Subscriber access provided by UNIV OF SOUTHERN INDIANA
Environmental Modeling
Modeling Particle Emissions from 3D printing with ABS Polymer Filament Tracy Zontek, Scott Hollenbeck, Burton R Ogle, and John T Jankovic Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.9b02818 • Publication Date (Web): 26 Jul 2019 Downloaded from pubs.acs.org on July 28, 2019
Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.
Page 1 of 23
Environmental Science & Technology
RUNNING HEAD: Modeling Particle Emissions
1
Modeling Particle Emissions from 3D printing with
2
ABS Polymer Filament
3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23
Tracy L. Zontek, PhD, CIH, CSP* University of Tampa 401 W. Kennedy Blvd. Tampa, FL 33606
[email protected] Scott Hollenbeck, MPH, CIH Oak Ridge National Laboratory, Center for Nanophase Materials Sciences PO Box 2008 MS-6487 Oak Ridge, TN 37831-6487 Burton R. Ogle, PhD, CIH, CSP Western Carolina University 4121 Little Savannah Road Cullowhee, NC 28723 John Jankovic, MSPH, CIH Oak Ridge National Laboratory, Center for Nanophase Materials Sciences PO Box 2008 MS-6487 Oak Ridge, TN 37831-6487
1 ACS Paragon Plus Environment
Environmental Science & Technology
RUNNING HEAD: Modeling Particle Emissions 24
Abstract
25
An eddy diffusion model using data from a desktop 3D printer was developed
26
under laboratory conditions and then coupled with Monte Carlo analysis to
27
estimate the potential range of particulate concentrations in and around various
28
industrial-size 3D printers. In this case large additive manufacturing processes
29
using acrylonitrile-butadiene-styrene. polymer feedstock. The model employed
30
mass emission estimates determined from thermal gravimetric analysis and
31
printer enclosure particle loss rates. Other model inputs included ranging terms
32
for extrusion rate. temperature, print time, source-to-receiver distance, printer
33
positions, particle size fraction, and environmental diffusivity estimates based
34
on air changes per hour Monte Carlo analysis bracketed measured
35
environmental particulate concentrations associated with large scale additive manufacturing processes
36
(3D printing). Statistically there was no difference between the average near field particle concentrations
37
measured and that of the model-derived average. However, the model began to vary higher statistically, if
38
not practically, from air monitoring results in the far field. Diffusivity and extrusion rate emerged as the
39
two most important variables in predicting environmental concentrations. This model can be used to
40
estimate air concentrations over a range of varying conditions, such as one might employ in a “what if”
41
type of evaluation to estimate employee exposure. For example, as a compliance effort with OSHA
42
standard 29 CFR Part 1910.132 requireing a formal hazard assessment for work environments as a
43
“before exposure” effort to determine if respiratory protection is needed.
44 45
2 ACS Paragon Plus Environment
Page 2 of 23
Page 3 of 23
Environmental Science & Technology
RUNNING HEAD: Modeling Particle Emissions 46
Introduction
47
There has been a substantial increase in use of additive manufacturing and associated materials;
48
projections of the future market range from $20 billion by 2020 and $100-250 billion by 2025 (1) (2) (3).
49
The main industries utilizing some form of additive manufacturing include aerospace and defense,
50
automotive, medical, and consumer-goods industries (2). Additive manufacturing has resulted in new
51
anthropogenic sources of nanoscale or ultrafine particulate (particles < 0.1 um or 100 nm, UFP). Early
52
research has identified that nanoscale materials can reach all areas of the respiratory system, including the
53
alveoli and thus have the potential to move throughout the body (4). Specific research in the field of
54
additive manufacturing has identified an asthma case study (5), asthma and allergic rhinitis in those
55
working with acrylonitrile butadiene styrene (ABS) filament more than 40 hours per week (6), and
56
inhalational studies of rats documented acute hypertension (7). Emerging research of additive
57
manufacturing has reported particle emission rates of 108 to 1011 particles per minute in size ranges
58
classified as UFP during additive manufacturing (3D printing) with desktop size printers (8). It has been
59
reported in clinical studies that inhalation of ultrafine carbon particles causes subtle alterations in vascular
60
function in healthy non-exercising subjects at about 10µg/m3 (9) (10). Further, an increase in outdoor
61
UFP concentrations of approximately 10,000 #/cc has been associated with an increased risk of mortality
62
by 3% (11).
63 64
Regulatory limits for ultrafine particles include the Occupational Safety and Health Administration
65
(OSHA) Particulate Not Otherwise Classified, Respirable (< 4 µm, 5 mg/m3) measured as an eight-hour
66
time weighted average. The Environmental Protection Agency (EPA) has a National Ambient Air Quality
67
Standard for PM2.5 (35 µg/m of particulate matter less than 2.5 µm, measured as a 24-hour average) (12).
68
Additive manufacturing particulate emissions, mostly in the UFP range have no specific exposure limit.
69
Aerosol mass concentration is low, even at high particle concentrations, making traditional industrial
70
hygiene filter monitoring an aerosol that is composed of carbonaceous materials purportedly capable of
71
impacting respiratory health, highly problematic (13). 3 ACS Paragon Plus Environment
Environmental Science & Technology
RUNNING HEAD: Modeling Particle Emissions 72 73
Thermal oxidative degradation of various polymers used as filament materials during heating and
74
extrusion are known to release a variety of irritants and systemic toxins in low amounts (14).
75
Manufacturing applications using 3D printing are burgeoning, and the availability of low-cost desk-top
76
size printers suggest their use in non-industrial settings, where poor ventilation may exist, will become
77
more prevalent as well (13). Azimi, Fazli, and Stephens (15) used particle emissions and volatile organic
78
compound concentrations from published studies to estimate the impact of different ventilation scenarios;
79
the conclusions drawn mimic traditional industrial hygiene controls, specifically the importance of
80
controlling the contaminant at the source. They found that high flow/high capture efficiency spot
81
ventilation systems, followed by using a 3D printer with an enclosure that filters emissions to be the most
82
effective (15).
83 84
The expanding use of additive manufacturing, limited data in the literature, a lack of exposure limits, as
85
well as the absence of standardized air monitoring protocols and methods of data analysis, make a strong
86
case for using readily available models coupled with uncertainty analysis to elucidate aerosol
87
concentration and dispersion during 3D printing operations (16) (17). Modeling can provide an estimate
88
of aerosol concentration that can be used to conduct a risk assessment and determine appropriate controls.
89
This study uses particle emissions from a desktop 3D printer to develop and validate a modeling
90
approach; then applies the approach to a large scale area additive manufacturing process.
91 92
4 ACS Paragon Plus Environment
Page 4 of 23
Page 5 of 23
Environmental Science & Technology
RUNNING HEAD: Modeling Particle Emissions 93
Materials and Methods
94
A Da Vinci XYZ model 1.0 3D desktop printer (DTP) was used in poorly ventilated room (~1.8 air
95
changes per hour) in order to obtain emission estimates and air concentration maps for model inputs.
96
Time series measurements were collected inside and outside the DTP enclosure. The printer enclosure
97
itself was not designed to contain printing emissions as there were numerous openings allowing free air
98
movement from and into the environment. Speculatively, the enclosure was meant to prevent contact with
99
the heated/ moving elements of the printer. These openings served as sampling ports inside the enclosure;
100
temperature data inside the DTP enclosure was not monitored since it was open to free air flow. The
101
monitoring position outside the enclosure was located at a point representative of the breathing zone of a
102
person sitting at the table on which the printer was located (Figure 1). Background particulate
103
concentrations were determined prior to filament heating and extrusion.
104 105
Figure 1. Enclosed DTP and breathing zone/ambient air monitoring positions.
106 107
Room concentration maps were constructed for background, heating, early printing, and late stage
108
printing using 3DField mapping freeware (18) and a handheld TSI® model 3007 Condensation Particle
109
Counter (CPC) with size detection from 10nm to > 1µm size at concentrations up to 105 particles/cm3).
110
Mapping was used to compare model results with air sampling results. Particle size and mass
111
concentration was determined using a combination of scanning mobility particle analyzers (SMPS)
112
including a TSI® SMPS 3080 equipped with either a long differential mobility analyzer (DMA) or nano
113
DMA (TSI® 3085). The long DMA and nano DMA were alternated in order to obtain particle sizes from
114
2 nm to 300 nm. A TSI® optical particle sizer (OPS) was simultaneously used to measure particle size
5 ACS Paragon Plus Environment
Environmental Science & Technology
RUNNING HEAD: Modeling Particle Emissions 115
information from 300 nm to 10 µm. TSI’s MIM merging software (19), was used to combine the small
116
fraction mobility diameters with the large fraction optical diameters into one normalized particle size
117
distribution as either ΔN/Δlog dp or ΔM/Δlog dp. By definition, both electrical mobility and optical
118
diameters refer to equivalent spherical particle behavior in an electric field or in a scattered light beam
119
respectively. These instruments provided corresponding number and mass concentrations using TSI®
120
algorithms provided in their respective AIM® software. The concentration measurements from the DTP
121
trials were used in comparison with model predictions in order to refine input variables. The conversion
122
from count to mass on the basis of sphericity is justified on the basis that the instruments used to measure
123
mass were also based on light scattering and the assumption of sphericity. Additionally, the density of
124
ABS plastic is about 1g/cc.
125 126
The DTP used in the test room was operated at a printing temperature of 213°C using an ABS filament.
127
These are fixed parameters for this particular printer. The resolution was set at best quality (fine 0.1 mm)
128
resulting in the longest printing time. Filament feed rate is a variable function of the part being printed, as
129
is the amount of filament used. The test printer did not provide the precise amount of filament used.
130
Therefore, the same part was printed for all of the trial measurements thereby keeping quantity and print
131
time constant. The final part mass was not measured; if the printing build had any issues it was re-started.
132 133
The near-field eddy diffusion model was selected in favor of a one or two-compartment box model
134
because it does not require an assumption of a “well mixed” environment as do the others. (20)
135
Further, this model accounts for varying distances, more characteristic of 3D printing operations where
136
printer operators and ancillary personnel are not stationary. When accompanied with concentration
137
mapping, the model can provide useful information for time and motion type exposure assessment. Either
138
the number or mass emission rate of the process is necessary to estimate concentration with models that
139
account for removal by general ventilation (21), or more complex models such as the eddy diffusion
140
model for predicting concentration at various distances and times (22). Since personnel may move about 6 ACS Paragon Plus Environment
Page 6 of 23
Page 7 of 23
Environmental Science & Technology
RUNNING HEAD: Modeling Particle Emissions 141
in the printing area, the eddy diffusion model was used to estimate concentrations at various points in the
142
near exposure field. The number emission rate (E) was calculated from CPC measured particle
143
concentration decay after extrusion was completed (Eq. 1) (23). The loss rate factor and emission rate
144
contained all of the particle sinks such as removal by ventilation, wall losses, and agglomeration (Eq 1,2)
145
(8).
146
147
Eq.(1) 𝐿 =
(𝐶𝑠𝑡𝑎𝑟𝑡 ― 𝐶𝑏𝑔𝑠𝑠) 𝑙𝑛 (𝐶 ― 𝐶 𝑒𝑛𝑑 𝑏𝑔𝑠𝑠) ∆𝑡
, Where
148
L is total particle loss rate by all particle removal mechanisms (min -1)
149
Cstart is particle concentration at end of printing (#/cm3)
150
Cend is particle concentration at end of decay period (#/cm3)
151
Cbgss is background particle concentration before printing (#/cm3)
152
Δt is elapsed time between Cstart and Cend
153
Note: background is a measured quantity either taken at a time just preceding the printing operation or it
154
was derived from historical monitoring during extended periods when printing is not
155
taking place.
156
Eq. (2) 𝐸 = 𝐿 ∙ 𝐶𝑝𝑠𝑠 ∙ 𝑉, where
157
E is particle emission rate (#/min)
158
Cpss is printer enclosure or room concentration at steady state minus background
159 160
(#/cm3) V is volume of printer or room enclosure (cm3)
161 162
It was necessary to convert CPC measured particle concentrations to mass concentrations for comparison
163
with mass-based exposure data both by us and others such as that by Frampton et al (10). The relationship
164
between number concentration and mass concentration, as functions of geometric mean particle diameter
165
and geometric standard deviation, was approximated from SMPS data. The algorithm used to convert #/cc 7 ACS Paragon Plus Environment
Environmental Science & Technology
RUNNING HEAD: Modeling Particle Emissions 166
to µg/m3 used the mean diameter from the distribution of diameters and assumed particle sphericity. The
167
justification for this approach was discussed earlier. Mass emission rates for ABS filaments used in
168
printing at various temperatures were determined experimentally by thermal gravimetric analysis (TGA)
169
using a TGA Q5000; this study focused on particle emission rates as printing temperatures were not high
170
enough for much vapor formation. A Monte Carlo analysis (Analytica 2.0) using the eddy diffusion
171
model was performed to evaluate the distribution of possible aerosol concentrations as extrusion rate,
172
extrusion temperature, printing time, distance of observer from source, and diffusivity variables that were
173
allowed to vary (Figures 2 and 3) (24).
174 175
Eq. (3)
𝐺
C𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑎𝑡 𝑝𝑜𝑖𝑛𝑡 r = 2𝜋𝐷𝑟𝑒𝑟𝑓𝑐
[
𝑟 (4𝐷 ∙ ∆𝑡)
], where
176 177
D
= eddy diffusivity
178
r
= sample point distance from source
179
Δt
= elapsed time since start of release
180
G
= continuous emission rate
181
erfc = 1- error function
182 183
Figure 2. Model variables and outcomes
184
8 ACS Paragon Plus Environment
Page 8 of 23
Page 9 of 23
Environmental Science & Technology
RUNNING HEAD: Modeling Particle Emissions 185
Variable importance, the relative contribution to uncertainty in the outcome, was used to indicate which
186
variables were most critical to the exposure estimates; and, where possible, additional efforts were made
187
to refine those variables. Filament extrusion rate is governed by operator choices such as build quality
188
and build rate. Sophisticated printers (Figure 3) may provide accurate information on printing time and
189
polymer consumption thus providing an accurate average extrusion rate. Less expensive printers provide
190
less accurate or no information from which to determine average extrusion rate. The test printer provided
191
filament usage accurate to the nearest meter. This study measured printing time (hh/mm/ss) rather than
192
using the printer estimates; the extrusion rate in length per minute was converted to weight per minute
193
based on the density of the filament type.
194 195
Eddy diffusion is a process by which a substance mixes in ambient air due to air currents. We initially
196
used diffusivities reported for various industrial processes other than 3D printing, which were later
197
replaced with more current information (25) relating diffusivity to ventilation in terms of ACH (Eq. 4),
198
experimentally derived by Cheng (26).
199 200
Eq (4)
Diffusivity (m2/min) = L2((0.6∙ACH)+0.25)/60, where
201
L
202
ACH = mixing air changes in the room volume (min-1)
= cube root of the room volume (m)
203 204
The DTP derived model was used to estimate aerosol concentrations from two Big Area Additive
205
Manufacturing (BAAM) operations involving 3D printing changing only the relevant operational
206
parameters used by the printers. The BAAMs used were a prototype system (7’x7’x3’ build volume,
207
10lb/hr deposition rate) and a Cincinnati 100 ALPHA size 2 (8’x2’x‘6’ build volume, 100 lb/hr
208
deposition rate). As with the DTP, the aerosol concentrations were monitored (CPC, SMPS, OPS) at the
209
printer location in the large open-bay operation (Figure 3); the equipment cart was placed between the
210
Cincinnati and gantry printers, as determined by space and electrical resources, while not interfering with 9 ACS Paragon Plus Environment
Environmental Science & Technology
RUNNING HEAD: Modeling Particle Emissions 211
egress or normal working operations. An additional CPC was located approximately 20 feet away from
212
the cart with the CPC, SMPS, and OPC; again, location was based on space conditions. A third point at
213
some distance and on a level above the printer floor was also monitored (mezzanine level). Plate flow
214
around the extruder was assumed to be laminar as the head movement is on the order of a few feet per
215
minute. Thus, eddy currents were not expected to result from the printer itself.
216 217
Figure 3. Large scale open-bay gantry 3D printer
218 219 220 221 222 223
Results The particles emitted by the DTP printer, presented as a cumulative frequency distribution in Figure 4a,
224
are almost entirely within the ultra-fine particulate classification (23). Particles collected near the printer
225
in the theoretical breathing zone of someone monitoring the operation are also presented as a normalized
226
number distribution. The aerosol has a bimodal distribution with modes at about 7 and 15 nm (Figure 4b).
227
This was typical of BZ values for most printing runs in the early stages of extruder heating and printing.
228
As time of printing progressed, often the particles grew in size to between 20 and 30 nm (not depicted).
229
Sixty-eight percent of the particle mass was present as UFP (Figure 4c). The normalized size distribution 10 ACS Paragon Plus Environment
Page 10 of 23
Page 11 of 23
Environmental Science & Technology
RUNNING HEAD: Modeling Particle Emissions 230
again presented as bimodal with the largest mode at about 90 nm. A second, smaller mode was centered at
231
about 230 nm (Figure 4d). Particle size and concentration numerical data is presented in Table 2. Figure 5
232
depicts size variation over a 60-minute print job.
233 234
Fig 4. Cumulative number/mass frequencies (a,c) and representative aerosol number/mass particle size
235
(b,d) in BZ from SMPS (7 to 294 nm size instrument resolution).
236 237 238 239 240 241 242
11 ACS Paragon Plus Environment
Environmental Science & Technology
RUNNING HEAD: Modeling Particle Emissions
number mobility dia. (nm)
number mobility dia. (nm)
mass mobility dia. (nm)
mass mobility dia. (nm)
243
Figure 5. Inside printer enclosure; variability in size and cumulative frequency distributions from SMPS
244
with Nano DMA (2 to 100 nm size resoultion).
245 246 247
Eddy diffusion modeling results for the test room containing the small enclosed 3D printer are presented
248
in Figure 6, modeling results for the large scale printing process are presented in Figures 7 and 8. The
249
measured values in Figure 7 are determined from a Monte Carlo analysis using the mean and standard
250
deviation (SD) from the large printing facility. The predicted values are derived from the eddy
251
diffusion/Monte Carlo model. As expected, allowing for variability in the inputs resulted in a wider data 12 ACS Paragon Plus Environment
Page 12 of 23
Page 13 of 23
Environmental Science & Technology
RUNNING HEAD: Modeling Particle Emissions 252
spread; however, the model average was in good agreement with the sampling location averages (-1% to
253
+20%). Modeling results for the large printing facility (Figure 8) suggest about a 5% chance that an
254
exposure could exceed 10 µg/m3 (alterations in vascular function in healthy adults (9) (10)). Statistically
255
there was no difference in mean values obtained from the model and ambient measurements for the two
256
large-scale printers tested or the mezzanine. P values for a one-way ANOVA followed with a Post Hoc
257
Tukey HSD test are presented in Table 1.
258
Table 1. P values for model comparison P value Gantry with model prediction
0.344
Cincinnati with model prediction
0.899
Mezzanine with model prediction
0.155
259 260
Although the averages are in good agreement; individual point predictions vary widely but do bracket the
261
range of measured concentrations (Figure 7). The model’s utility then is in providing a probability
262
distribution from which one can consider the likelihood of some established limit being exceeded.
263
Autocorrelation in time series data is frequently an issue when normality and randomness are required in
264
order to apply normal statistics. Measured concentration data was tested for autocorrelation and was
265
found to be random (white noise) with p values >> 0.05. Tests were performed using an autocorrelation
266
function (ACF) in RealStat-2010 for Microsoft Excel. The ACF score was 0.08 where a value
267
approaching 1 is considered highly correlated.
268
Figure 6. Mapped mass concentration (a) and eddy diffusion model exposure prediction (b) for the test
269
printer
13 ACS Paragon Plus Environment
Environmental Science & Technology
RUNNING HEAD: Modeling Particle Emissions
a P of exceeding 10 µg/m3 ≈ 0
270 271 272 273 274 275
Figure 7. Modeling predictions bound the monitoring values by location in the large printing facility
14 ACS Paragon Plus Environment
Page 14 of 23
Page 15 of 23
Environmental Science & Technology
RUNNING HEAD: Modeling Particle Emissions
Gantry
Cincinnati
Mezzanine
Model
Concentration (µg/m3)
1E+05
1E+04
1E+03 0
20
40 60 Iteration (Run)
80
100
276 277 278 279 280 281
Figure 8. PM0.1 mass exposure prediction values for the large printing process.
282
15 ACS Paragon Plus Environment
Environmental Science & Technology
Page 16 of 23
RUNNING HEAD: Modeling Particle Emissions 283
Table 2. Aerosol parameters measured inside and outside DTP enclosure during printing (ABS 213°C)
284
(13). Inside printer enclosure
Outside printer enclosure in breathing zone
SMPS
CPC
Calculated
(Avg, ~ 1
(Avg, ~ 1
hour)
hour)
SMPS
Printer Parameter function GM
Mode
GS
#/cc
µg/m3
GM (nm)
Mode
GSD
(nm)
(nm)
D
Mean
24.2
16.4
20.7
522,000*
83.3
14.7
9.3
1.79
SD
3.5
2.4
0.34
582,258*
70.2
2.9
2.5
0.56
Mean
30.5
34.1
1.95
71,450
7.6
16.3
9.4
1.71
SD
4.6
13.2
0.12
45,068
6.2
0.5
2.1
0.01
Mean
16.3
14.3
1.50
66,308
0.4
N = 10 for both sample sets.
SD
1.1
1.0
0.05
38,234
0.2
Door
Mean
25.6
19.2
2.17
834
0.2
open
SD
3.3
4.7
0.21
33
0.1
(nm)
Heating
Printing
Cooling
285
*Value underestimates actual concentration and requires dilution or coincidence correction not performed
286
here.
287 288
16 ACS Paragon Plus Environment
Page 17 of 23
Environmental Science & Technology
RUNNING HEAD: Modeling Particle Emissions 289
TGA emission rates were determined for the range of extrusion temperatures expected in the printing
290
processes (Table 3). Temperatures varied during warm-up, filament changing/loading, and cool-down;
291
this variation was included in the modeling process using Equation 5 in the temperature variable.
292 293
294 295
Table 3. TGA derived mass emission rates for 1.75 mm diameter ABS filament. T (°C)
200
213
215
230
E (µg/mg)
9.2
10.9
11.7
14.8
Note: data represents the mass fraction estimates of the emissions only.
Eq. (5).
𝜇𝑔 𝑚𝑔
= 0.3733𝑒0.016𝑇, where
296 297
µg/mg is µg emitted/mg of filament extruded
298
T is extrusion temperature (°C)
299 300
Discussion
301
The eddy diffusion model as applied here is not novel. The utility of the approach here is to introduce the
302
use of modeling data in a visualized probabilistic format, i.e., model results plus a Monte Carlo analysis
303
to incorporate uncertainty and predicted concentration mapping to aid in visualization of possible
304
outcomes. Other researchers have implemented the eddy diffusion model for use by field industrial
305
hygienists (16) (22) (24) and this provides guidance to determine particle emissions from the emerging
306
field of additive manufacturing where traditional mass concentration measurements and regulatory limits
307
may not adequately describe the potential health risk. This technique, in contrast to a 3D numerical
308
simulation by Computational Fluid Dynamics, is more readily available to field industrial hygienists as it
309
can run in a spreadsheet and does not require additional software/training. Further, it only requires the use
310
of a CPC; the SMPS and OPC data were included to provide the basis for mass conversions to compare to
311
health effects literature, as developed in the Introduction.
17 ACS Paragon Plus Environment
Environmental Science & Technology
RUNNING HEAD: Modeling Particle Emissions 312 313
Keeping in mind that the aim is not to provide a precise estimate of a point exposure, we never the less
314
determined the normalized root mean square error (NRMSE) between the model and each of the
315
printers/areas in order to evaluate the model’s accuracy. If the model’s prediction is too large the
316
NRMSE would be greater than 1. All NRMSEs were below 1 (0.39 for the Gantry, 0.44 for the
317
Cincinnati, and 0.41 for the mezzanine).
318 319
As another means of assessing uncertainty we performed a type of sensitivity analysis in the form of
320
variable importance. A function in Analytica™, the software used to run the model and the Monte Carlo
321
trials. The two most important variables (Figure 9) were filament extrusion rate and the eddy diffusion
322
coefficient.
323 324
Figure 9. Model Variable Importance
325
326 327
Modeling provides insight into the range of possible air concentrations pre-exposure, the implications of
328
which are obvious. Using a CPC, concentration maps, generation rates, and simple modeling techniques
329
are useful in hazard assessments for purposes of specifying personal protective equipment a priori,
330
requiring ventilation recommendations, and establishing suitable printer locations with respect to
331
occupied locations. Creating an exposure distribution allows one to view the probability of an exposure 18 ACS Paragon Plus Environment
Page 18 of 23
Page 19 of 23
Environmental Science & Technology
RUNNING HEAD: Modeling Particle Emissions 332
exceeding a pre-determined value, i.e., an exposure limit when the conditions resulting in the exposure
333
are variable providing advanced information upon which to inform hazard assessment. Additional
334
printing trials at different extrusion temperatures, feed rates, filament sizes and types would aid in
335
providing better bounding for both mass and particle generation rates for future modeling.
336
Statistically there was no difference in the averages of the model prediction and the various printers;
337
however, the statistical agreement between averages fails to tell the whole story. The model by itself
338
would fail to accurately predict a single point determination at some distance from the source in real time
339
with any statistical degree of accuracy. This is because the model, as applied here, uses distributions for
340
the input parameters rather than discrete values. The output from the model was designed to be used as a
341
simulation from which to develop a probability density function (use of the Monte Carlo routine). The
342
utility of this approach is its probabilistic output from which one can develop the likelihood of exceeding
343
some predetermined concentration as part of a hazard assessment.
344
It should also be noted that the model is based on mixing gases. In the case of 3D printing the emitted
345
particulate is well down in the nanoscale region of the aerosol transition regime (molecular mean free
346
path ≈ particle diameter) with Knudsen numbers approaching 10. Thus, for nanoscale particles it is
347
reasonable to treat their movement similar to other molecules forming a field (27).
348
Conclusion
349
Using process filament extrusion rates and temperature specific mass emission rates, the eddy diffusion
350
model coupled with Monte Carlo analysis reasonably estimates ranges of mass and number
351
concentrations encompassing the actual process ambient air concentrations. The SMPS data was used to
352
provide diameters and subsequent mass conversions as health effects literature is primary mass-based.
353
Model input data is easily obtainable, requiring only a means of obtaining the process parameters, a
354
sampler such as a CPC to verify the model performance, and both model and analysis routines are
355
available with existing freeware. Modeling, once developed, can be used to predict air concentrations 19 ACS Paragon Plus Environment
Environmental Science & Technology
RUNNING HEAD: Modeling Particle Emissions 356
over a range of varying conditions, such as one might employ in a “what if” type of evaluation. Some
357
OSHA standards require formal hazard assessments for work environments where PPE may be needed
358
(29 CFR Part 1910.132). Modeling data may be useful in meeting such a requirement.
359 360
Conflict of Interest
361
There is no conflict of interest to disclose in the study.
362
This manuscript has been authored by UT-Battelle, LLC under Contract No. DE-AC05-00OR22725 with
363
the U.S. Department of Energy. The United States Government retains and the publisher, by accepting
364
the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-
365
up, irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or
366
allow others to do so, for United States Government purposes. The Department of Energy will provide
367
public access to these results of federally sponsored research in accordance with the DOE Public Access
368
Plan (http://energy.gov/downloads/doe-public-access-plan).
369
Acknowledgements
370
This research was conducted at the Center for Nanophase Materials Sciences, which is sponsored at Oak
371
Ridge National Laboratory (ORNL) by the Scientific User Facilities Division, Office of Basic Energy
372
Sciences, U.S. Department of Energy. Additionally, this research was supported by the U.S. Department
373
of Energy (DOE) Higher Education Research Experience (HERE) and was administered by the Oak
374
Ridge Institute for Science and Education (ORISE).
375 376
References
377
1. Eigel-Miller, N.; Kline Jr, S. World machine-tool output and consumption survey. [Online] February
378
27, 2014. https://www.gardnerintelligence.com/report/world-machine-tool.
20 ACS Paragon Plus Environment
Page 20 of 23
Page 21 of 23
Environmental Science & Technology
RUNNING HEAD: Modeling Particle Emissions 379
2. McKinsey & Co. Additive manufacturing: A long-term game changer for manufacturers. [Online]
380
McKinsey & Co., September 2017. https://www.mckinsey.com/business-functions/operations/our-
381
insights/additive-manufacturing-a-long-term-game-changer-for-manufacturers.
382
3. Flynn, H.; Hwang, D.; Holman, M. Nanotechnology update: Corporations up their spending as
383
revenues for nano-enabled products increase. UN Environment Depository, 2013.
384
http://hdl.handle.net/20.500.11822/20163
385
4. Oberdorster, G.; Oberdoster, E.; Oberdorster, A. Nanotoxicology: An emerging discipline evolving
386
from studies of ultrafine particles. Environ Health Perspect. 2005, 113 (7), 823-39.
387
5. House, R.; Rajaram, N.; Tarlo, S.M. Case report of asthma associated with 3D printing. Occup Med.
388
2017, 67, 652-54.
389
6. Chan, F.L.; House, R.; Kudla, I.; Rajaram, N.; Tarlo, S.M. Health survey of employees regularly using
390
3D printers. Occ Med. 2018, 68 (3), 211-214.
391
7. Stefaniak, A.B.; LeBouf, R.F.; Duling, M.G.; Yi, J.; Abukabda, A.B.; McBride C.R.; Nurkiewicz,
392
T.R..Inhalation exposure to three-dimensional printer emissions stimulates acute hypertension and
393
microvascular dysfunction. Toxicol Appl. Pharmacol. 2017, 335, 1-5..
394
8. Stephens, P.; Azimi, P.; El Orch, Z.; Ramos,, T. Ultrafine particle emissions from desktop 3D printers.
395
Atmos.Environ. 2013, 79, 334-39.
396
9. Alessandrini, F.; Schutz, H.; Takenaka, S.; Lentner, B.; Karg, E.; Behrendt, E.; Jakob, T. Effects of
397
ultrafine carbon particle inhalation on allergic inflammation of the lung. Allergy Clin. Immunol. 2007, 117
398
(4), 824-30.
399
10. Frampton, M. W.; Utell, M. J.; Wojciech, Z.; Oberdorster, G.; Cox, C.; Huang, L. Effects of exposure
400
to ultrafine carbon particles in healthy subjects and subjects with asthma. Res. Rep. Health Eff. Int. 2004,
401
126, 49-63.
402
11. Stolzel, M.; Breitner, S.; Cyrys, J.; Pitz, M.; Wolke, G.; Kreyling, W.; Heinrich, J.; Wichmann, H-E.;
403
Peters, A. Daily mortality and particulate matter in different size classes in Erfurt, Germany. Journal of
404
Exp. Sci. Environ. Epi., 2007, 17, 458-67. 21 ACS Paragon Plus Environment
Environmental Science & Technology
RUNNING HEAD: Modeling Particle Emissions 405
12. U.S. Environmental Protection Agency. Particulate matter. 2016. https://www.epa.gov/pm-pollution
406
13. Zontek, T. L.; Ogle, B. R.; Jankovic, J. T.; Hollenbeck, S. M. An exposure assessment of desktop 3D
407
printing. J. Chem. Health Saf., 2017, March/April, 15-25.
408
14. Rutkowski, J. V.; Levint, B. Acrylonitrile-butadiene-styrene copolymers (ABS): Pyrolysis and
409
combustion products and their toxicity - a review of the literature. Fire and Mats. 1986, 10 (3-4), 93-105.
410
15. Azimi, P.; Fazli, T.; Stephens, B. Predicting concentrations of ultrafine particles and volatile organic
411
compounds resulting from desktop 3D printer operation and the impact of potential control strategies. J.
412
Ind.l Eco. 2017, 21 (1), S107-19.
413
16. Keil, C. Patterns of exposure: The power and utility of mathematical models. Synergist. 2017,
414
January.
415
17. Hewett, P. Easy modeling: Forecasting occupational exposures using "well mixed room" models.
416
Synergist, 2017, April.
417
18. Galouchko, V. 3D Field. [Online] 2012. http://3dfmaps.com.
418
19. TSI, Inc. Users guide: Multi-instrument manager (MIM) software for SMPS spectrometers and OPS
419
sizers. TSI, Inc. 2014. www.tsi.com
420
20. Jaycock, M. A major advance in exposure modeling tools. Human health risk assessment to
421
chemicals: The eddy diffusion model is now usable. [Online] December 2013. https://jayjock-
422
associates.blogspot.com/2013/12/the-eddy-diffusion-near-field-model-is.html
423
21. American Conference of Governmental Industrial Hygienists (ACGIH). Industrial ventilation: A
424
manual of recommended practice for design. Cincinnati, OH. 1995.
425
22. Donovan, B. L.; Sahmel, J.; Scott, P. K.; Pauenbach, D. J. Evaluation of bystander exposures to
426
asbestos in occupational settings: A review of the literature and application of a simple eddy diffusion
427
model. Crit. Rev. Toxicol. 2011, 41 (1), 52-74.
428
23. Wallace, L. A.; Emmerich, S. J.; Howard-Reed, C. Source strengths of ultrafine and fine particles due
429
to cooking with a gas stove. Env. Sci. Technol. 2004, 38 (8), 2304-11.
22 ACS Paragon Plus Environment
Page 22 of 23
Page 23 of 23
Environmental Science & Technology
RUNNING HEAD: Modeling Particle Emissions 430
24. Shade, W. D.; Jaycock, M. A. Use of Monte Carlo uncertainty analysis of a diffusion model for the
431
assessment of halogen gas exposure during dosing of brominators. Amer. Ind. Hyg. Assoc. J. 1997, 58 (6),
432
418-24.
433
25. Jaycock, M. A major advance in exposure modeling tools. Human health risk assessment to
434
chemicals: IH Mod 2.0 – A major advance in exposure modeling tools. [Online] September 2018.
435
https://jayjock-associates.blogspot.com/2018/09/ih-mod-20-major-advance-in-exposure.html
436
26. Cheng, K-C.; Acevedo-Bolton, V.; Jiang, R-T.; Klepeis, N. E.; Ott, W. R.; Fringer, O. B.; Hildemann,
437
L. M. Modeling exposure close to air pollution sources in naturally ventilated residences: Association of
438
turbulent diffusion coefficient with air change rate. Environ. Sci. Technol. 2011, 45 (9), 4016-22.
439
27. Madler, L.; Friedlander, S.K. Transport of nanoparticles in gases: Overview and recent advances. Aer.
440
and Air Qual. Res. 2007, 7 (3), 304-342.
441 442
23 ACS Paragon Plus Environment