THE NEWSLETTER OF ASTM COMMITTEE D24 ON CARBON BLACK 12.0107 the 6 Carbon Carbon Aggregate C www.astm.org SUMMER 2011 VOL. 11, Number 1 Using D6602-03b to Investigate Dark ASTM Technical Committee D24 Environmental Particles on Carbon Black By J. R. MIllette (MVA Scientific Consultants) Main Committee Officers: INTRODUCTION and 100,000 times and above. The TEM is equipped he ASTM Standard Practice D6602- with a camera and X-ray energy dispersive analysis 03b: “Sampling and Testing of Possible equipment (EDS). CHAIRMAN TCarbon Black Fugitive Emissions or Other Ricky W. Magee Environmental Particulate, or Both,” provides an ANALYSIS PROCEDURES Columbian Chemical Co. excellent framework for the microscopy studies The initial light microscopy examination including phone: 770.792.9472 necessary to determine the identity and possible PLM is used to sort out the various particle types rmagee@columbian source of dark surface contamination including that present on the surface and to determine the chemicals.com caused by carbon black. The ASTM Standard Test approximate relative percentages by volume of the Method D3274 and the ASTM Standard D4610 deal different components. TEM analysis is then used in with discoloration and deterioration of paint films conjunction with energy dispersive x-ray analysis to VICE- and are also useful in some cases. identify the “fine” (small) size fraction of the dark CHAIRMAN particulate and is especially useful in differentiating John A. Bailey Jr. Continential Carbon Co. When the question arises about the identity of between carbon black and various carbon soots. phone: 281.391.1336 a “sooty”-appearing contamination on outdoor Carbon soots and carbon blacks are characterized [email protected] surfaces, a combination of the mandatory sections by their aciniform (grape-like clusters) morphology of Practice D6602 that involve transmission electron microscopy (TEM) and the non-mandatory microscopical examination by stereomicroscope and SECRETARY polarized light microscopy (PLM) provides a very Thomas D. Powell useful approach. The following microscopy tools, Evonik Degussa listed in D6602, are used: a stereomicroscope capable Corporation of 40 to 60x magnification, a PLM equipped with phone: 330.665.5120 thomas.powell@ objectives in the 10 to 50x range of magnification evonik.com (for a total magnification between 40 and 500x), and a TEM capable of magnifications between 10,000 INSIDE THIS ISSUE Figure 1. TEM Image of Aciniform Carbon typical of carbon black and some carbon soots. Using D6602-03b to Investigate Dark Environmental Pariculate. 1 John A. Bailey receives ASTM’s highest award, the Award of Merit. 4 (Figure 1), elemental composition and range of D24 Meeting Schedule. 5 primary particle size distribution. Carbon black ASTM Carbon Black Committee Forms New Subcomitee on Environment, is distinguished by its characteristic morphology Health and Safety. 6 (size, shape, and appearance), simple elemental New U.S. EPA Regulations Lead to ASTM Standard for Carbon composition (Figure 2) and controlled (tight) Black Carbon Content. 6 particle size distribution. Soots have a wide range New ASTM Carbon Black Standard Inspired by New U.S. EPA Regulations . 7 of morphologies, elemental compositions and often D24 Activitites . 7 12.0107 6 CARBON AGGREGATE CarbonC wide particle size distributions (Figure 3). It is important to note that while some carbon blacks exhibit turbostratic layering within the primary particles, other aciniform black carbon particles including diesel exhaust and candle soot also exhibit turbostratic layering (Figure 4). The investigation of outdoor dark stains or disfigurement begins with an examination by stereomicroscope followed by a PLM analysis. At this stage, if the major cause of the darkening is determined to be biological in nature (fungal or algal), no further analysis may be necessary. If a significant amount of fine black carbon material is determined by PLM, additional analysis by TEM-EDS is necessary to confirm the presence of aciniform soot and determine if it is consistent with carbon black. EXAMPLES The value of using the combination of the PLM/TEM analysis procedures described in D6602 is illustrated in results of 4 different types of samples. The Carbon Aggregate Volume 11, Number 1 Summer 2011 Editor Jeff Melsom Michelin Americas Research Co. 864.422.4079 [email protected] Assistant Editor George Joyce Columbian Chemicals Co. 770.792.9467 [email protected] Figure 2. X-ray spectrum from a carbon black particle (above). X-ray spectrum from a carbon soot particle(below). Designer Jake Palmer Sample VBNGF3 was collected from a vehicle Sample H5TG80 was collected from the ASTM Staff Manager hood. The PLM analysis showed that the siding of a building near a carbon black plant. Joe Koury particulate collected on a wipe was primarily The PLM analysis showed that the particulate 610.832.9804 composed of fungal (mold) material (70- was primarily composed of soot in the form [email protected] 80%), soil minerals (10-20%), rubber particles of aciniform carbon material (80-90%), Any questions and/or comments concerning the (5-15%) and soot including both char and soil minerals (5-10%), and plant fragments activities of ASTM D24, please call either the main aciniform carbon (trace – 1%). There were (1 - 5%). There was a trace level (less than committee officers, or ASTM Staff Manager Joe trace levels (less than 1%) of rust particles 1%) of insect parts. TEM analysis found a Koury at 610.832.9804. and insect parts. TEM analysis found one majority of the aciniform carbon particles The Carbon Aggregate is published semi-annually aciniform carbon particle that was consistent were consistent with carbon black. Carbon by ASTM to provide information about Committee with carbon black. Fungal material was black was determined to be the major cause D24 to the carbon black community. determined to be the major cause of darkening of darkening on the building surface. Copyright © ASTM International, 2011 on the vehicle. 2 SUMMER 2011 www.astm.org 12.0107 6 CARBON AGGREGATE CarbonC Figure 4. High resolution TEM image showing showing turbostratic layering in a paraffin candle soot particle. Distance between the layers is approximately 0.34 nm. CONCLUSION The systematic microscopical investigation of outdoor surface darkening agents involving the non-mandatory stereomicroscope and polarized light microscope examination followed by the mandatory transmission electron microscope procedures in ASTM D6602-03b provides an excellent way to determine the cause of a “sooty” surface problem. REFERENCES ASTM D6602-03b, Standard Practice for Sampling and Testing of Possible Carbon Black Fugitive Emissions or Other Environmental Particulate, or Both, ASTM International, West Conshohocken, PA ASTM D3274-02, Standard Test Method for Evaluating Degree of Surface Disfigurement of Paint Films by Microbial (Fungal or Algal) Growth or Soil and Dirt Accumulation, ASTM International, West Conshohocken, PA Figure 3. Primary particle size distribution from carbon black (above). Primary particle size distribution ASTM D4610-04, Standard Guide for Determining from carbon soot (below). the Presence of and Removing Microbial (Fungal or Algal) Growth on Paint and Related Coatings, ASTM International, West Conshohocken, PA Sample JPR6Y8 was collected from the surface (40-50%), rubber particles (10-20%) and soot of a stone walkway. The PLM analysis showed including both char and aciniform carbon Millette, J.R., P. Few, W. Hill, and M. Ritorto. Sizing Nano-Range Primary Particles in Aciniform that the particulate was primarily composed (20 - 30%). There were trace levels (less than Carbon Aggregates Using ImageJ. Microscope of fungal (mold) material (85-95%) and plant 1%) of plant fragments, pollen, synthetic 54(2):51-59, 2006 fragments (1 - 5%). There were trace levels (less fibers and insect parts. TEM analysis found than 1%) of soil minerals and rubber particles. that approximately half the aciniform carbon Millette, J.R., W. Turner, W.B. Hill, P. Few, and TEM analysis found no aciniform carbon particles were consistent with carbon black. J.P. Kyle. Microscopic Investigation of Outdoor “Sooty” Surface Problems. Environmental particles. Fungal material was determined to be Other soot particles were consistent with the Forensics, 8:37-51, 2007. the major cause of darkening on the walkway. burning of vegetation. The cause of darkening on the mailbox was determined to be a Sample AK72WR was collected from a mixture of mold, soil minerals, rubber, and residential mailbox. The PLM analysis showed black carbon including carbon black and soot. that the particulate was primarily composed of fungal (mold) material (10-20%), soil minerals www.astm.org SUMMER 2011 3 12.0107 6 CARBON AGGREGATE CarbonC John A. Bailey Receives ASTM International Award of Merit ohn A. Bailey was recently awarded City, AL plant. He moved on to become subcommittee is not normally for the faint ASTM International’s Award of Quality Control Manager, SPC Coordinator of heart for it requires a through knowledge JMerit. The Award of Merit is and eventually the company’s Quality Systems and application of statistics. When John the highest society award granted to an Manager. He has held that position for more initially assumed this position his knowledge individual member for distinguished service than 19 years and has been with Continental of statistics was good but has since improved and outstanding participation in ASTM Carbon for more