1、Designation: D 1135 86 (Reapproved 2009)Standard Test Methods forChemical Analysis of Blue Pigments1This standard is issued under the fixed designation D 1135; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revisi
2、on. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () 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 the chem
3、icalanalysis of blue pigments known commercially as iron blue,copper phthalocyanine blue, and ultramarine blue.1.2 The analytical procedures appear in the following order:SectionsIRON BLUE PIGMENTSIdentification 6Moisture by the Brabender Moisture Tester 7 and 8Moisture by Toluene Distillation 9Wate
4、r-Soluble Matter by Extraction 10Water-Soluble Salts by Electrical Conductivity 11Detection of Acid-Insoluble Extenders 1213Detection of Acid-Soluble Extenders 14 to 17Detection of Organic Colors and Lakes 18COPPER PHTHALOCYANINE BLUE PIGMENTSIdentification 19Moisture and Other Volatile Matter 20Det
5、ection of Basic Dye Derivatives 21Detection of Other Organic Coloring Matter 22Detection of Ultramarine Blue 23Detection of Iron Blue 24ULTRAMARINE BLUEIdentification 25Moisture and Other Volatile Matter 26Water-Soluble Matter 27Detection of Basic Dye Derivatives 28Detection of Other Organic Colorin
6、g Matter 291.3 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.4 This standard does not purport to address the safetyconcerns associated with its use. It is the responsibility of theuser of this standard to establish appropria
7、te safety and healthpractices and determine the applicability of regulatory limita-tions prior to use.2. Referenced Documents2.1 ASTM Standards:2D 280 Test Methods for Hygroscopic Moisture (and OtherMatter Volatile Under the Test Conditions) in PigmentsD 1193 Specification for Reagent WaterD 1208 Te
8、st Methods for Common Properties of CertainPigmentsD 2448 Test Method for Water-Soluble Salts in Pigments byMeasuring the Specific Resistance of the Leachate of thePigmentE11 Specification for Wire Cloth and Sieves for TestingPurposes3. Significance and Use3.1 These test methods are suitable for det
9、ermining ifimpurities are present and establishing that the required pig-ments are present. These test methods may be used formanufacturing quality control.4. Purity of Reagents and Water4.1 Purity of ReagentsUnless otherwise indicated, it isintended that all reagents shall conform to the specificat
10、ions ofthe Committee onAnalytical Reagents of theAmerican Chemi-cal Society, where such specifications are available.3Othergrades may be used, provided it is first ascertained that thereagent is of sufficiently high purity to permit its use withoutlessening the accuracy of the determination.4.2 Puri
11、ty of WaterUnless otherwise indicated, referencesto water shall be understood to mean reagent water conformingto Type II of Specification D 1193.1These test methods are under the jurisdiction of ASTM Committee D01 onPaint and Related Coatings, Materials, and Applications and are the directresponsibi
12、lity of Subcommittee D01.31 on Pigment Specifications.Current edition approved June 1, 2009. Published June 2009. Originallyapproved in 1950. Last previous edition approved in 2004 as D 1135 86 (2004).2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Servi
13、ce at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.3Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For suggestions on the testing of reagents notlisted by
14、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.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Consh
15、ohocken, PA 19428-2959, United States.5. Preparation of Sample5.1 Mix the sample thoroughly and take a representativeportion for analysis. Reduce any lumps or coarse particles to afine powder by grinding.5.2 Grind extracted pigments to pass a No. 80 (180-m)sieve.4Discard any skins that do not pass t
16、hrough the sieve.Mix the finely ground pigment thoroughly.IRON BLUE(Prussian Blue, Chinese Blue, Milori Blue)IDENTIFICATION6. Procedure6.1 To approximately 0.1 g of pigment in a 50-mL beaker,add 15 mLof NaOH solution (50 g/L). Heat to boiling. In a fewminutes the blue color should be completely dest
17、royed, givingin its place the characteristic reddish brown precipitate of ferrichydroxide. Add HCl (1+1) until faintly acid to litmus. The ironblue should be reformed, yielding again the characteristic bluecolor.NOTE 1If the NaOH treatment does not completely destroy the bluecolor, the evidence is s
18、trong that a foreign pigment is present. If thisoccurs, it is best to filter the alkaline solution, weakly acidify the filtratewith HCl (1+1), and add approximately 2 mL of a ferric salt solution(ferric sulfate or ferric alum (20 g/L). The formation of a blue precipitateestablished the pigment as co
19、nsisting, at least in part, of iron blue.MOISTURE BY THE BRABENDER MOISTURETESTER7. Apparatus7.1 Brabender Moisture TesterThe Brabender moisturetester (Fig. 1) consists of a constant-temperature oven withweighing apparatus attached. Specimens placed in the ovenmay be weighed without opening the oven
20、 door or removingthe specimen from the oven, as the balance scale is calibratedto read directly in percent of moisture.8. Procedure8.1 Set the temperature control at 160C and allow the ovento reach this temperature before checking or making anyweighing. Check the scale by placing a sample dish conta
21、ining9.200 g standard analytical balance weights in the oven. Theapparatus should read 8.0 % moisture. If it does not, adjust toa reading of 8.0 % by turning either the right hand or left handfoot screw.8.2 Weigh 10.000 g of the sample into the aluminum dishand place in the oven. For a series of spe
22、cimens, all should beplaced in the oven at as nearly the same time as possible. Nospecimen should occupy the position directly in front of thedoor. Weigh the specimen at the end of each hour for 5 h. Aftereach weighing, return the specimen to its original place in theoven.NOTE 2The dried pigment is
23、very hygroscopic. In order to obtainconsistent results, the specimen position must not be changed and the ovendoor must not be opened.8.3 Calculation and ReportPlot time against percent lossin weight on rectilinear cross-section paper. Extrapolate thelinear portion of the curve to zero time. That po
24、rtion beyondabout 2 h will be essentially linear. Report the percent loss inweight at the extrapolated zero time as the percent moisture inthe pigment.NOTE 3The pigment undergoes a slight loss in weight due todecomposition during the heating. The method of plotting and extrapola-tion corrects for th
25、is loss. An approximate value for moisture content maybe obtained by taking the reading at the end of the first hours heating. Anoccasional pigment may decompose rapidly at the oven temperature. Insuch cases, determine moisture by the toluene distillation method (Section9).MOISTURE BY TOLUENE DISTIL
26、LATION9. Procedure9.1 Determine the moisture content in accordance withSections 7 and 8 of Test Method D 1208, but using 25 g ofpigment and 200 mL of toluene and adjusting the calculationaccordingly.WATER-SOLUBLE MATTER BY EXTRACTION10. Procedure10.1 Determine whether or not the pigment is easily we
27、t bywater at room temperature by adding a little to some water ina beaker. If it tends to float on top of the water with very little,if any, tendency to sink to the bottom or disperse throughoutthe solution, even after agitation, it contains a hydrophobictreating agent.10.2 Weigh to 1 mg about 2.5 g
28、 of the pigment into a250-mL volumetric flask. If the pigment is hydrophobic astested above, moisten thoroughly with a few mL of ethylalcohol (Note 4). If the pigment is easily wet with water, noalcohol is necessary. Fill the flask about half full with waterand shake to disperse the pigment thorough
29、ly. Fill to the markand again shake. Allow to remain at room temperature for notless than 15 h, shaking from time to time, preferably with anautomatic shaking device.NOTE 4Ethyl alcohol denatured with acetone (Formula No. 23A) ordenatured with methyl alcohol (Formula No. 3A) has been found suitable.
30、10.3 Let settle, filter through a dry filter paper, and discardthe first 20 mL of the filtrate. Transfer 100 mL of the clearfiltrate to a weighed dish, and evaporate to dryness on a steambath. Dry for1hinanoven at 105 6 2C, cool, and weigh.4Detailed requirements for this sieve are given in Specifica
31、tion E11.D 1135 86 (2009)210.4 CalculationCalculate the percent of water-solublematter as follows:Water2soluble matter, % 5 grams of residue 3 100WATER-SOLUBLE SALTS BY ELECTRICALCONDUCTIVITY11. Procedure11.1 Determine water-soluble salt content in accordancewith Test Method D 2448.DETECTION OF ACID
32、-INSOLUBLE EXTENDERS12. Scope12.1 Acid-insoluble extenders include barium sulfate, silica,and silicates. Alumina may also be found, in part, with thisgroup.13. Procedure13.1 Ignite about 1 g (weighed to 0.1 mg) of the sample ata low temperature, just enough to decompose the last trace ofpigment but
33、not high enough to render the iron difficultlysoluble in HCl (Note 5). Cool, and add 15 mL of HCl (sp gr1.19) and a few drops of bromine. Cover with a watch glassand evaporate to a sirup. Add about 15 mL of water, and boil.It may be necessary to add a drop or two of HCl to effectcomplete solution of
34、 the ferric iron residue. Filter and washwith hot water. Save the filtrate for the determination ofalumina hydrate (Section 16).NOTE 5The ignition can conveniently be carried out in a 250-mLbeaker or a porcelain dish over a free flame. Oxidation of the specimen isevidenced by a dull glowing. While b
35、eing heated, it is advisable to roll thespecimen around in the beaker or dish exposing all of the surface to theoxygen of the air. A moderately low flame should be used and the ignitionis complete when the specimen ceases to glow and acquires a uniformbrown color.13.2 A residue of less than 3 mg tha
36、t appears as small blackspecks can be neglected, since quite frequently a small amountof iron is rendered insoluble or a small amount of blue pigmentescapes destruction. Ignite the residue and weigh. If apprecia-bly more than 3 mg are present, extenders should be suspected,and if it is required to k
37、now which extenders are present,analyze the residue for silica, barium sulfate, and alumina.FIG. 1 Brabender Moisture TesterD 1135 86 (2009)3NOTE 6If alumina is present, it may appear both with the acid-insoluble and acid-soluble extenders.As a rule, most of it will appear withthe acid-soluble exten
38、ders.DETECTION OF ACID-SOLUBLE EXTENDERS14. Scope14.1 Acid-soluble extenders include the alkaline earth car-bonates or sulfates, magnesium carbonate, and alumina hy-drate.15. Reagents15.1 Ammonium Oxalate SolutionDissolve 40 g of am-monium oxalate monohydrate in warm water and dilute to 1 L.15.2 Amm
39、onium Phosphate SolutionDissolve 100 g of(NH4)2HPO4in water and dilute to 1 L.16. Procedure for Alumina Hydrate16.1 To the filtrate from 13.1, add NaOH solution (50 g/L)until just alkaline; then add 5 mL excess. Boil for about 2 minand let stand in a warm place until the hydrous iron oxide iscoagula
40、ted. Filter through a rapid filter paper, wash a few timeswith hot water, and discard the precipitate.16.2 To the filtrate add 7 mL of HCl (1+1). Add NH4OH(1+4) until just ammoniacal. Boil about 2 min. If no precipitateis apparent, allow to stand about12 h. If the solution is stillclear, no alumina
41、hydrate is present. A white gelatinousprecipitate indicates alumina hydrate. Filter and save thefiltrate for the detection of alkaline earth and magnesium salts(Section 17).16.3 If a rough estimate of the amount of alumina hydrate isdesired, the residue may be washed, dried, ignited, andweighed as A
42、l2O3.17. Procedure for Alkaline Earth and Magnesium Salts17.1 To the filtrate from Section 16, add HCl (1+1) untilfaintly acid. Divide the filtrate into two portions.17.2 To one portion of the filtrate, add 15 mL of (NH4)2HPO4solution and neutralize with NH4OH (sp gr 0.90).Add10 mL excess NH4OH. If
43、no precipitate forms immediately, letstand for a short time in a cool place with occasional vigorousstirring. Rub the inside of the beaker from time to time with aglass rod to initiate crystallization. A white microcrystallineprecipitate indicates the presence of magnesium salts andpossibly some alk
44、aline earth salts as well.17.3 To the other portion of the filtrate, add 5 mL ofammonium oxalate solution. Make slightly alkaline withNH4OH (sp gr 0.90). If no precipitate forms immediately,warm on a hot plate and let stand for a short time. A whitemicrocrystalline precipitate indicates the presence
45、 of alkalineearth salts. If it is required to know specifically which acidsoluble extenders are present, any of the established tests forthese metal salts may be employed.DETECTION OF ORGANIC COLORS AND LAKES18. Procedure18.1 Boil2gofthesample for 2 min with 25 mL of water.Let settle and decant the
46、supernatant liquid. Similarly, boil theresidue with 25 mL of denatured ethyl alcohol (95 %) anddecant as before. Likewise boil with 25 mL of chloroform andagain decant. If any one of the above solutions is colored,organic colors are present. If all solutions remain colorless,disregarding a slight ye
47、llowish cast, organic colors are presum-ably absent. The presence of organic colors resistant to theabove reagents is unlikely, but may be tested by reference toprocedures given in standard reference works.5COPPER PHTHALOCYANINE BLUEIDENTIFICATION19. Procedure19.1 To about 0.05 g of the sample in a
48、50-mL beaker, add30 mL of H2SO4(sp gr 1.84). Stir occasionally for 15 min; thesample should dissolve, forming a dark greenish yellowsolution (color best seen on the side of the beaker). Pour thesolution into 250 mL of water and stir. The copper phthalo-cyanine should immediately precipitate as a bri
49、lliant blueflocculent mass.19.2 Filter off the precipitate, washing once or twice withwater. Scrape a small amount of the precipitate off the filter,place on a clean platinum wire moistened with HCl, andsubject it to the low flame of a bunsen burner.As the precipitateburns, a light blue-green flame should be clearly evident. Thisindicates organically combined copper.NOTE 7Characteristic spectrophotometric absorption spectra in thenear infrared range (700 to 900 nm) are exhibited by dilute solutions ofcopper phthalocyanine blue pigments in H2SO4(sp gr 1.84) (2 t
