ASTM D6602-03b(2010)e1
(Practice)Standard Practice for Sampling and Testing of Possible Carbon Black Fugitive Emissions or Other Environmental Particulate, or Both
Standard Practice for Sampling and Testing of Possible Carbon Black Fugitive Emissions or Other Environmental Particulate, or Both
SIGNIFICANCE AND USE
Particulate emissions are major contributors to air contamination in industrial and urban environments. Soot is formed as an unwanted by-product of combustion and consequently varies widely with the type of fuel and combustion conditions. Carbon black, on the other hand, is purposely produced under a controlled set of conditions. Therefore, it is important to be able to distinguish carbon black from soot, as well as other environmental contaminants.
SCOPE
1.1 This practice covers sampling and testing for distinguishing ASTM type carbon black, in the N100 to N900 series, from other environmental particulates.
1.2 This practice requires some degree of expertise on the part of the microscopist. For this reason, the microscopist must have adequate training and substantial on-the-job experience in identifying the morphological parameters of carbon black. In support of this analysis, Donnet's book is highly recommended to be used as a technical reference for recognizing and understanding the microstructure of carbon black.
1.3 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.4 This standard may involve hazardous materials, operations, and equipment. This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.
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Designation: D6602 − 03b(Reapproved 2010)
Standard Practice for
Sampling and Testing of Possible Carbon Black Fugitive
Emissions or Other Environmental Particulate, or Both
This standard is issued under the fixed designation D6602; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
´ NOTE—Editorially corrected Annex A1 in May 2010.
1. Scope 3. Terminology
1.1 This practice covers sampling and testing for distin- 3.1 Definitions of Terms Specific to This Standard:
guishingASTMtypecarbonblack,intheN100toN900series,
3.1.1 aciniform—shaped like a cluster of grapes.
from other environmental particulates.
3.1.1.1 Discussion—The spheroidal primary particles of
carbon black are fused into aggregates of colloidal dimension
1.2 This practice requires some degree of expertise on the
forming an acinoform morphology.
partofthemicroscopist.Forthisreason,themicroscopistmust
haveadequatetrainingandsubstantialon-the-jobexperiencein
3.1.2 aciniform carbon—colloidal carbon having a mor-
identifying the morphological parameters of carbon black. In
phology consisting of spheroidal primary particles (nodules)
support of this analysis, Donnet’s book is highly recom-
fused together in aggregates of colloidal dimension in a shape
mendedtobeusedasatechnicalreferenceforrecognizingand
having grape-like clusters or open branch-like structures
understanding the microstructure of carbon black.
3.1.3 carbon black, n—an engineered material, primarily
1.3 The values stated in SI units are to be regarded as
composed of elemental carbon, obtained from the partial
standard. No other units of measurement are included in this
combustion or thermal decomposition of hydrocarbons, exist-
standard.
ing in the form of aggregates of aciniform morphology which
are composed of spheroidal primary particles characterized by
1.4 This standard may involve hazardous materials,
operations, and equipment. This standard does not purport to uniformity of primary particle sizes within a given aggregate
and turbostratic layering within the primary particles.
address all of the safety concerns, if any, associated with its
use. It is the responsibility of the user of this standard to
3.1.3.1 Discussion—Particle size and aggregate size (num-
establish appropriate safety and health practices and deter-
ber of particles per aggregate) are distributional properties and
mine the applicability of regulatory limitations prior to use.
vary depending on the carbon black grade. Transmission
electron micrographs shown in Annex 1 of Practice D6602
2. Referenced Documents
demonstratethatwhileparticleandaggregatesizesvarygreatly
2.1 ASTM Standards: within a given grade of carbon black, the primary particle size
D1619Test Methods for Carbon Black—Sulfur Content is essentially uniform within an individual aggregate.
D3053Terminology Relating to Carbon Black
3.1.4 chain of custody—a document describing the condi-
D3849 Test Method for Carbon Black—Morphological
tion of a sample during its collection, analysis, and disposal.
Characterization of Carbon Black Using Electron Micros-
3.1.5 char—a particulate larger than 1 µm made by incom-
copy
plete combustion which may not deagglomerate or disperse by
ordinary techniques, may contain material which is not black,
This practice is under the jurisdiction of ASTM Committee D24 on Carbon
and may contain some of the original material’s cell structure,
Black and is the direct responsibility of Subcommittee D24.66 on Environment,
minerals, ash, cinders, and so forth.
Health, and Safety.
CurrenteditionapprovedJan.1,2010.PublishedMay2010.Originallyapproved
3.1.6 fugitive dust—transitory, fleeting material comprised
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in 2000. Last previous edition approved in 2003 as D6602–03b . DOI: 10.1520/
of particulates foreign to the surface of deposition.
D6602–03BR10E01.
Hess, W.M. and Herd, C.R., Carbon Black Science and Technology, Edited by
3.1.7 fungus, sooty mold, mildew—particulates from a su-
Donnet, J.B., Bansal, R.C., and Wang, M.J., Marcel Dekker, Inc., New York, NY,
perficial growth that grows on living and decaying organic
1993, pp. 89–173.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or matter.
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
3.1.8 mineral and urban dust—airborne,naturallyoccurring
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. inorganic particulates inherent to the area.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
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D6602 − 03b (2010)
3.1.9 pollen—particulates from a mass of microspores in a 4.3 AblockdiagramispresentedinFig.1togiveapossible
seed plant. scheme to follow in performing this analysis. However, it
should be noted that this scheme is a suggestion, not a
3.1.10 rubber dust—finely divided soft particulates abraded
requirement.
from rubber.
3.1.11 sample—a small fractional part of a material or a 5. Significance and Use
specified number of objects that are selected for testing,
5.1 Particulate emissions are major contributors to air con-
inspection, or specific observations of particular characteris-
tamination in industrial and urban environments. Soot is
tics.
formed as an unwanted by-product of combustion and conse-
3.1.12 soot—a submicron black powder generally produced
quently varies widely with the type of fuel and combustion
as an unwanted by-product of combustion or pyrolysis. It
conditions. Carbon black, on the other hand, is purposely
consists of various quantities of carbonaceous and inorganic
produced under a controlled set of conditions. Therefore, it is
solids in conjunction with adsorbed and occluded organic tars
important to be able to distinguish carbon black from soot, as
and resins.
well as other environmental contaminants.
3.1.12.1 Discussion—The carbonaceous portion also is col-
6. Sampling
loidal and often has the aciniform morphology. Soot may have
several carbon morphologies. Examples of soot are carbon
6.1 The area to be sampled must be representative of the
residues from diesel and gasoline engines, industrial flares,
contaminated area. For sampling, choose an area that appears
sludge pits, burning tires, and so forth.
to contain black particulates. The same general surface should
be used for gathering all test samples for each property site
3.1.13 sticky tape—a section of tape with a sticky, solvent-
location.
soluble adhesive used in the collection of particles from
surfaces.
6.2 Equipment:
6.2.1 Polyester/Cotton Balls or Glass Fiber Pads.
3.1.14 surface—theoutersurface,facing,orexteriorbound-
aryofanobjectcapableofsupportingcarbonandotherfugitive
and natural occurring dusts and particulates.
3.1.15 turbostratic—a type of graphitic crystallographic
structure in which there is no symmetry along the z-axis.
3.2 Acronyms:
3.2.1 EDS—energy dispersive spectroscopy associated with
SEMandTEMfortheidentificationofelementalcomposition,
3.2.2 LM—light microscope,
3.2.3 PLM—polarizing light microscope,
3.2.4 SEM—scanning electron microscope,
3.2.5 TEM—transmission electron microscope.
NOTE1—Standardterminologyrelatingtocarbonblackcanbefoundin
Terminology D3053.
4. Summary of Practice
4.1 This practice describes the procedures and protocols to
follow in order to collect fugitive emission/environmental
samples and identify if these samples contain materials con-
sistent or inconsistent with manufactured carbon black (re-
ferred to simply as carbon black).
4.2 Section 6 provides guidelines for proper sampling and
handling of fugitive emission/environmental samples. Section
7 describes the analysis of the sample using transmission
electron microscopy (TEM). This analysis is critical in deter-
miningifthecollectedsampleisconsistentorinconsistentwith
the morphology of carbon black. Use of this analysis is
mandatory in applying this practice. Section 8 describes
additional ancillary techniques that may be included in a
sample analysis for purposes of providing supporting informa-
tion as to the nature of the sample material. These are
situation-dependent methods and can provide critical identifi-
FIG. 1 Block Diagram of Suggested Analysis Scheme for
cation information in certain cases. Samples
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D6602 − 03b (2010)
6.2.2 Sticky tape (Scotch Crystal Clear Tape, No. 25 or However,thesesamplesalwaysrequirethoroughidentification
equivalent). taken at the time of sample collection.
6.2.3 Petri Dishes or Polyethylene Bags.
6.6 It is advisable in the case of repeated incidents to clean
6.3 Samples are to be collected by the following two the surface between sampling.
techniques in accordance with 6.3.1 and 6.3.2. Precautions
should be taken to carefully collect, handle, and transport
7. Examination by Transmission Electron Microscopy
samples in a manner that will not cause further contamination.
(TEM)
6.3.1 Technique I:
7.1 Summary of Test Method:
Collect the sample by rubbing the surface to be sampled with
7.1.1 This test method is a mandatory evaluation of the
apre-weighedpolyesterballorglassfiberfilterpadwithalight
aciniform materials present in the sample to determine primar-
back-and-forth motion to remove surface particulates and
ily if their morphology is consistent with grape-like or branch-
solids. Do not try to remove “old” or aged contaminants from
likestructurestypicallyassociatedwithcarbonblackandsoots.
the surface. Light pressure on the ball or pad should be
Inordertodiscriminatediscretemorphologicalparameters,the
sufficient. Place the exposed ball or pad in a plastic bag and
resolving power of a TEM is required. In addition to TEM
label.
examination, the ancillary methods in accordance with Section
6.3.2 Technique II:
8 may provide supporting information as to the nature and
Remove particulates and solids from surfaces by placing an
amount of the material.
appropriate length of sticky tape on the surface to be sampled.
7.1.2 Thesampleisextractedintochloroformbysonication.
Carefullyremovethetapeandplaceacrossapetridishopening
Theresultingsuspensionisdepositedontoapreparedsubstrate
orinapolyethylenebag.Allsamplescollectedmustbeclearly
attached to a 200 or 300-mesh copper grid. The grid is placed
identifiedatthetimeofcollection.Thistechniquemaybeused
into the transmission electron microscope (TEM) and repre-
for samples intended for further examination via light micros-
sentativefieldsareexamined.Theaciniformmaterialsarethen
copy or X-ray spectroscopy or both.
evaluated for overall morphology.
6.3.3 All collected samples must be clearly identified at the
7.2 Apparatus and Chemicals:
time of collection. Measure the surface area sampled to the
nearest 60.25 cm (each measurement has to be taken to the 7.2.1 Transmission Electron Microscope, equipped with a
nearest 60.5 cm) and record the measurement in Table 1. suitable camera.
ThesesamplesmaybeusedformicroscopyandTGAanalysis.
7.2.2 Ultrasonic Bath or Ultrasonic Probe, of satisfactory
Please note that if TGA analysis is a possibility, the samples power to disperse the particles.
should be collected on the fiber pad instead of the polyester
7.2.3 Copper TEM Grids, 3-mm 200 or 300-mesh, with
ball.
carbon substrate.
7.2.4 Scissors.
6.4 At the time of sample collection, complete a sampling
7.2.5 Glass Test Tubes, 10 by 75 mm, or Glass Vial,3by5
andmeteorologyrecord(Table2)andalsocompleteachainof
cm.
custody record (Table 1).
7.2.6 Pipettes, disposable.
6.5 This practice does not preclude examination of samples
7.2.7 Chloroform, spectrophotometric grade.
collected by other means than the preceding, such as polyeth-
7.2.8 Polyester Balls or Glass Fiber Filter Pad.
ylene glove wipes, filter paper, samples of clothing, and so
forth, or a large sample taken in other containers at a spill site. 7.3 Procedure:
TABLE 1 Chain of Custody Record
Surface Area
Sample ID Date Sampled Sampled By Sample Container Comments
Sampled
1.
2.
3.
4.
5.
Sample
Relinquished By Received By Time Date Reason for Change:
Number
1.
2.
3.
4.
5.
Comments:
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D6602 − 03b (2010)
TABLE 2 Sampling and Meteorology Record
Sample Identification Number: ___________________________________________________________
Complainant: _________________________________________________________________________
Date of Complaint: ____________________________________________________________________
Complainant Phone Number: ____________________________________________________________
Complainant Address: __________________________________________________________________
Nature of Complaint (What, when, where):
.
Weather Data (Wind speed and direction during time of occurrence):
Source of Weather Data:
Plant Upsets Reported (During time of occurrence):
Other Area Environmental Releases (During time of occurrence):
7.3.1 Snipoffanappropriatesoiledportionofthepolyester/ 7.4 Material Identification:
cotton ball or fiber filter pad with a clean pair of scissors and 7.4.1 Classify the aggregates as being consistent with or
place in a freshly cleaned test tube or vial. inconsistent with the morphology of aciniform material. Car-
7.3.2 Add1to4cm ofchloroformtoatesttubeor10to20 bon black and some soot(s) are considered to contain be
cm to a glass vial until the entire sample is totally immersed aciniform in nature.
in chloroform.
NOTE2—Itishighlyrecommendedtotakeintoconsiderationthegrades
7.3.3 An ultrasonic probe or bath may be used to disperse
of carbon black manufactured in the area sampled. If acinoform material
the material into chloroform. If an ultrasonic probe is used, set
is found in the sample, it is advisable to also examine possible manufac-
tured carbon blacks from the area to be used as controls versus the
thevialintoacontainerfilledwithiceandwater.Ultrasonicate
environmental sample.
a sufficient amount of time (typically 10 min) to disperse the
material.Ifthesampleunderexaminationisnotdispersedwell, 7.4.2 Iftheaggregatesareaciniform,thencontinuewiththe
re-prepare the sample using more ultrasonic energy or dilute identification process. Examine the overall morphology of the
the suspension. aggregate in the magnification range of 30 000× to 50 000×
7.3.4 Place a copper grid with the carbon substrate upward and examine the microstructure of the primary particles in the
on a filter membrane. Place the filter membrane in a hood. range of 100 000×. In support of the analysis, it is recom-
7.3.5 Using a volumetric pipette, deliver from 5 to 10 mm mended to generate phot
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