous filters are diffusion, interception, and inertial impaction (Lee and Byh,1982). Electrostatic forces and gravitational settling may also contribute to particle collection in afibrous medium.However,particle collection is not uniformly distributed over the surface and thickness ofa filter (Thomas et al., 2001). The effect of particle loading is an initial increase of the filter performance. In the beginning, particles deposit in the depth of filters (Thomas et al., 2001) with surface layers eventually becoming more loaded than depth layers. However,aftersometime,adecreaseinparticlecollection efficiencywillresultwithapointwhereparticlecollection will no longer be efficient. Recognizing when this transition is beginning to take place is an important part of particle collection activities. The filters used in this research were selected because of their properties or because of their previous applications in quantifying occupational exposures to airborne contaminants: glass fiber (heat resistance, high collection efficiency), mixed cellulose esters (asbestos, metals), polycarbonate (cellulose insulation) and polyvinyl chloride (particulate matter). While each filter selected offers specific advantages with their use, their use can include disadvantages that may include potential overloading, static electricity, sampling interferences and physical damage problems that must be accounted for during use. MATERIALS AND METHODS Materials Multi-walled carbon nanotubes were selected for this research. These CNTs were produced by chemical vapor deposition and purchased from Nanolab, Inc. of Waltham, MA. They were reported to be 15 +/- 5 nm in diameter, 1 – 5 µm in length, and > 95% purity. The sample filters selected were Millipore glass fiber (Lot #RODA25758), SKC mixed cellulose ester (Lot #8459- 7D9pask-190), SKC polycarbonate (Lot # 10271- 7dapask-278) and SKC polyvinyl chloride (Lot # T91021) and a SKC incorporated 37 mm, 3-piece air sampling cassettes were also used. An Aldrich 250 ml two-neck round bottom flask (part # Z516872) was selected to serve as the test chamber.An air moving pump (Zefon product # Zefon Z-lite) was used to draw air through the test chamber. A Bjornax smoke pen was used to assess mixing within the chamber. CNT and filter analyses was accomplished with a JOEL JSM-6510 scanning electron microscope (SEM), X-ray energy-dispersive X-ray spectroscopy (EDS) and a Shimadzu TGA-50 thermogravimetric analyzer (TGA). Tygon tubing was used to connect the sampling cassette to the pump. Methods To evaluateCNT mixing within the chamber, a smoke pen (part # S221, manufactured by Bjornax) was used to generate smoke particulates to be drawn into the 190
  • 3. Global J. Environ. Sci. Manage., 1(3): 189-198, Summer 2015 test chamber and through the testchamber assembly. This was accomplished without a filter in the assembly. Prior to assessing CNT deposition in sample filters at low and high volume air collection rates, and at short and long collection times, baseline data on the carbon nanotubes and sample filters had to be establish. To establish the carbon nanotube baseline data, and verifythe manufacturer’sdata, asampleoftheCNTs were spread with a spatula across the face of mounting tape for visualization under the SEM. Additionally, 5 mg of CNT were also analyzed using TGA. To establish the baselinedataforeachfilter,thefilterswerecutinto squares with a sample of each visualized under SEM and approximately 5 mg of the cuttings analyzed using TGA. The test chamber assembly, consisting of the test chamber, air sampling cassette, and air moving pump (Zefon product # Zefon Z-lite) were assembled in the order as indicated in Fig. 1, rinsed twice with acetone, and allowed to air dry. After allowing the test chamber to dry, the top cover and inner ring of the 37 mm filter cassette were removed from the cassette body (these were not used during the experiment) and the experimental filter was then inserted into the lower ring. The lower ring was then attached to the test chamber using duct tape. The assembly was configured so that there were no obstructions between the air drawn into the test chamber and the experimental filters. CNTs were then introduced into the chamber as indicated in Table 1. With the pump on, room air entered chamber where it would mix with the test CNTs introduced into the Air flow Test chamber Test filters Air moving pump Fig. 1: Test chamber assembly set up 2 lpm for 71 minutes 4 lpm for 71 minutes 2 lpm for 35 minutes 4 lpm for 35 minutes CNTs introduced into system 200 mg 200 mg 200 mg 200 mg 1st batch CNT Introduction Start of test Start of test Start of test Start of test 2nd batch CNT Introduction 23 minutes into test 23 minutes into test 11 minutes into test 11 minutes into test 3rd batch CNT Introduction 46 minutes into test 46 minutes into test 23 minutes into test 23 minutes into test Table 1: Experimental filters tests 191 chamber, was drawn through the filter into the tubing, and exhaust through the pump. At the end of each run, the filter was removed from the assembly. It was then cut into 6 mm squares for analysis by SEM and EDS as indicated in Table 2. The entire surface of the mounted squares was viewed in a left to right, top to bottom pattern. The visual and SEM observations of each filter square and an estimate of the number of agglomerates (Froeschke et al., 2003) and the sizes of each were recorded. Photographs were also taken for illustrative purposes. EDS scans were then taken of each sample filter. RESULTS AND DISCUSSION The smoke pen test resulted with what appeared to be complete mixing in the text chamber. Upon assuring the test chamber would enable the complete mixing of the CNTs introduced within it, the focus then shifted to the CNTs themselves. Figs. 2, 3 and 4 depict SEM images of CNTs spread across the face of mounting tape, the accumulation of several agglomerations within a sample filter, and an indication of the large numbers of CNTs within a single agglomerate. The TGA traces of the CNTs and sample filters are presented in Fig. 5. The Y axis presents the sample mass (in mg) in the crucibleand the X axis presents the temperature in 0 C ranges of the TGA during the sample run. The colored lines (traces) indicate the mass of the sample in crucible at the start and end of the sample run for the CNTs and test filters. The SEM images of the CNT laden glass fiber (GF) filter are presented in Figs. 6 and 7. Fig. 6 is the GF filter upon removal from the test chamber. It is readily observable that equal particulate deposition has not taken place on the face of the filter. As particles tend to deposit only by touching and sticking to a capillarywall orother immobilized particles (Elmoe et al., 2009), significant shading at the edges of the filter is visible. The SEM (13000X magnification)
  • 4. Global J. Environ. Sci. Manage., 1(3): 189-198, Summer 2015Deposition of carbon nanotubes analysis of the CNT agglomerates within the filter is presented in Fig. 7. The blue box in Fig. 6 indicates where the sample square was taken from the filter. The CNT agglomerates ranged from 1– 63 µm in diameter. The GF filter was the preferred of all the experimental filters to work with because its strength made it easy to handle and cut and it did not stick to other objects. The SEM images of the CNT laden mixed cellulose ester (MCE) filter are presented in Figs. 8 and 9. Fig. 8 is the MCE filter upon removal from the test chamber. An uneven particulate deposition is observable across the face of the filter. Shading at the edges of the filter is visible. The blue box in Fig. 8 indicates where the sample square was taken from the filter. The SEM (2700X magnification) analysis is of the CNT agglomerates (Fig. 9) within the bed of the filter. The CNT agglomerates ranged from 1– 63 µm in diameter. The MCE filter was moderately difficult to work with as it had a tendency to stick to most object used during its handling. The SEM images of the CNT laden polycarbonate (PC) filter are presented in Figs. 10 and 11. Fig. 11 is the PC filter upon removal from the test chamber. Almost no particulate deposition is visible across the face of the filter. Shading at the edges of the filter is visible. The blue box in Fig. 6 indicates where the sample square was taken from the filter. The SEM (4000X magnification)analysisof the CNT agglomerates on the filter face is presented in Fig. 11. The CNT agglomerates ranged from 1– 63 µm in diameter. The polycarbonate filter was enormously difficult to handle because it had a tendency to “roll-up” and stick to most objects used during its handling. The SEM images ofthe CNT laden polyvinyl chloride (PVC) filter are presented in Figs. 12 and 13. Fig. 12 is the PVC filter upon removal from the test chamber. An uneven particulate deposition is observable across the face of the filter; with more caking at the face than the other experimental filters. Light to moderate shading at the edges of the filter is visible. The blue box in Fig. 6 indicates where the Filter Glass fiber - Blank Glass fiber- Single filter Mixed cellulose ester - Blank Mixed cellulose ester - Single filter Polycarbonate - Blank Polycarbonate - Single filter Polyvinyl chloride - Blank Polyvinyl chloride - Single filter Manufacturer and lot number MilliporeLot # RODA25758 MilliporeLot # RODA25758 SKCLot # 8459-7D9PASK-190 SKCLot # 8459-7D9PASK-190 SKCLot #10271-7DAPASK-278 SKCLot #10271-7DAPASK-278 SKCLot # T91021 SKCLot # T91021 Diameter 37 mm 37 mm 25 mm 25 mm 25 mm 25 mm 37 mm 37 mm SEM filter squares 4 32 4 16 4 16 4 32 Table 2: Filters analyzed by scanning electron microscopy andenergy-dispersive X-rayspectroscopy Fig. 2: CNT agglomerates on carbon adhesive tabs Fig. 3: CNT agglomerates on the face of a glass fiber filter Fig. 4: Tightly agglomerated CNTs 192
  • 5. Global J. Environ. Sci. Manage., 1(3): 189-198, Summer 2015 Fig. 5: CNT sample and test filters TGA traces Fig. 6: GF filter upon removal from test chamber Fig.7: SEM analysis of particles within depth of GF filter Fig. 8: MCE filter upon removal from test chamber Fig. 9: SEM analysis of particles within depth of MCE filter Tempetature 0 C Mass(mg) 193
  • 6. Global J. Environ. Sci. Manage., 1(3): 189-198, Summer 2015B.D. Smith; S.B.H. Bach sample square was taken from the filter. The SEM (1300X magnification) analysis of the CNT agglomerates within the filter is presented in Fig. 13. The CNT agglomerates ranged from 1– 63 µm in diameter. The filter tendency to stick to objects make it difficult to work with. Figs. 14, 15, 16 and17 present the EDS scans of the CNT laden filters. The filter spectra presented in Figs. 14, 15, 16 and 17 were collected from the highest, a medium and the lowest areas of deposits on the test filters. As the SEM and EDS operate in tandem, the spectra were obtained after the SEM analysis. EDS is capable of providing spectra data for any element with an atomic number above six (carbon). Identified elements were then classified according to their probable source and are listed accordingly. In the obtained spectra, there was no observation of elements that did not originate from the CNT synthesis, filter manufacturing, sample collection apparatus, or analytical support materials in any of the samples. The smoke pen particles average about 1micron in diameter (Van Zant, 2000). However, the large quantity generated by the pen enabled the smoke stream to be seen with the unaided eye. Because of this, it was possible to visualize what appeared to be complete mixing of the particles in the test chamber. The SEM, EDS and TGA of the stock CNT validated the manufacturer’s listed properties in terms of the physical properties and the percent CNT purity. The observed impurities that were listed at 5% by the manufacturer were believed to be amorphous carbon and trace metals since CNT batches typically contain other carbonaceous and transition metal particles (Oswald et al., 2005). The EDS scans ofthe CNT laden samples seemed to verify this. TheSEMvisualizationofCNTagglomerationinFigs. 2, 3 and 4 highlight the literature references that the normaltendencyofCNTs is to agglomerate(Curtzwiler, 2008). It also answers the question as to why, unlike asbestos, determining a number of CNTs per a given air volume would prove nothing more than an impossible Fig. 12: PVC filter upon removal from test chamber Fig. 13: SEM analysis of particles within depth of PVC filter Fig. 10: PC filter upon removal from test chamber Fig. 11: SEM analysis of particles on the surface of PC filter 194
  • 7. Global J. Environ. Sci. Manage., 1(3): 189-198, Summer 2015 Manufacturing catalysts: iron, molybdenum Support materials: aluminum, manganese, silica Filter: carbon, nitrogen, oxygen SEM specimen mounts and mounting tape: aluminum, carbon A B C B C A Manufacturing catalysts: iron, molybdenum Support materials: aluminum, manganese, silica Filter: carbon, oxygen, sodium, silicon, barium, fluorine, potassium, zinc, magnesium SEM specimen mounts and mounting tape: aluminum, carbon A B C AA A C B Fig. 14: Glass fiber filter spectra Fig. 15: Mixed cellulose ester filter spectra Manufacturing catalysts: iron, molybdenum Support materials: aluminum, manganese, silica Filter: carbon, oxygen, sodium, silicon, barium, fluorine, potassium, zinc, magnesium SEM specimen mounts and mounting tape: aluminum, carbon Manufacturing catalysts: iron, molybdenum Support materials: aluminum, manganese, silica Filter: carbon, nitrogen, oxygen SEM specimen mounts and mounting tape: aluminum, carbon 195 Full scale counts: 7790 Base(3)-pt1 Cursor: 4.500 keV 105 Counts Full scale counts: 46791 Base(2)-pt1 Cursor: 4.500 keV 121 Counts Full scale counts: 49743 Base(4)-pt1 Cursor: 4.500 keV 141 Counts Full scale counts: 339 Base(10)-pt1 Cursor: 4.500 keV 0 Counts Full scale counts: 2643 Base(9)-pt2 Cursor: 4.500 keV 4 Counts Full scale counts: 3614 Base(8)-pt2 Cursor: 4.500 keV 3 Counts
  • 8. Global J. Environ. Sci. Manage., 1(3): 189-198, Summer 2015Deposition of carbon nanotubes Manufacturing catalysts: iron, molybdenum Support materials: aluminum, manganese, silica Filter: carbon SEM specimen mounts and mounting tape: aluminum, carbon A B C A B C Fig. 16: Polycarbonate filter spectra analytical data point to obtain because, as seen in Fig. 4, the CNTs areso tightly agglomerated thatit is impossible to tell where one CNT stops and the other starts. A challenge related to utilizing the TGA for the analysis of carbon nanotube exposed air sample filters is the 10 mg mass limit for samples placed into the TGA sample crucible. Because of the mass of the filters (GFF = 53.7 - 54.5 mg, MCE= 20 - 21.7 mg, PC = 3.4-4.8 mg, and PVC = 15.6 - 16.1 mg), all (with the exception of the polycarbonate filter) must be cut prior to placement into the TGA sample crucible. These cuts could require 8 – 20 samples per filter and may cause significant carbon nanotube sample loss resulting from the handling and cutting of the filter. With regard to theTGAshown datain Fig. 5, thetraces indicates that CNT mass loss beginsat approximately420 0 C and concludesatapproximately580 0 C. Theglass fiber filter,shows no mass loss through 10000 C, the upper limit oftheTGA.Theremainingthreesamples,themixedcellulose ester filter, the polycarbonate filter, and the polyvinyl chloride filter, illustrate mass losses that either begin or conclude within the CNT loss ranges, thereby making it impossible to define what portion of sample in those temperature ranges were CNTs and what portion of the sample in those ranges were the particular filter. Because of this, those three filters were not suitable for CNT collectionactivities. The data is summarized in Table3. Increasing the flow rate or sample time had almost no bearing on the collection or deposition of CNTs using the glass fiber filters. Likewise, no difference was observed with the other three filters under the same parameters. Decreasing the flow rate or sample time decreased the volume of CNTs collected by the glass fiber filters and again made no difference whatsoever with the other three filters. As indicated previously, EDS can be used to identify non-carbon sample constituents and may help differentiate CNTs from other possible elemental carbon containing particles such as diesel soot or carbon black or contaminants. Using the EDS point and shoot mechanism, the elements listed in Figs. 14, 15, 16 and 17 are those anticipated to be found in each of the CNT exposed filters. Manufacturing catalysts: iron, molybdenum Support materials: aluminum, manganese, silica Filter: carbon SEM specimen mounts and mounting tape: aluminum, carbon 196 Full scale counts: 2314 Base(8)-pt1 Cursor: 4.500 keV 0 Counts Full scale counts: 3479 Base(7)-pt1 Cursor: 4.500 keV 0 Counts Full scale counts: 2936 Base(1)-pt1 Cursor: 4.500 keV 0 Counts
  • 9. Global J. Environ. Sci. Manage., 1(3): 189-198, Summer 2015 CONCLUSION This research project illustrated that CNTs are not evenly distributed across the face of air sampling filters during sample collection events. It bears mentioning that, since CNT disposition across the sample filter is not uniform, the filter portion selected for analysis when following the NIOSH analytical method may significantly underestimate or overstate the true sample concentration. Consequently, analysis of the entire sample filter will generally be required to obtain an accurate CNT mass. It is for these reasons that the deposition of CNT on commonly used sample filter media is important data. A second point that needs to be made regarding airborne carbon nanotubes is given their current use, it is unlikely that in most cases a sufficient mass of CNTs for thermogravimetric analysis. Therefore, it remains important that the analysis of airborne carbon nanotubes be accomplished by two methods in tandem, one that estimates the mass of the CNTs and one that enables the visualization of the number of particles, their shapes, sizes and states of agglomeration. olycarbonate filter spectra Manufacturing catalysts: iron, molybdenum Support materials: aluminum, manganese, silica Filter: carbon SEM specimen mounts and mounting tape: aluminum, carbon A B A C C B Fig. 17: Polyvinyl chloride filter spectra Manufacturing catalysts: iron, molybdenum Support materials: aluminum, manganese, silica Filter: carbon SEM specimen mounts and mounting tape: aluminum, carbon 197 Full scale counts: 2605 Base(15)-pt1 Cursor: 4.500 keV 21 Counts Full scale counts: 7770 Base(14)-pt1 Cursor: 4.500 keV 22 Counts Full scale counts: 2742 Base(10)-pt1 Cursor: 4.500 keV 31 Counts Sample Beginning of sample degradation (0 C) End of sample degradation (0 C) Maximum TGA temperature setting (0 C) CNT 420 580 1000 GF n/a n/a 1000 MCE 100 500 1000 PC 380 550 1000 PVC 200 550 1000 Table 3: Thermogravimetricanalysis of CNTs and sample filters
  • 10. Global J. Environ. Sci. Manage., 1(3): 189-198, Summer 2015B.D. Smith; S.B.H. Bach CONFLICTOFINTEREST The authors declare that there is no conflict ofinterests regarding the publication of this manuscript. REFERENCES Ahmadi, A.; Beheshtian, J.; Hadipour, N., (2011). Interaction of NH3 with aluminum nitride nanotube: Electrostatic vs. covalent. Physica E: Low-dimensional Sys, Nanostructures, 43(9): 1717-1719 (3 pages). Beheshtian, J.; Baei, M.; Peyghan, A.; Bagheri, Z., (2012). Electronic sensor for sulfide dioxide based on AlN nanotubes: a computational study, J. Mol. Model., (18): 4745-4750 (6 pages). Bernholc, J.; Roland, C.; Yakobson, B., (1997). Current opinion in solid state and materials science, Nanotubes, 2(6): 706– 715 (10 pages). Buzea, C.; Ivan, I.; Blandino, P.; Robbie, K., (2007). Nanomaterials and nanoparticles: Sources and toxicity, Biointerphases, 2(4), MR17-MR172. Che, J.; Cajin, T.; Goddard, W., (2000). 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Res., (33): 419–501 (83 pages). Thomas, D.; Penicot, P.; Contal, P.D.; Leclerc, D.; Vendel, J., (2001). Clogging of fibrous filters by solid aerosol particles Experimental and modeling study, Chem. Eng. Sci., 56(11): 3549-3561 (13 pages). Van Zant, P., (2000). Mircochip fabrication – A practical guide to semiconductor processing. 4th. edition. McGraw-Hill: New York. AUTHOR (S) BIOSKETCHES Smith, B.D., Ph.D. Candidate, Department of Civil Engineering, University of Texas at San Antonio, One UTSA Circle, San Antonio, Texas 78249, USA. Email: bioenvengineer@aol.com Bach, S.G.H., Ph.D., Associate Professor; Department of Chemistry, University of Texas at San Antonio, One UTSA Circle, San Antonio, Texas 78249, USA. Email: stephan.bach@utsa.edu How to cite this article: (Harvard style) Smith, B.D.; Bach, S.B.H., (2015). Deposition of carbon nanotubes in commonly used sample filter media, Global J. Environ. Sci. Manage., 1(2): 189-198. 198