1、Designation: D 1301 91 (Reapproved 2003)Standard Test Methods forChemical Analysis of White Lead Pigments1This standard is issued under the fixed designation D 1301; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last
2、revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.This standard has been approved for use by agencies of the Department of Defense.1. Scope1.1 These test methods cover procedures for t
3、he chemicalanalysis of basic carbonate white lead and basic sulfate whitelead.NOTE 1If it is necessary to separate these pigments from others, referto Practice D 215.1.2 The values stated in SI units are to be regarded as thestandard. The values given in parentheses are for informationonly.1.3 The a
4、nalytical procedures appear in the following order:SectionPreparation of Sample 6Basic Carbonate White Lead:Small Amounts of Iron 7Total Lead 8Moisture and Other Volatile Matter 9Carbon Dioxide (Evolution Method) 10Carbon Dioxide and Combined Water (Combustion Method) 11Lead Carbonate 12Total Matter
5、 Insoluble in Acetic Acid 13Total Matter Insoluble in Acid Ammonium Acetate 14Total Impurities Other Than Moisture 15Coarse Particles 16Basic Sulfate White Lead:Small Amounts of Iron 17Total LeadMoisture and Other Volatile Matter 19Total Sulfate 20Zinc Oxide 21Basic Lead Oxide 22Total Impurities 23C
6、oarse Particles 241.4 This standard does not purport to address the safetyconcerns, if any, associated with its use. It is the responsibilityof the user of this standard to establish appropriate safety andhealth practices and determine the applicability of regulatorylimitations prior to use.2. Refer
7、enced Documents2.1 ASTM Standards:2C 25 Test Methods for Chemical Analysis of Limestone,Quicklime, and Hydrated LimeD 185 Test Methods for Coarse Particles in Pigments,Pastes, and PaintsD 215 Practice for Chemical Analysis of White Linseed OilPaintsD 280 Test Methods for Hygroscopic Moisture (and Ot
8、herMatter Volatile Under the Test Conditions) in PigmentsD 1193 Specification for Reagent WaterD 2371 Test Method for Pigment Content of Solvent-Reducible PaintsD 2372 Practice for Separation of Vehicle from Solvent-Reducible PaintsD 3280 Test Methods for Analysis of White Zinc PigmentsE 11 Specific
9、ation for Wire Cloth and Sieves for TestingPurposes3. Significance and Use3.1 These test methods are suitable for determining the levelof purity and for determining the levels of various impurities.They may be used to establish compliance with specificationrequirements.4. Reagents4.1 Purity of Reage
10、ntsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents shall conform to specifications of the Committeeon Analytical Reagents of the American Chemical Society,1These test methods are under the jurisdiction of ASTM Committee D01 onPaint and R
11、elated Coatings, Materials, and Applications and are the directresponsibility of Subcommittee D01.31 on Pigment Specifications.Current edition approved Dec. 1, 2003. Published December 2003. Originallyapproved in 1953. Last previous edition approved in 1991 as D 1301 91 (1999).2For referenced ASTM s
12、tandards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocke
13、n, PA 19428-2959, United States.where such specifications are available.3Other grades may beused, provided it is first ascertained that the reagent is ofsufficiently high purity to permit its use without lessening theaccuracy of the determination.4.2 Purity of WaterUnless otherwise indicated, refere
14、ncesto water shall be understood to mean reagent water conformingto Type II of Specification D 1193.4.3 Concentration of Reagents:4.3.1 Concentrated Acids and Ammonium HydroxideWhen acids and ammonium hydroxide are specified by nameor chemical formula only, it shall be understood that concen-trated
15、reagents of the following specific gravities or concen-trations are intended:Acetic acid, CH3COOH 99.5 %Hydrochloric acid, HCl sp gr 1.19Hydrofluoric acid, HF 48 %Nitric acid, HNO3sp gr 1.42Sulfuric acid, H2SO4sp gr 1.84Ammonium hydroxide, NH4OH sp gr 0.90The desired specific gravities or concentrat
16、ions of all otherconcentrated acids are stated whenever they are specified.WarningSee Section 5.4.3.2 Diluted Acids and Ammonium HydroxideConcentrations of diluted acids and ammonium hydroxide,except when standardized, are specified as a ratio stating thenumber of volumes of concentrated reagent to
17、be diluted witha given number of volumes of water, as in the followingexample: HCl (1 + 99) means 1 volume of concentrated HCl(sp gr 1.19) diluted with 99 volumes of water.5. Hazards5.1 The concentrated acids bases and other reagents used inthese test methods can be dangerous. Check their MaterialSa
18、fety Data Sheets, (MSDS) before use.6. Preparation of Sample6.1 Grind dry pigments, if lumpy or not finely ground, to afine powder for analysis. Large samples may be thoroughlymixed and a representative portion taken and powdered iflumpy or not finely ground. Mix the sample in all casesthoroughly an
19、d comminute before taking specimens for analy-sis.6.2 In cases of pastes in oil, extract the oil from the pigmentas described in Test Method D 2371 or Practice D 2372, butwithout straining.6.3 Dry pigments separated from paints or pastes in oil in anoven at 95 to 98C (203 to 210F) for 2 h, grind to
20、a finepowder, pass through a No. 80 (180-m) sieve (Note 2) toremove skins, and mix thoroughly. Such pigments, afterweighing, should be moistened with a little ethyl alcohol(95 %) before adding reagents for analysis.NOTE 2Detailed requirements for this sieve are given in SpecificationE11.6.4 Preserve
21、 all samples in stoppered bottles or containers.BASIC CARBONATE WHITE LEAD7. Small Amounts of Iron7.1 Reagents:7.1.1 Ammonium Hydroxide (sp gr 0.90). WarningSee5.1.7.1.2 Hydrofluoric Acid (48 %). WarningSee 5.1.7.1.3 Nitric Acid (sp gr 1.42). WarningSee 5.1.7.1.4 Sulfuric Acid (sp gr 1.84). WarningS
22、ee 5.1.7.2 Procedure:7.2.1 Weigh to 10 mg about1gofspecimen into a 400-mLbeaker. Treat the sample with 10 mL of HNO3(1 + 1) anddilute to about 200 mL with water. If insoluble matter remainsfollowing treatment with HNO3and dilution, filter and washthe residue with hot water until lead free. Evaporate
23、 the filtrateand washings to about 200 mL. Add 20 mL of H2SO4(1+1)to precipitate the bulk of the lead (it is unnecessary toevaporate down). Cool, filter, and wash with diluted H2SO4(1 + 99). Save the precipitate for determination of total lead(Section 8).7.2.2 Ignite the HNO3-insoluble matter and tr
24、eat with HFand H2SO4. Bring into solution, filter (any precipitate isprobably BaSO4), and add to the PbSO4filtrate.7.2.3 Colorimetrically determine iron in the combined fil-trates by the thiocyanate method,4using the same amounts ofreagents in preparing the reference standards. If copper ispresent i
25、n the filtrate, as shown by the characteristic blue-greenor yellow color, remove it by precipitating the iron withNH4OH, filtering, washing, redissolving the Fe(OH)3in 10 mLof HNO3(1 + 1), and diluting to about 200 mL before proceed-ing with the thiocyanate method.8. Total Lead8.1 Apparatus:8.1.1 Go
26、och Crucible, prepared prior to use.8.2 Reagents:8.2.1 Acetic Acid (glacial)WarningSee 5.1.8.2.2 Ammonium Hydroxide (sp gr 0.90)WarningSee5.1.8.2.3 Ethyl Alcohol (95 volume %)WarningSee 5.1.8.2.4 Potassium Dichromate Solution (100 g K2Cr2O7/L)WarningSee 5.1.8.3 Procedure:8.3.1 Ignite the PbSO4precip
27、itate and filter paper from 7.2.1at or below 550C (1020F), and transfer the residue to a400-mL beaker. (If preferred, a new 1-g specimen of pigmentmay be weighed to 10 mg into a 400-mL beaker. Proceed to8.3.2.)8.3.2 Moisten with water and add 5 mL of glacial aceticacid. Warm to dissolve the material
28、 and dilute to about 200 mLwith water. Neutralize the solution with NH4OH and then makeslightly acid with acetic acid, adding about 3 mL excess. Filteroff any insoluble residue and wash thoroughly with hot water.3Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society,
29、Washington, DC. For suggestions on the testing of reagents notlisted by the American Chemical 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.4Desc
30、ribed in Scott, Standard Methods of Chemical Analysis, Fifth Edition, D.Van Nostrand Co., New York, NY, 1939, p. 486.D 1301 91 (2003)28.3.3 Unite the filtrate and washings, heat to boiling, andadd 15 mL of K2Cr2O7solution. Stir and heat until the yellowprecipitate assumes an orange color. Let settle
31、 and filter on aweighed Gooch crucible. Wash by decantation with hot wateruntil the washings are colorless. Finally transfer all theprecipitate from the beaker to the crucible and wash with ethylalcohol (95 %). Dry at 105 6 2C (220 6 4F) for 1 h. Coolin a desiccator and weigh as PbCrO4.8.4 Calculati
32、on:PbO, % 5 P 3 0.691 / S! 3 100where:P = PbCrO4precipitate, g,S = specimen, g, and0.691 = PbO/PbCrO4= 223.19/323.18.9. Moisture and Other Volatile Matter9.1 ProcedureDetermine moisture and other volatile mat-ter in accordance with Method A of Test Methods D 280.10. Carbon Dioxide (Evolution Method)
33、10.1 ApparatusKnorr type of CO2evolution apparatuswith dropping funnel, condenser, and suitable purifying train.NOTE 3A description of a suitable purifying train, is found in theCarbon Dioxide Standard Method section of Test Methods C 25.10.2 Reagent:10.2.1 Nitric Acid (1 + 19).10.3 ProcedureTransfe
34、r about2gofthesample, weighedto 10 mg, to a clean, dry evolution flask. Connect the evolutionflask to the absorption train, which previously has been flushedfree of any CO2, and add 100 mL of HNO3, (1 + 19) througha separatory funnel. When all of the HNO3has been introducedinto the flask, close the
35、stopcock from the separatory funnel.Heat the solution in the flask to gentle boiling and boil for 5min. Turn off the heat and aspirate CO2free air through thesystem for 20 min. Remove the absorbing tube from thesystem, seal, cool in a desiccator, and weigh. The increase inweight is CO2.10.4 Calculat
36、ionCalculate the percent of carbon dioxideas follows:CO2,%5 C1/S1! 3 100where:C1=CO2,g,andS1= specimen, g.11. Carbon Dioxide and Combined Water (CombustionMethod)11.1 ApparatusCombustion Train, consisting of the fol-lowing parts connected in the order specified; tank of purifiedcompressed nitrogen,
37、purifying jars including a CO2absorp-tion jar, drying tube, combustion tube, tube furnace providedwith suitable controls to maintain the temperature from 450 to550C (840 to 1020F), absorption bulb for water, and anabsorption bulb for CO2.11.2 Procedure:11.2.1 Heat the furnace, without the combustion
38、 tube, from450 to 550C (840 to 1022F). Connect the combustion tubebeside the furnace, connect the absorption tubes to the nitrogensupply, and pass a slow stream of nitrogen (about 30 mL/min)through them, to clear out any residual moisture and CO2.Accurately weigh the absorption bulbs and reconnect t
39、hem inthe train. Transfer1gofthespecimen, weighed to 10 mg, to acombustion boat that has been previously ignited and cooled.11.2.2 With the nitrogen still flowing, disconnect the trainand place the boat containing the specimen in the middle of thetube with the aid of a hooked wire. Flush the combust
40、ion tubethoroughly with nitrogen and reconnect with the train. Placethe tube in the furnace.11.2.3 Continue the combustion for 30 min, or until thewater that condenses in the inlet arm of the first absorption bulbhas been completely swept into the bulb. Disconnect theabsorption bulbs from the combus
41、tion tube, after closing allstopcocks, place in a desiccator to cool, and then weigh.11.3 Calculation:Carbon dioxide, % 5 100 3 C1Combined water, % 5 100 W12 MCombined water as PbOH!2,%5 100 W12 M! 3 13.39where:C1=CO2,g,W1= total water, g,M = free moisture, %, and13.39 = Pb(OH)2/H2O = 241.20/18.015.
42、12. Lead Carbonate12.1 CalculationCalculate the percent of PbCO3from theCO2content, as follows:PbCO3,%5 C13 6.071/S23 100where:C1=CO2(10.4 or 11.3), g,S2= specimen weight used in the CO2determination, g,and6.071 = PbCO3/CO2= 267.20/44.01.13. Total Matter Insoluble in Acetic Acid13.1 ApparatusGooch C
43、rucible, prepared and weighedprior to use.13.2 ReagentAcetic Acid (3 + 2).13.3 ProcedureTransfer 10 g of the sample, weighed to10 mg, to a 250-mL beaker and add 40 mL of acetic acid(2 + 3). Heat until solution is complete and filter through apreviously prepared and weighed Gooch crucible. Wash thor-
44、oughly with hot water, dry at 105 6 2C (220 6 4F) for 1 h,cool, and weigh.13.4 CalculationCalculate the percent of total matterinsoluble in acetic acid as:R/S3! 3 100where:R = residue, g, andS3= specimen, g.14. Total Matter Insoluble in Acid Ammonium Acetate14.1 ApparatusGooch Crucible, prepared and
45、 weighedprior to use.D 1301 91 (2003)314.2 ReagentAcid Ammonium Acetate SolutionMix 150mL of acetic acid (3 + 2) with 100 mL of water and then with95 mL of NH4OH (sp gr 0.90).14.3 ProcedureTransfer about 10 g of the sample,weighed to 10 mg, to a 250-mL beaker. Add 40 mL of acidammonium acetate solut
46、ion and heat until solution is complete.Filter through a previously prepared and weighed Goochcrucible and wash thoroughly with hot water. Dry at 105 to110C for 1 h, cool, and weigh.14.4 CalculationCalculate the percent of total matterinsoluble in acid ammonium acetate as:R/S4! 3 100where:R1= residu
47、e, g, andS4= specimen, g.15. Total Impurities Other Than Moisture15.1 Calculations:15.1.1 Calculate the percent of total impurities other thanmoisture as:100 2 L 1 C 1 H 1 M!where:L = PbO % (8.4),C =CO2% (10.4 or 11.3),H = combined water, % (11.3), andM = free moisture, % (9.1).15.1.2 In the case of
48、 extracted pigments where directdetermination of combined water cannot be made conve-niently, calculate the impurities other than moisture as: 100(L + 1.205 D + M) where L, D, are as defined in 15.1.1 and1.025 = 2 CO2+H2O/2 CO2= 106.035/88.02.16. Coarse Particles16.1 ProcedureDetermine coarse partic
49、les in accordancewith Test Methods D 185.BASIC SULFATE WHITE LEAD17. Small Amounts of Iron17.1 ProcedureDetermine small amounts of iron in ac-cordance with Section 7.18. Total Lead18.1 ProcedureDetermine total lead in accordance withSection 88.19. Moisture and Other Volatile Matter19.1 ProcedureDetermine moisture and other volatilematter in accordance with Method A of Test Methods D 280.20. Total Sulfate20.1 ApparatusGooch Crucible, ignited and weighedprior to use.20.2 Reagents:20.2.1 Barium Chloride Solution (100 g BaCl2
