Document pzQeOq4g69xaweZDrxzjy2Da

CONFIDENTIAL Groin?: z.i-alCz D'vfflf June 25, 1976 PAGE 1 PROBLEM TITLE: Perform quantitative analysis of one-bag samples of'MK-4 and MK-5 (already in Cambridge) SIGNIFICANCE: To determine amount of tremolite present. SPECIFIC CBJECTIVE: Approximation of analysis results which might be obtained by a laboratory facility other than ours.- '* . .. SUGGESTED APPROACH: Perform analysis twice. The first approach utilize methodst equipment, and procedures which CPD laboratory personnel would use based on experience, etc. Second approach to be that (or those), which an outside facility would use (possibly .same as CPD; if different from CPD, possibly more than a single alternate). DEADLINE (Last day information yiH be of value): There is not now an identified deadline. However results are requested within a 30 to 45 day period if practical. DETAILS OF PRQ3LHM: Duecker is familiar with' all' pertinent details. 4 4 P.E.Korenberg, R.H.Locke, R.A.Merther, L.S.Shu, B.R.Williams, J.W.Wolter, E.S.Wood, R.M.Vining,' CFD-T&A, File: 71-048 15171792 REQUEST FOR TECHNICAL SERVICE: CONFIDENTIAL HUMBER: 49189_________________ GROUP: ZONOLITE ACTUAL COST: $2500.00 REPORTING PAT'S: May 26,~ 1977 SUMMARY: Three bags of standard MK-4 product from plant locations in California from Los Angeles, Santa Ana, and Newark), and four MK-5 samples (from Los Angeles, Santa Ana, and Omaha) have been examined for their tremolite content. All seven samples as received showed no detectable tremolite fiber content by x-ray determinations (our detection limit for tremolite is 0.2$). However, the materials were fractioned; glass fibers were mostly retained on a +6 mesh screen, vermiculite was floated off; most of the plaster of Paris was dissolved in water; and, CELIF fibers and organic matter were burnt off. The concentrated fines, collected on Millipore filter of 0.45/1, showed the presence of trace amounts of tremolite fiber in two of the trace MK-4 samples (Santa Ana and Newark). By petrographic microscopic examination, this was estimated to be less than 0.015$ of the total sample. The concentrates were then submitted to Arthur D. Little, Inc., for transmission and scanning electron microscopic analysis (GEM and SEM), selected area electron diffraction (SAED) and energy dispersive x-ray analysis (EDAX). By these sophisticated and time-consuming instrumental analyses, the amphibole fibers were positively identified and analyzed. On a mass basis, it was found to be less than 0.006$ of the concentrates which corresppnded to 1.7 ppm * (Santa Ana) and 4.1 ppm (Newark) of the total MONOKOT# sample weight. EXPERIMENTAL." Concentration The concentration procedure of M0N0K0TE is shown in Figure 1. The results are tabulated as follows: parts per million, or 0.00017$. 15171793 4 I.V.1 4 > > 3 W CQ P 3 CJ g Pm g: 1 s VO < -3 or-i o p- vO t>! o to r-l aV *8 5 a .c *o t* fl] r-l pm ao o # V* aS <D 0} C.V: O xass oo . VO OO -d* OJ* eoo ro ooon I A}-"' 0L5l VtOs S0S) o'--o 0 1 vO -=t I to oo CVI O P- <flVCOH p co 00 CM OO irv LTV ov -4 CM ON -4* VirOv t-4 Ov VirOv oo Ctrv- oo -4 o or-l oo r- o *o vo CO rH c o 8rl ov vo ov cv I s* oo H H 01 iu U. fi: 0) -p U to <U ^ 1- e*(D m e a? o5 T-l H a> Pi-P 6 a) S Ip Pi Vi O u ,o a U 4) O p *3 tO0-4) HO19 1H3 5h O -P n Vl C C tJ 0) 8 H aa a w a> A Pi A to rta-osl Ow6 3a > c o H a *&proa 0) P V H s o irv + o to vO vo +i 8 EHm g1 P, S CM OO St No d e te c ta b le tre m o lite found In any o f th e fra c tio n s o f the seven samples. CONFIDENTIAL > o * X REQUEST FOR TECHNICAL SERVICE: - NUMBER: 49189 GROUP: ZONOLITE ACTUAL COST: REPORTING DATE: $2300.00 M1/_a_yor2T6, 1977 Petrographic Microscopic Examination Based on the characteristic refractive indices and optical properties of vermiculite and tremolite fibers, using the liquid immersion technique, a trace of tremolite was found in the -50M +0.45/1 portion of Santa Ana MK-4, and Newark MK-4 samples. Analysis by Arthur D. Little, Inc. Even though the original request made by R. H. Locke was on one MK-4 and one MK-5 sample, we have decided to do several more since the product from each plant looked and behaved very differently. The MK-4 from Newark was very dense and the vermiculite present was poorly expanded in comparison with the others. Product from Santa Ana was very bulky and the plaster of Paris pres ent in the composition dissolved more readily than the others. The two concentrated samples suspected to have tremolite fibers were sub mitted to Arthur D. Little for fiber characterization and counting on transmis sion micrographs (Figures 2 and 3). Each fiber being counted was analyzed by SAED (selected area electron diffraction) to determine the structure of the fiber. It was found that 25-40$ of fibers did not yield an SAED pattern indi cating the fiber was amorphous, mostly organic and glass fibers. The breakdown of the fiber types and amounts is listed in Table 1. Scanning electron micrographs were also taken on some of the fibers. They are shown in Figures 4 and 5 and energy dispersive x-ray analysis (EDAX) was ' employed to analyze the elements present in each fiber. The results are shown in Table 2. CONCLUSIONS and COMMENTS: - The conclusion reached by A. D. Little, Inc. was that the amphibole fiber content, on a mass basis, corresponded to less than 0.006$ of the supplied con centrated sample. Letter from Dr. E. Peters of ADL is attached. Computing the amphibole content in the M0N0K0TE samples from Santa Ana and Newark, this corresponds to less than 1.7 ppm and 4.1 ppm, respectively. The level of tremolite fiber present was extremely low. JCY:mlr attachment 15171795 REQUEST FOR TECHNICAL SERVICE: PAGE 2Ct CONFIDENTIAL NUMBER: U9189 GROUP: ZONOLITE ACTUAL COST: $2500.00 REPORTING DATS: May 2o, 1977 TABLE 1 - Fiber analysis by TSM (A.D.Little) Fiber Observed Total fibers observed Sample 22281-1 Fines Fraction from Santa Ana, MK-4 Sample 104 * Amphibole % Other Mineral (mostly gypsum) * Ambiguous Mineral (with insuf ficient data for positive identification) i Amorphous (organic, glass fiber) 6 33.5 34.5 26 10c# Sample 22281-2 Fines Fraction from Newark, _______MK-4 Sample 54 4 35 22 _32 100* TABLE 2 - EDAX Microchemical Analysis of Fibers Observed by Scanning Electron Microscopy (A.D.Little) Sample 22281-1 Fiber 1 Fiber 2 Fiber 3 Fiber 4 Figure 6a Figure 6b Figure 4a Figure 4b Relative X-ray Intensity Strong Medium Weak A1 S Si,Al Mg,Ca,S . A1 -. Si,Al,Mg,S Ca,Fe Mg Fe,K Ca,S,Si K Sample 22281-2 Fiber 5 Figure 3 S,Ca,Al Probable I.D. amphibole or glass . . gypsum (?) amphibole or glass gypsum T l5l7l79fc Arthur D Little, Inc. ACORN PARK - CAMBRIDGE MASSACHUSETTS 02140 - (617) 864-5770 April 5, 1977 Dr. Julie C. Yang Manager,. Research Technologies Construction Products Division W. R. Grace & Co. 62 Whittemore Avenue Cambridge, Mass. 02140 Dear Julie: C76494 As we discjssed during your visit on March 11, 1977, low magnifi cation transmission electron microscope photographs have been obtained from two representative grid pore openings of samples 22281-1 and 22281-2 to permit an estimate of the percentage of mass attributable to fibers. In particular, amphibole fibers. A previous analysis of these samples, reported on January 24, 1977, identified the presence of fibers, most of which were mineral. These results can be summarized as follows: 22281-1 22281-2 Fibers observed Percent amphibole Percent other mineral (mostly gypsum) Percent ambiguous mineral Percent amorphous (organic, glass fiber) 104 6 34 35 26 54 4 35 22 39 As some of the ambiguous mineral category may be amphibole, it is prudent to estimate a maximum amphibole fiber content of 10 percent. Due to a slightly larger fiber size, the amphibole fiber volume is about 15 percent of the total fiber volume, which corresponds to 1.6 x 10"'* cm3 per grid pore opening. f To estimate the relative amount of fibrous material present in the samples, low magnification TEM photographs were obtained from two repre sentative pore openings of both samples. These, were assembled into ATHENS BRUSSELS CARACAS LONOON CAMBRIDGE, MASSACHUSETTS PARIS P'0 DE JANEIRO SAN FRANCISCO TORONTO WASHINGTON WIESBACEN Arthurl) Little, Inc April 5, 1977 2- Dr. Julie C. Yang W. R. Grace & Co. montages, which covered entire pore openings. Particle volumes per pore opening were calculated for the two montages prepared for sample 22281-1A (exhibiting the heaviest particle loading) from the projected surface area and an estimated thickness of each particle, as follows: 0.2pm - particles showing electron beam penetration over whole area 0.5pm - particles showing electron beam penetration at edges l-2pm - electron opaque particles From these estimates, the ratio of fiber volume to total particle volume was estimated to be 0.04 percent (0.006 percent for amphibole fibers). For the assumption that the densities of all particles are equivalent, these percentages apply on a mass basis, as well. From this analysis, we conclude that the amphibole fiber content, on a mass basis, corresponds to less than 0.006 percent of the supplied ' v sample, which represented the insoluble residue fraction of a leached f Monokote sample. This estimate should be reliable within a factor of two times. Please contact me if you have any questions. Very truly yours. Edward T. Peters /rdl 15171798 i FIGURE 1 CONCENTRATION 0? FINES IN MONOKOTrP MCNOKOTE (200 g) screening +6m ri glass fiber f+50M Vm. & Glass Fiber -5QM plaster of Paris some fibers & fines J,.C.Yang:mlr 151 7] 7qq I Figure X. j Transmission Electron Image of Fibrous Particles and Corresponding SAED Patterns, Sample 22281-1; 10,000x. 1 M HO Arthur D Little, Inc. Figure 3. Transmission Electron Image of Fibrous Particles and Corresponding SAED Pattern, Sample 22281-2; 10,000x. 15171801 Arthur D Little; inc. Figure 4--I Scanning Electron Micrographs of Fibrous Particles in Sample 22281-1 a) 5500x, b) 5500x 15171802 Arthur D Little, Inc Figure 5 | Scanning Electron Micrograph of a Fibrous Particle in Sample 22281-2, 5500x. 15171803 y Arthur D Little; Inc. Figure &) Scanning Electron Micrographs of Fibrous Particles in Sample 22281-1. a) 2400x, b) llOOx i 15171804