1、Designation: D5547 95 (Reapproved 2009)Standard Test Method forClay and Zeolite in Powdered Laundry Detergents by AtomicAbsorption1This standard is issued under the fixed designation D5547; the number immediately following the designation indicates the year oforiginal adoption or, in the case of rev
2、ision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 This test method covers atomic absorption tests appli-cable to powdered laundry detergents containi
3、ng clay andzeolite.21.2 The values stated in SI units are to be regarded as thestandard.1.3 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices
4、 and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:3E180 Practice for Determining the Precision of ASTMMethods for Analysis and Testing of Industrial and Spe-cialty Chemicals43. Summary of Test Method3.1 The test sample is fused with li
5、thium metaborate,dissolved in acid, its silicon and aluminum content measuredby atomic absorption, and the silicon/aluminum (Si/Al) ratiocalculated. The clay and zeolite content of the test sample iscalculated from the Si/Al ratio of the test sample and the Si/Alratio of the clay and zeolite expecte
6、d in the test sample.4. Interferences4.1 Materials other than clay and zeolite that contain siliconor aluminum, or both, will interfere.5. Principle5.1 Clay and zeolite contain silicon and aluminum at differ-ent relative levels.5The silicon/aluminum ratio is then ameasure of the relative level of cl
7、ay and zeolite in detergentpowders. That is, detergent powders with a Si/Al ratio match-ing clay or zeolite contain only clay or zeolite, respectively.Detergent powders with Si/Al ratio falling between the Si/Alratio of clay and zeolite contain both clay and zeolite.5.2 This test method is based on
8、the linear relationshipbetween the relative composition (or ratio) of clay/zeolite indetergent powders and the Si/Al ratio of such detergents.5.3 A calibration equation is derivable, therefore, from justtwo experimental points: the Si/Al ratio of the zeolite standard(100 zeolite, 0 % clay) and the S
9、i/Al ratio of the clay standard(0 % zeolite, 100 % clay).6. Apparatus6.1 Suitable Atomic Absorption Spectrophotometers, fittedwith a nitrous oxide-acetylene burner and aluminum andsilicon hollow cathode source lamps.6.2 Nitrous Oxide and Acetylene Tanks, with suitable regu-lators.6.3 Muffle Furnace,
10、 capable of reaching 1000C.6.4 Analytical Balance.6.5 Fisher Burner or Equivalent.6.6 20-mL or Larger Platinum Crucibles.6.7 Platinum-tip Tongs.6.8 25-mL Buret.6.9 100-mL and 200-mL Polypropylene Volumetric Flasks.6.10 10-mL and 25-mL Graduated Cylinders.6.11 150-mL Plastic Beakers.6.12 Magnetic Sti
11、rrer and Magnetic Stirring Bars.6.13 Blender, such as Waring6or Osterizer7or an industriallab model, or a mortar and pestle, if a blender is not available.7. Reagents7.1 Purity of ReagentsReagents grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended that1This test me
12、thod is under the jurisdiction of ASTM Committee D12 on Soapsand Other Detergents and is the direct responsibility of Subcommittee D12.12 onAnalysis and Specifications of Soaps, Synthetics, Detergents and their Components.Current edition approved Oct. 1, 2009. Published March 2010. Originallyapprove
13、d in 1994. Last previous edition approved in 2003 as D5547 95(2003).DOI: 10.1520/D5547-95R09.2Silicon and aluminum measurements are by atomic absorption in this testmethod. ICP can be used to make such measurements as well.3For referenced ASTM standards, visit the ASTM website, www.astm.org, orconta
14、ct ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.4Withdrawn. The last approved version of this historical standard is referencedon www.astm.org.5The Si/Al ratio is usually about 1 in zeol
15、ites and about 3 in clays.6Waring blenders are available commercially.7Osterizer blenders are widely available commercially.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.all reagents conform to the specifications of the Committee o
16、nAnalytical Reagents of the American Chemical Society, wheresuch specifications are available.8Other grades may be used,provided it is first ascertained that the reagent is of sufficientlyhigh purity to permit its use without lessening the accuracy ofthe determination.7.2 Purity of WaterUnless other
17、wise indicated, referenceto water shall be understood to mean distilled water or water ofequal purity.7.3 Aluminum Standard, 1000 g Al/mL9or equivalent.7.4 Silicon Standard, 1000 g Si/mL.97.5 Potassium Chloride, Baker-analyzed reagent or equiva-lent.7.6 Potassium Chloride Solution (1 %)Dissolve1gofp
18、otassium chloride in 100 mL of distilled water. Mix well andstore in plastic container.7.7 Concentrated Hydrochloric Acid, Baker-analyzed re-agent or equivalent.7.8 Hydrochloric Acid Solution (1 + 1)Mix equal parts ofconcentrated HCl and distilled water by volume. Mix well andstore in plastic contai
19、ner.7.9 Potassium Iodide, Baker-analyzed reagent or equiva-lent.7.10 Lithium Metaborate SPEX Grade, Special for Fu-sions10.7.11 Zeolite StandardThe same material expected in thetest sample, to be used as standard.7.12 Clay StandardThe same material expected in the testsample, to be used as standard.
20、8. Instrumental Conditions8.1 Following the instrument manufacturers instructions,set up the atomic absorption instrument as follows:To measure Aluminum To measure SiliconWavelength, nm 309.3 251.6Range UV UVSlit, nm 0.2 0.2Flame Nitrous oxide-acetylene. Nitrous oxide-acetylene.Rich, red. Strongly r
21、educing red cone 23cm high with yellow outeredge.9. Procedure9.1 Determination of Aluminum:9.1.1 Accurately weigh 0.1 g (to the nearest 0.1 mg) ofzeolite standard (the same material expected in the test sample)into a clean, dry, platinum crucible. Also accurately weigh 0.2g of clay standard (the sam
22、e material expected in the testsample) into another clean, dry, platinum crucible.9.1.2 Grind a representative powdered detergent test samplein a blender to a fine, homogenous powder. (If a blender is notavailable, use a mortar and pestle).9.1.3 Accurately weigh 0.3 g (to the nearest 0.1 mg) of theg
23、round test sample(s) into still another clean, dry, platinumcrucible.9.1.4 Add2g(60.1 g) of lithium metaborate to eachplatinum crucible, and mix the contents with a plastic rod.9.1.5 Place the crucibles containing the mixtures in a coolmuffle furnace and turn on the heat. When the temperaturereaches
24、 1000C, maintain heat for at least 5 additional min.NOTE 1The sample will ignite and splatter if placed in a hot furnace.If it is not possible to start with a cool furnace, gently char the sample witha Fisher burner first, avoiding ignition, then place in the furnace.9.1.6 Place 90 mL of distilled w
25、ater into 150-mL plasticbeakers. (Use as many beakers as there are standards andsamples).9.1.7 Add a magnetic stirring bar to each beaker, and placeon a magnetic stirrer. Mix rapidly to make the water swirl inthe beaker, but do not allow anything to splash out. Thisapparatus should be near the furna
26、ce containing the ashedstandards and sample(s).9.1.8 Using platinum-tip tongs, remove one crucible at atime from the furnace, and immediately place over a Fisherburner flame without allowing the melted sample to solidify.9.1.9 Add about 2 mg (a pinch on the end of a spatula) ofpotassium iodide (KI)
27、to the melted sample. A molten ball willform. Roll the ball around the inside of the dish to pick up anydroplets or particles. The KI releasing agent is volatile, and itis necessary to carry out this step rather quickly (about 2 min).If the ball collapses and flows into the dish, start again byaddin
28、g fresh KI.9.1.10 Drop each molten ball quickly into the swirling waterof each plastic beaker.NOTE 2Precaution: Use face shield and protective clothing.9.1.11 Add 20 mL of 1 + 1 HCl and 20 mL of 1 %potassium chloride solution and mix until completely dis-solved. Quantitatively transfer to a 200-mL p
29、lastic volumetricflask with distilled water. Dilute to volume and mix well.9.1.12 Using a buret, add 5, 7.5, and 10 mL of 1000-ppmaluminum standard into 3 separate 100-mL plastic volumetricflasks. These standards contain 50, 75, and 100 g Al/mLrespectively. (Make these standards fresh each day).9.1.
30、13 Add 10 mL 1 + 1 HCl, 10 mL 1 % KCl, and1goflithium metaborate to each flask. Dilute to volume withdistilled water and mix until completely dissolved.9.1.14 Prepare a reagents blank.9.1.15 Set up the atomic absorption instrument as describedin 8.1.9.1.16 Zero the instrument with the reagents blank
31、. Measurethe absorbance of the aluminum standards, the zeolite standard,the clay standard and the test sample at 309.3 nm. Repeat themeasurement three more times for each flask and calculate theaverage absorbance. Save the solutions, except the aluminumstandards, for silicon determination in 9.2.9.1
32、.17 Prepare a standard curve by plotting the averageabsorbance versus concentration in g/mL of each aluminumstandard.8Reagent Chemicals, American Chemical Society Specifications , AmericanChemical Society, Washington, DC. For suggestions on the testing of reagents notlisted by the American Chemical
33、Society, see Analar Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.9Available from Fisher Scientific Co., Fairlawn, NJ 07410.10Available from SPEX Industries, Box 798
34、, Metuchen, NJ 08840.D5547 95 (2009)29.1.18 Determine the concentration of aluminum in the testsample(s) by comparing the average absorbance to the standardcurve and reading aluminum concentration in g/mL directly.NOTE 3This test method describes manual data gathering and calcu-lation from a calibra
35、tion curve so that the technique can be carried outusing all atomic absorption units. It is acceptable to use the automaticconcentration modes in modern atomic absorption units if so equipped.9.1.19 Calculation:C 3 200wt. 3 10 0005 % aluminum (1)where:C = aluminum concentration (g/mL),200 = final di
36、lution in mL,wt. = weight of zeolite and clay standards, and testsample(s), in g, and10 000 = conversion factor, g/g to percent.9.2 Determination of Silicon:9.2.1 Pipet 5, 10, and 15 mL of 1000-ppm silicon standardinto three separate 100 mL plastic volumetric flasks.9.2.2 Add 10 mL 1 + 1 HCl, 10 mL
37、1 % KCl, and1goflithium metaborate to each flask. Dilute to volume withdistilled water and mix until completely dissolved. Thesestandards contain 50, 100, and 150 g Si/mL respectively.(Make these standards fresh each day.)9.2.3 Prepare a reagents blank and dilute with distilled water50.0 mL of the c
38、lay standards from 9.1 to 100.0 mL in a100-mL plastic volumetric flask.9.2.4 Set up the atomic absorption instrument as describedin 8.1.9.2.5 Zero the instrument with the reagents blank. Measurethe absorbance of the silicon standards at 251.6 nm. Measure,also at 251.6 nm, the absorbance of the zeoli
39、te standard, theclay standard, and the test sample(s) from 9.1. Repeat themeasurement three more times for each flask and calculate theaverage absorbance.9.2.6 Prepare a standard curve by plotting the averageabsorbance versus concentration in g/mL of each siliconstandard.9.2.7 Determine the concentr
40、ation of silicon in the testsample(s), the zeolite standard, and the clay standard bycomparing the average absorbance to the standard curve andreading the silicon concentration in g/mL directly.NOTE 4This test method describes manual data gathering and calcu-lation from a calibration curve so that t
41、he technique can be carried outusing all atomic absorption units. It is acceptable to use the automaticconcentration modes in modern atomic absorption units if so equipped.9.2.8 Calculation:C 3 200wt. 3 10 0005 % silicon (2)where:C = silicon concentration from curve (g/L),200 = final dilution in mL,
42、wt. = weight of zeolite and clay standards and testsample(s), in g, and10 000 = conversion factor, g/g to percent.10. Calculation of Percent Clay and Percent Zeolite inTest Samples10.1 Calculate the Si/Al ratio for the clay standard, thezeolite standard, and the test sample(s) from percent aluminuma
43、nd percent silicon obtained in 9.1 and 9.2, respectively.10.2 Derive the equation of the straight line, y=mx+c,connecting the points:x1, y15 Si/Al C!, 0 (3)x2, y25 Si/Al Z!, 100where:Si/Al(C) = Si/Al ratio of clay standard,Si/Al(Z) = Si/Al ratio of zeolite standard,0 = concentration of zeolite in cl
44、ay standard, and100 = concentration of zeolite in zeolite standard.10.3 Calculate the relative level of zeolite in the testsample(s) using the equation from 10.2 and the Si/Al ratio ofthe test sample(s) from 10.1:yRLZ! 5 mx 1 c (4)where:y(RLZ) = relative level of zeolite in the test sample,m = slope
45、 of the line (10.2),x = Si/Al ratio of test sample, andc = intercept of the line (10.2).10.4 Percent Zeolite in Test Sample:ATS!RLZ!AZ!5 % zeolite (5)where:ATS = percent aluminum in test sample (9.1),RLZ = relative level of zeolite in test sample (10.3), andAZ = percent aluminum in zeolite standard.
46、10.5 Percent Clay in Test Sample:ATS!100 2 RLZ!AC!5 % clay (6)where:ATS = percent aluminum in test sample (9.1),RLZ = relative level of zeolite in test sample (10.3), andAC = percent aluminum in clay standard.10.6 Sample Calculation for a Typical Clay, Zeolite, andPowdered Detergent:10.6.1 Experimen
47、tal Results:ClaystandardZeolitestandardPowderdetergent% Aluminum 8.8 16 3.3% Silicon 27.3 17.6 5.4Si/Al ratio 3.1 1.1 1.6410.6.1.1 Using the points x1, y1= 3.1, 0; x2, y2= 1.1, 100,the equation of the line is:y 5250x 1 155 (7)10.6.1.2 Relative Level of Zeolite (RLZ) in Detergent Pow-der:D5547 95 (20
48、09)3y 5250!1.64! 1 155 5 73 (8)10.6.1.3 Percent Zeolite in Detergent Powder:ATS!RLZ!AZ!53.3!73!16!5 15.1 (9)10.6.1.4 Percent Clay in Detergent Powder:ATS!100 2 RLZ!AC!53.3!100 2 73!8.8!5 10.1 (10)11. Precision and Bias11.1 Six laboratories collaborated in analyzing two powderdetergents (A and B). Se
49、e Table 1.11.2 The standard deviations for clay, covering the 5.2 to9.9 % clay range, and the standard deviations for zeolite,covering the 19.6 to 28.9 % zeolite range, were pooled. SeeTable 1.11.3 The following criteria should be used to judge theacceptability of the results.11,1211.3.1 Repeatability (Single Analyst) of ClayThe standarddeviation of results (each the average of duplicates), obtainedby the same analyst on different days, has been estimated to be0.7 % weight absolute, at 12 of freedom. Two such averagesshould be co
