BCIRA Broadsheet 16-1 Routine test procedures on prepared moulding sand—methylene blue test for active-clay content in greensands ‘The importance of active-clay content Active clay forming the bond in greensand moulds is destroyed by the heat from molten cast iron. This depletion causes deterioration in sand properties, which are corrected by the addition ofan appropriate amount of fresh or ‘active’ clay during remilling ofthe sand, and the discarding ofa proportion ofthe sed sand. Strict control of the elay content ofthe giesnsand mixture is necessary. ‘The methylene blue test An approximate estimate of the amount of active and spent clay can be obtained! indirecdly from changes in the greenstrength and shatter index of the sand mixture (cee BCIRA Broadsheets 16-4, 16-5, 16-6), but the Girect determination of active-clay content can be carried out by utilizing the strong adsorption and bese-exchange properties which clays possess for certain dyes,* such as methylene blue. The methylene blue test for active clay exploits the reactivity which active clay has for the dye, and the inert narure of “dead” clay.67 Method of preparation for the methylene blue test 1 Take 250 g sample representative ofthe sand mixture to be examined and dry in an oven at 110°C for Lhour. 2 Weigh accurately a 5 g sample of this material and place in a clean, dry 250 ml conical flask. 3 Add 50 ml distilled water using 2 pipette, and boil gently on a hor piate for 10 minutes, taking precau- tions to aveid bumping. 4 Cool to room temperature. Using a graduated pipette, add 1-5 ml of 0:5 N sulpburic acid and shake wel. 5 Add, using a burette, | ml of 2 previously standard- zed ‘methylene biue solution to the mixture which should be continuously stirred, preferably with ‘magnetic stirrer. By means of a glace rod transfer drop of the slurry on to a filer paper. The size of the drop is not important. 6 Examine the appearance of the filter paper. Initially 2 faint blue spot of solids will be observed surrounded by a transparent ring of colourless liquid. The letter scon evaporates and disappears. Repeat steps S and 6, As titration proceeds the colour ‘of the inner spot will become a progressively darker blue as the clay absorbs more dye, but the boundary ff the blue spot will remain clearly marked and distinct (Fig. 1a). 8 Continue until the end-point is reached when the ‘outline boundary of the inner blue spot breaks down into a diffuse light-blue halo, rediating outwards as if the colour from the central spot had ‘run’ outwards (Fig. 1b). At the first appearance of this halo stop the ‘tration, Fig.l Appearance of spot on filter paper during titration, before end-point. Fig. 1b Appearance of @ spot on filter paper during. titration, at end-point.Tivatien methylene blue soltion. mi Fig. 2 Typical calibration curve, 9 Continue stirring for two minutes and repeat the drop test without further addition of the titrant. If the halo persists the end-point has been reached; if not, continue titration ntl it does. 10 Note the final burstte reading at this point, end ‘deduct from it the intial reeding to give the volume of methylene blue added (the methylene biue value). 11 Using @ calibration graph (Fig. 2), prepared for the particular clay in use, read off from the volume fof titrant added the active clay content of the sand, The operation of the methylene blue test is shown in Fig. 3. +" Fig. 3 Carrying out the methylene blue test. Members can Birmingham B48 7QB © 1976 BCIRA, Alvechurch, Bimingham 848 706. Preparation of methylene blue solution ‘The concentration of methylene blue solution should be O01 moblitre. For methylene blue containing three molecules of water (Lc. CygifyNjS CL3H,0) the mole hhas a mass of 373.9 g, so 3-739 g of methylene blue sould be weighed out accurately and dissolved in I litre of distilled water. Grades of dye having varying amounts of H,0 are available, and the weight must be edjusted accordingly: for example, @ componnd having 2H,O in the molecule would require 3-559 g of dye per litte 10 give a 0-01 mollitee selution, ‘Standardization of methylene blue solution ‘The solution made up as above will be satisfactory for pormal control laborstory use. Where accurate inter= laboratory checking is required, the methylene blue solution mast be standardized by chemical titration. The ‘method for carrying out this operation isconteined in the British Pharmacopoeia."” Proparation of calibration graph 1 Make sand mixtures containing 2. 4,6, 8 & 10 percent of clay by adding the appropriate quentity of clay to the mill. 2 Add to the mill in the order: sand, water, and clay, with 2 brief intermediate milling treatment after each addition, The water content should be equal to half that of the clay content used. 3 Mill the eend for 10 minutes. 4 Teke samples of the sand mixture, and test a5 de- scribed above. 5 Construct a calibration graph relating the volume of metaylene blue solution added to the known clay conteat (Fig. 2). 6 Construct calibration graphs for exch kind of clay in uae, Always ensure chat the relevant greph is used. References 1 PARKES (W. B.) k SEALEY (A. G): BCIRA Journal of ‘Researchand Development 1955,¥. 3, FEDTURTY,pp.385-62. 2 VINGAS (G. J}: Teansections of the American Foundey- men’s Socety, 1965, v.73, pp. 61-3 3 HEINE (R. W.), KING. H.) & SCHUMACHER J. ‘Transactions ofthe American Founcrymen’s Society, 1960, ¥. 68 pp. 86-8, 4 OUTHWAITE (J): Unpublished work at BCIRA, 5 NEVINS (M. J.) & WEINTRITT (D. J. American (Cesamic Society Bulletin, 1967, v. 46, June; pp. 587-92 6 DODD (C. G.} Gaye and clay technology bulletin, No. 169, July, 1955, Site of Calforala Departinenc of Natural Resrces Division of Mines. 7 JONES (F.O.): O4Gas journal, 1964 v, 22, No. 62,PD. 76-8. 8 AKESSON (K) & ARCHENHOLTZ (A): Svenska Gterifoeningen Mekncesutat, No. 67508, Jay, 1967 9 YEARLEY (B. C.): Foundry, 1967, v.95, June, pp. 87, 10 British Pharmacopocis, 1968, pp. 616-17 in free copies of any BCIRA Broadsheet, from BCIRA, Alvechurch,