Document jLk95gp3abRExM83Qp4ozKZZ

'A. G, Armour J. 1, Dye J. C, Fang E. B, FitzGerald J. Hochberg B. G. Hunt H. L. Jakubauskas D. M. Marsh P. H. Pettit W. Pregmon J. A. Simms J, J, Troy J. A. Vasfa S. Wu, F. F; Huppe - - - -7 - F. A. Fiuegge - C. W. Bullock - C, Ambrosio - T. P. Anderson L, W. Crissey - F. M. Gavin R. A. Hiss - R. O. Kenworthy - A. F. Nugent - T. A. Reftig - R. J. Sheppard - C. L. Steiner R, D. Vest -- J. L, Allen - V, Ananthakrishnan - J. A, Antonelli - W. S, Armstrong L. A. Becton G. C, Bell, Jr, R. D. Breazeale - D. C, Carba ugh J, G, Carson - M. M. Cobum B, V, Gregorovich P. Demchur - RECEIVED F&F, Exp, Sta. F&F, Exp. Sta. F&F, Exp. Sta, F&F, Exp. Sta. F&F, Exp. Sta. F&F, Exp. Sta F&F, Exp. Sta. * F&F, Exp. Sta, F&F, Exp. Sta, F&F, Exp. Sla. F&F, Exp. Sta". F&F, Exp. Sta. F&F, Exp. Sta. F&F, Exp. Sta. Eng. Physics Lab. Exp. Sta. Fairfield Troy Lab. Troy Lab. Troy Lab. Troy Lab, Troy Lab. Troy Lab, Troy Lab, Troy Lab. Troy Lab. Troy Lab. Troy Lab. Troy Lab. Marshall Lab Marshall Lab. Marshall Lab. Marshall Lab. Marshall Lab, Marshall Lab. Marshall Lab. Marshall Lab. Marshall Lab. . Marshall Lab. Marshall Lab. Marshall Lab. DEC, 3 1975 ..aARSHMJL LAB. f il e sJ, A, Devlin - A, V. Seance!la - C. E, DeBoer - G. L, Evans J. W. Gkonos W. C. Golton - D. M. Gowing H. Halpin - H. P. Hanisch J. H, Hartshorn - G. W, Hiddemen - S. Hochberg - R. W, Laurrell Y, K. Lee ? G. E, Lewis ~ R. G. Lindsey O. C. C, Lin - G. W. Mansell - R. L. Manley - E. P. H. Meibohm - M, P. Morse - D. K. Ogg - F. E. Schweitzer - R. J. Shuba - F, J, Shannahan - C. B. Sheridan C. D, Smith - C, M. Smyrk - W. B. Van der Linde E. M. Vary - F. Welfy - J. P. Wineburg - D. T, Wu E. L. Yuan - W, S, Zimmt E, J. Zinser - J. A. Haase - C. W. Johnson - R, L. McFarland 7- W, R, Williamson R, A. Sandsted - Marshall Lab. Marshall Lab, Marshall Lab. Marshall Lab, Marshall Lab. Marshal 1 Lab, Marshall Lab Marshal) Lab. Marshall Lab. Marshal 1 Lab. Marshall Lab. Marshal! Lab, Marshal | Lab. Ma rshal 1 Lab. Marshall Lab. Marshall Lab. Marshall Lab. Marshall Lab. Marshall Lab. Marshall Lab. Marshall Lab. Marshall Lab. Marshall Lab. Marshall Lab. Marshall Lab. Marshall Lab. Marshall lab. Marshall Lab. Marshal! Lab. Marshall Lab Marshall Lab. Marshall Lab. Marshall Lab, Marshal! Lab. Marshal! Lab, Marshall Lab. Chicago Plant Parlin Plant Toledo Plant Pfasti cs. Chest. S. S. Francisco File: 1815 Marshall R&D Laboratory November 25, 1975 FABRICS & FINISHES MARSHALL R&D LABORATORY LABORATORY TECHNICAL SERVICES " MON i i iLY RLiORT NOVEMBER, 1975 OSHAAND RELATED GOVERNMENTAL REGULATIONS R. M. KIRKPATRICK Occupational Cancer To avert emergency situations such as those associated with vinyl chloride, methyl butyl ketone, and arsenic, the National Institute for Occupational Safety and Health (NIOSH) is beefing up.its research programs on occupational cancer for the next three fiscal years. NIOSH hopes to help decrease the number of newly induced occupational cancers through,a program of surveillance, industry-wide studies, and laboratory research. The projected budget for the program is $6.8 million for 1976 and $11 million for 1977. NIOSH plans 15 industry-wide studies to be conducted when there is evidence of high rates of cancer among certain occupational groups or when animal studies indicate a particular substance used in the workplace causes cancer. NIOSH is also planning to develop a use-permit and registration system as part of its recommended criteria for standards on carcinogens. Since October 1974 the National Cancer Institute has issued alerts on the following substances: e Ethylene dihromide e Chlordane e Heptachlor Trichloroethylene NIOSH has already taken action on some of these and is studying others: Chloroprene e Asbestos Chromate pigments RMK/meg 11/25/75 7 N42520.01 DUP030025368 AIR TRANSPORTATION OF HAZARDOUS MATERIALS R, M. KIRKPATRICK On January 1, 1976 the U.S. Department of Transportation's new regulations on closed-cup flash point classification of materials becomes mandatory. F. & F. has been voluntarily shipping under these rules since July 1, 1975. However, we feel it is imperative to again emphasize-that every F. & F. employee is respons ible for complying with existing regulations. Heavy fines, and or imprisonment, can be levied on an individual employee for violation of the rules. At Marshal! Laboratory we offer assistance by requiring all air shipments to be authorized by Bob Kirkpatrick or in his absence, Sal Mansi , Hazardous materials shall not be carried as baggage. For your protection, special papers can be provided at the Philadelphia Works Office which will enable you to transport non-hazardous materials. In any event it is an F. & F. Departmental policy not to ship by air any corrosive, oxidizing, poisonous. Or compressed gas materials. Flammable, combustible and unregulated materials may be shipped when properly classified and packaged. Under no circumstances are laboratory personnel to deliver shipments directly to the airport without proper classification, packaging and labeling papers. RMK/meg 7 N42520.02 DUP030025369 GAS CHROMATOGRAPHY/MASS SPECTROMETRY R. J, SHUBA Problems With Trace Level Organics: Some recent analytical requests to identify low-level concentrations of organic materials required the use of gas chromatography/mass spectrometry equip-, ment outside of our own laboratory. At best, only one or two of the components present in each sample could be identified with our present equipment. Two different samples of Ft, Madison pond water were analyzed by GC/ MS. The first sample was analyzed using a DuPont Model 491 GC/MS/Data System, (CR & D, Experimental Station). A second sample was analyzed using the HewlettPackard Model 5980 GC/M5/Data System, (Elastomers, Experimental Station). The organic materials for both samples were absorbed on activated charcoal and recovered in CS2. The following components were identified in the wafer sample (AR-75-10-3185) using the duPont 491. diethyl ether methyl ethyl ketone fefrachloroefhylene toluene xylenes 1,1,2 trichloroefhane x-methyl dihydroindene cellosolve acetate C3 alkyl benzenes C4 alkyl benzenes naphthalene C5, C6/ C7 monobasic acids Note: COS (carbonyl sulfide) and CHCI3 (chloroform) were identified as impurities in CS2. The following components were identified in the water sample (AR 75-11-3360) using the Hewlett Packard 5980. carbon tetrachloride* chloroform* methylene chloride tetrachloroethylene toluene xylene 2 - methyl norbornene** vinyl cyclohexene ** * probable impurities in CS2 ** tentative identifications (interference from CS2) RJS/bg 11/25/75 7 N42520.03 DUP030025370 A NEW ENAMEL CROSSLINKER? J. H. HARTSHORN The computer infrared spectral search system along with GPC fractionation has frequently proven invaluable ~ for product analysis,but rare ly as dramatically as shown by a recent high solids enamel study. Survey had found the enamel to be a blend of a styrene-acrylic copolymer and a cellulosic. This package is to be-crossl inked with a hexamethylene diisocyanate adduct. The acrylic appeared to have been extended or reacted with some nitrogenous material which we suspected of being an isocyanate. Attempts to separate the resin with the usual solvents were complete failures. GPC however showed two distinct molecular weight peaks, which we believed would be the CAB and the modified acrylic. The higher molecular weight peak proved to be an unresolved mixture of the acrylic and the cellulosic; while the lower peak showed an unique double carbonyl compound, unlike anything in our files. A computer search of the full 150,000 spectra file provided a perfect spectral match for I, 3-Bis (2-Hydroxy ethyl)-5,5-Dimethyi Hydantoin. O = C - tjl-CH2 - CH2 - OH (CH3^- C-O CH2 - CH2 - OH. There is little doubt that this material is present, since other high solids samples from the same producer also showed the same compound. Without the aid of both GPC fractionation and computer IR file searching the identification or even detection of this compound would have been impossible. JHH:mb 11/20/75 7 N42520.04 D UP030025371 OSHA FILTERS LEAD AND CHROMIUM DETERMINATIONS IN AIR PARTICULATE SAMPLES_____ J, A. DEVLIN, JR. Methods have been established for the determination of lead and chromium in air particulate samples of lead chromate type pigment dusts, including Krolor, but excepting basic lead silicochromate. A method has also been developed for these two elements in paints containing lead chromate type pigments, excepting Krolor and basic lead silicochromate. Work is currently progressing on the Krolor-pigmented paints and we are now recovering about 82-90% of both the lead and chromium contents. Because of the small incidence of use of basic lead silicochromate (1500 ^ of both W-666 and W-698 from January I to September 30, 1975 and probably less next year) we are not planning at present to expend any effort here on methods for either pigment dust or paint spray analysis. Analysis of air particulate samples involving lead chromate type pigments presents a special problem. Ordinarily, different procedures in sample preparation are employed for each constituent sought, but the uniqueness of the particulate sample precludes such multi-faceted approach, and a method must be synthesized or invented which is specific for the sample type so that all the desired constituents may be determined from the one work-up. Other difficulties are sometimes introduced, too, by the OSHA-specifJed MCE filters, and methods of ashing, necessary when the sample is a paint spray, are much more critical in these filter analyses than in examination of a pigment, pig ment fraction, or whole paint. All in all, it appears that individual methods, tailored to fit the specific sample type, will be necessary for each new type en countered. ^JAD,Jr./mb 11/19/75 I { j \ >; j !* ; f j 7 N42520.05 DUP030025372 LIQUID CHROMATOGRAPHY E. P. H'. MEIBOHM Work has now started to employ the DuPont 830 liquid chronr* graph. The first runs made to become familiar with instrument operation included the separation of benzene, toluene, and xylene using a Permaphase ODS column and MeOH/HjO eluents. In a second series of tests, a mixture of benzyl alcohol, methyl benzoate, benzyl acetate, methyl cinnamate, and dimethyl isophthalate was separated on a Permaphase ODS column using a linear gradient with H-O as the A solvent and 25% MeOH/75% H2O as the B solvent. We are now trying to find a way to separate MDA from epoxies in Wellex. The molecular weight of the epoxies may be too high for a simple LC procedure and some sort of preliminary extraction may be needed to precede the LC work. r. r. w EPHMrmb 7 N42520.06 DUP030025373 GEL PERMEATION CHROMATOGRAPHY, LIQUID CHROMATOGRAPHY E. P. H, ME IBOHM Gel Permeation Chromatography Values For Polydispersity: The significance of the polydispersity factor, d, in GPC is not always understood. By definition d - Mw/Mn and must always be I or greater. For most polymers d = 2 - 3. Several computer normalized GPC chromatograms are attached to illustrate typical distributions. In the polystyrene example, d - Mw/Mn = 95900/88600 = 1.08. According to the suppl ier d should be less than 1.06. Our slightly greater value may be due to the lack of a column broad ening correction in the present computer program. Note that Mw is slightly less than the peak molecular weight. Mw is greater than the peak molecular weight for a symmetrical peak but not necessarily so for a skewed peak. Newly Acquired High Pressure Liquid Chromatography: In liquid chromatography the components of our system - a DuPont 830 liquid chromatograph, a DuPont 837 spectrophotometer, and an LDC two pen recorder have been set up. We are calibrating and otherwise getting acquainted with the operation of these instruments. An LDC refractive index detector will be worked in, Currently, we shall begin by setting up procedures for liquid chroma tography and then add competence in high performance gel permeation chromato graphy (HPGPC). E, P. H. Meibohm 7 N42520.07 D U PO3002 5374 N42520.08 DUP030025375 TILLEY 75-2127 10546-83--A ~ " "~ ^GPC^OLT7Em"r"TT.TmiTfDROFOR'Afr^----- ^ C T : r> f*-> ?.>;? 3 .C 0 3.?0 4,00 4.RC <5.00 ---------------------- --- .:r ? r .00 2 .5 0 3 .0 0 3.50 < .0 0 4 .5 0 5 .0 0 S. 5' 6 .0 0 6 .5 0 <f:* DUP030025378 ANALYSIS OF PURPLE STAINS ON RED ENAMEL J. P, WINEBURG Investigations were recently conducted into the cause of purple stains appearing on equipment painted with red enamel at New Holland, Pa. Scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDXA), and electron probie analysis (EPA) of stained and unstained surfaces showed that the stained areas contain comparatively larger amounts of sulfur. The valence state of the sulfur was found to be +6 by ESCA (electron spectroscopy for chemi cal analysis), indicating that the sulfur is present as sulfate. These results indi cate that the stains are caused by atmospheric pollution interacting with dew to produce acidic droplets which attack the pigment in the enamel. SEM, EDXA, and EPA were performed by W. E. Gresham of Micron, Inc., Wilmington, Delaware. ESCA work was done by R. S. Swingle, II of CR & D. "KAPTON" ADHESION PROBLEM ESCA (electron spectroscopy for chemical analysis) was recently used to investigate a problem involving "Kapton" polyimide film adhesively bound to specially treated copper plate, "Kapton" separation from the metal was occuring and appeared to be a result of either adhesive failure or "Kapton" film failure. How ever, ESCA analysis conclusively showed that "Kapton" separation was a result of co hesive failure of the Sn/Pb solder electroplated on the copper; neither the adhesive nor the "Kapton" was involved. The copper plate had been electrocoated with 60/40 Sn/Pb solder, etched with ammonium persulfate, rinsed with water, and coated with a thin Sn immersion coating. The adhesive used to apply the "Kapton" was predominately acrylic (35% acrylonitrile/5% methacrylic acid/60% butyl acrylate). Three samples were examined by ESCA: (I) the metal surface after tinning but before the "Kapton" was applied, (2) the under side of a piece of "Kapton" peeled from the metal strip, and (3) the metal surface ex posed by peeling off the "Kapton. " The most important sample proved to be the under side of the peeled "Kapton. " It showed the presence of substantial amounts of Sn, smaller amounts of Pb, but only trace amounts of nitrogen. Had either the adhesive or the "Kapton" failed, substantial amounts of nitrogen would have been detected, ESCA analyses were performed by R. S. Swingle, II, of CR & D, * Iti: I I i i i I t JPW:mb 11/19/75 7 N42520.09 DUP030025379 MICROSCOPY G, W. HIDDEMEN DISPERSION QUALITY TEST; A series of color photomicrographs were taken for T. Nelson of the Manufacturing Support Group, These photographs will be used to illustrate the re sults of a new spot test that shows dispersion quality. The photographs below show a good and bad example of 547-5112 Dalamar Yellow Dispersion, in the bad dispersion you see a separation of the vehicle from pigment due to particle size. The photographs were taken with the Bquseh & Lamb dissecting micro scope using a I0X power. GWH:mb Bad Dispersion Good Dispersion N42520.1 DUP030025380