1、Designation: D 6602 03bStandard Practice forSampling and Testing of Possible Carbon Black FugitiveEmissions or Other Environmental Particulate, or Both1This standard is issued under the fixed designation D 6602; the number immediately following the designation indicates the year oforiginal adoption
2、or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.1. Scope1.1 This practice covers sampling and testing for distin-guishingASTM type carbo
3、n black, in the N100 to N900 series,from other environmental particulates.1.2 The values stated in SI units are to be regarded asstandard. The values given in parentheses are for information.1.3 This standard may involve hazardous materials, opera-tions, and equipment. This standard does not purport
4、 toaddress all of the safety concerns, if any, associated with itsuse. It is the responsibility of the user of this standard toestablish appropriate safety and health practices and deter-mine the applicability of regulatory limitations prior to use.1.4 This practice requires some degree of expertise
5、 on thepart of the microscopist. For this reason, the microscopist musthave adequate training and substantial on-the-job experience inidentifying the morphological parameters of carbon black. Insupport of this analysis, Donnets book2is highly recom-mended to be used as a technical reference for reco
6、gnizing andunderstanding the microstructure of carbon black.2. Referenced Documents2.1 ASTM Standards:3D 1619 Test Methods for Carbon BlackSulfur ContentD 3053 Terminology Relating to Carbon BlackD 3849 Test Method for Carbon BlackMorphologicalCharacterization of Carbon Black Using Electron Micros-c
7、opy3. Terminology3.1 Definitions of Terms Specific to This Standard:3.1.1 aciniformshaped like a cluster of grapes.3.1.1.1 DiscussionThe spheroidal primary particles ofcarbon black are fused into aggregates of colloidal dimensionforming an acinoform morphology.3.1.2 aciniform carboncolloidal carbon
8、having a mor-phology consisting of spheroidal primary particles (nodules)fused together in aggregates of colloidal dimension in a shapehaving grape-like clusters or open branch-like structures3.1.3 carbon black, nan engineered material, primarilycomposed of elemental carbon, obtained from the partia
9、lcombustion or thermal decomposition of hydrocarbons, exist-ing in the form of aggregates of aciniform morphology whichare composed of spheroidal primary particles characterized byuniformity of primary particle sizes within a given aggregateand turbostratic layering within the primary particles.3.1.
10、3.1 DiscussionParticle size and aggregate size (num-ber of particles per aggregate) are distributional properties andvary depending on the carbon black grade. Transmissionelectron micrographs shown in Annex 1 of Practice D 6602demonstrate that while particle and aggregate sizes vary greatlywithin a
11、given grade of carbon black, the primary particle sizeis essentially uniform within an individual aggregate.3.1.4 chain of custodya document describing the condi-tion of a sample during its collection, analysis, and disposal.3.1.5 chara particulate larger than 1 m made by incom-plete combustion whic
12、h may not deagglomerate or disperse byordinary techniques, may contain material which is not black,and may contain some of the original materials cell structure,minerals, ash, cinders, and so forth.3.1.6 fugitive dusttransitory, fleeting material comprisedof particulates foreign to the surface of de
13、position.3.1.7 fungus, sooty mold, mildewparticulates from a su-perficial growth that grows on living and decaying organicmatter.3.1.8 mineral and urban dustairborne, naturally occurringinorganic particulates inherent to the area.3.1.9 pollenparticulates from a mass of microspores in aseed plant.3.1
14、.10 rubber dustfinely divided soft particulates abradedfrom rubber.1This practice is under the jurisdiction of ASTM Committee D24 on CarbonBlack and is the direct responsibility of Subcommittee D24.81 on Carbon BlackMicroscopy and Morphology.Current edition approved Dec. 1, 2003. Published January 2
15、004. Originallyapproved in 2000. Last previous edition approved in 2003 as D 660203a.2Hess, W.M. and Herd, C.R., Carbon Black Science and Technology, Edited byDonnet, J.B., Bansal, R.C., and Wang, M.J., Marcel Dekker, Inc., New York, NY,1993, pp. 89173.3For referenced ASTM standards, visit the ASTM
16、website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United
17、States.3.1.11 samplea small fractional part of a material or aspecified number of objects that are selected for testing,inspection, or specific observations of particular characteris-tics.3.1.12 soota submicron black powder generally producedas an unwanted by-product of combustion or pyrolysis. Itco
18、nsists of various quantities of carbonaceous and inorganicsolids in conjunction with adsorbed and occluded organic tarsand resins.3.1.12.1 DiscussionThe carbonaceous portion also is col-loidal and often has the acinoform morphology. Soot may haveseveral carbon morphologies. Examples of soot are carb
19、onresidues from diesel and gasoline engines, industrial flares,sludge pits, burning tires, and so forth.3.1.13 sticky tapea section of tape with a sticky, solvent-soluble adhesive used in the collection of particles fromsurfaces.3.1.14 surfacethe outer surface, facing, or exterior bound-ary of an ob
20、ject capable of supporting carbon and other fugitiveand natural occurring dusts and particulates.3.1.15 turbostratica type of graphitic crystallographicstructure in which there is no symmetry along the z-axis.3.2 Acronyms:3.2.1 EDSenergy dispersive spectroscopy associated withSEM and TEM for the ide
21、ntification of elemental composition,3.2.2 LMlight microscope,3.2.3 PLMpolarizing light microscope,3.2.4 SEMscanning electron microscope,3.2.5 TEMtransmission electron microscope.NOTE 1Standard terminology relating to carbon black can be found inTerminology D 3053.4. Summary of Practice4.1 This prac
22、tice describes the procedures and protocols tofollow in order to collect fugitive emission/environmentalsamples 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 prope
23、r sampling andhandling of fugitive emission/environmental samples. Section7 describes the analysis of the sample using transmissionelectron microscopy (TEM). This analysis is critical in deter-mining if the collected sample is consistent or inconsistent withthe morphology of carbon black. Use of thi
24、s analysis ismandatory in applying this practice. Section 8 describesadditional ancillary techniques that may be included in asample analysis for purposes of providing supporting informa-tion as to the nature of the sample material. These aresituation-dependent methods and can provide critical ident
25、ifi-cation information in certain cases.4.3 A block diagram is presented in Fig. 1 to give a possiblescheme to follow in performing this analysis. However, itshould be noted that this scheme is a suggestion, not arequirement.5. Significance and Use5.1 Particulate emissions are major contributors to
26、air con-tamination in industrial and urban environments. Soot isformed as an unwanted by-product of combustion and conse-quently varies widely with the type of fuel and combustionconditions. Carbon black, on the other hand, is purposelyproduced under a controlled set of conditions. Therefore, it isi
27、mportant to be able to distinguish carbon black from soot, aswell as other environmental contaminants.6. Sampling6.1 The area to be sampled must be representative of thecontaminated area. For sampling, choose an area that appearsto contain black particulates. The same general surface shouldbe used f
28、or gathering all test samples for each property sitelocation.6.2 Equipment:6.2.1 Polyester/Cotton Balls or Glass Fiber Pads.6.2.2 Sticky tape (Scotch Crystal Clear Tape, No. 25 orequivalent).6.2.3 Petri Dishes or Polyethylene Bags.6.3 Samples are to be collected by the following twotechniques in acc
29、ordance with 6.3.1 and 6.3.2. Precautionsshould be taken to carefully collect, handle, and transportsamples in a manner that will not cause further contamination.6.3.1 Technique I:Collect the sample by rubbing the surface to be sampled witha pre-weighed polyester ball or glass fiber filter pad with
30、a lightFIG. 1 Block Diagram of Suggested Analysis Scheme forSamplesD 6602 03b2back-and-forth motion to remove surface particulates andsolids. Do not try to remove “old” or aged contaminants fromthe surface. Light pressure on the ball or pad should besufficient. Place the exposed ball or pad in a pla
31、stic bag andlabel.6.3.2 Technique II:Remove particulates and solids from surfaces by placing anappropriate length of sticky tape on the surface to be sampled.Carefully remove the tape and place across a petri dish openingor in a polyethylene bag. All samples collected must be clearlyidentified at th
32、e time of collection. This technique may be usedfor samples intended for further examination via light micros-copy or X-ray spectroscopy or both.6.3.3 All collected samples must be clearly identified at thetime of collection. Measure the surface area sampled to thenearest 60.25 cm2(each measurement
33、has to be taken to thenearest 60.5 cm) and record the measurement in Table 1.These samples may be used for microscopy and TGA analysis.Please note that if TGA analysis is a possibility, the samplesshould be collected on the fiber pad instead of the polyesterball.6.4 At the time of sample collection,
34、 complete a samplingand meteorology record (Table 2) and also complete a chain ofcustody record (Table 1).6.5 This practice does not preclude examination of samplescollected by other means than the preceding, such as polyeth-ylene glove wipes, filter paper, samples of clothing, and soforth, or a lar
35、ge sample taken in other containers at a spill site.However, these samples always require thorough identificationtaken at the time of sample collection.6.6 It is advisable in the case of repeated incidents to cleanthe surface between sampling.7. Examination by Transmission Electron Microscopy(TEM)7.
36、1 Summary of Test Method:7.1.1 This test method is a mandatory evaluation of theaciniform materials present in the sample to determine prima-rily if their morphology is consistent with grape-like orbranch-like structures typically associated with carbon blackand soots. In order to discriminate discr
37、eet morphologicalparameters, the resolving power of a TEM is required. Inaddition to TEM examination, the ancillary methods in accor-dance with Section 8 may provide supporting information as tothe nature and amount of the material.7.1.2 The sample is extracted into chloroform by sonication.The resu
38、lting suspension is deposited onto a prepared substrateattached to a 200 or 300-mesh copper grid. The grid is placedinto the transmission electron microscope (TEM) and repre-sentative fields are examined. The aciniform materials are thenevaluated for overall morphology.7.2 Apparatus and Chemicals:7.
39、2.1 Transmission Electron Microscope, equipped with asuitable camera.7.2.2 Ultrasonic Bath or Ultrasonic Probe, of satisfactorypower to disperse the particles.7.2.3 Copper TEM Grids, 3-mm 200 or 300-mesh, withcarbon substrate.7.2.4 Scissors.7.2.5 Glass Test Tubes,10by75mm,orGlass Vial,3by5cm.7.2.6 P
40、ipettes, disposable.7.2.7 Chloroform, spectrophotometric grade.7.2.8 Polyester Balls or Glass Fiber Filter Pad.7.3 Procedure:7.3.1 Snip off an appropriate soiled portion of the polyester/cotton ball or fiber filter pad with a clean pair of scissors andplace in a freshly cleaned test tube or vial.7.3
41、.2 Add 1 to 4 cm3of chloroform to a test tube or 10 to 20cm3to a glass vial until the entire sample is totally immersedin chloroform.7.3.3 An ultrasonic probe or bath may be used to dispersethe material into chloroform. If an ultrasonic probe is used, setthe vial into a container filled with ice and
42、 water. Ultrasonicatea sufficient amount of time (typically 10 min) to disperse thematerial. If the sample under examination is not dispersed well,re-prepare the sample using more ultrasonic energy or dilutethe suspension.TABLE 1 Chain of Custody RecordSample ID Date Sampled Sampled BySurface AreaSa
43、mpledSample Container Comments1.2.3.4.5.SampleNumberRelinquished By Received By Time Date Reason for Change:1.2.3.4.5.Comments:D 6602 03b37.3.4 Place a copper grid with the carbon substrate upwardon a filter membrane. Place the filter membrane in a hood.7.3.5 Using a volumetric pipette, deliver from
44、 5 to 10mm3(L) of the suspension onto the center of the grid and letthe solvent evaporate. When the liquid drop is placed on thegrid it overlaps onto the filter paper resulting in a spot size thatis larger than the size of the grid.7.3.6 If the spot is exceptionally light, repeat 7.3.5 withadditiona
45、l drops. Place the remaining suspension back into thetest tube, stopper, and place in the hood.7.3.7 Place the grid on the microscope sample holder andinsert the holder into the column.Atypical accelerating voltageof 80 KV is sufficient for carbon black. Determine an appro-priate magnification for t
46、he particles between 5 000 and100 0003 magnification.7.4 Material Identification:7.4.1 Classify the aggregates as being consistent with orinconsistent with the morphology of aciniform material. Car-bon black and some soot(s) are considered to contain beaciniform in nature.NOTE 2It is highly recommen
47、ded to take into consideration thegrades of carbon black manufactured in the area sampled. If acinoformmaterial is found in the sample, it is advisable to also examine possiblemanufactured carbon blacks from the area to be used as controls versus theenvironmental sample.7.4.2 If the aggregates are a
48、ciniform, then continue with theidentification process. Examine the overall morphology of theaggregate in the magnification range of 30 0003 to 50 0003and examine the microstructure of the primary particles in therange of 100 0003. In support of the analysis, it is recom-mended to generate photomicr
49、ographs of representative fields.Refer to Annex A1 to aid in particle identification.7.4.3 Elemental identification of the aciniform material isassumed to be predominately carbonaceous. If this is notknown, this can be accomplished using an X-ray spectrometerassociated with the electron microscope. If the aciniformparticles are not carbonaceous, then proceed to the reportsection.7.4.4 Morphology of Aggregates:7.4.4.1 Assess how the primary particles are joined togetherin the aggregates, that is, the dimensions (diameter and length)of the necks between
