1、Designation: D1135 86 (Reapproved 2014)Standard Test Methods forChemical Analysis of Blue Pigments1This standard is issued under the fixed designation D1135; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision
2、. 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 U.S. Department of Defense.1. Scope1.1 These test methods cover procedures for the c
3、hemicalanalysis 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 9W
4、ater-Soluble Matter by Extraction 10Water-Soluble Salts by Electrical Conductivity 11Detection of Acid-Insoluble Extenders 12 and 13Detection of Acid-Soluble Extenders 14 to 17Detection of Organic Colors and Lakes 18COPPER PHTHALOCYANINE BLUE PIGMENTSIdentification 19Moisture and Other Volatile Matt
5、er 20Detection 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
6、 Coloring 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 a
7、ppropriate safety and healthpractices and determine the applicability of regulatory limita-tions prior to use.2. Referenced Documents2.1 ASTM Standards:2D280 Test Methods for Hygroscopic Moisture (and OtherMatter Volatile Under the Test Conditions) in PigmentsD1193 Specification for Reagent WaterD12
8、08 Test Methods for Common Properties of CertainPigmentsD2448 Test Method for Water-Soluble Salts in Pigments byMeasuring the Specific Resistance of the Leachate of thePigmentE11 Specification for Woven Wire Test Sieve Cloth and TestSieves3. Significance and Use3.1 These test methods are suitable fo
9、r determining 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 speci
10、fications 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
11、 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean reagent water conformingto Type II of Specification D1193.1These test methods are under the jurisdiction of ASTM Committee D01 onPaint and Related Coatings, Materials, and Applications and are the directrespon
12、sibility of Subcommittee D01.31 on Pigment Specifications.Current edition approved Dec. 1, 2014. Published December 2014. Originallyapproved in 1950. Last previous edition approved in 2009 as D1135 86 (2009).DOI: 10.1520/D1135-86R14.2For referenced ASTM standards, visit the ASTM website, www.astm.or
13、g, orcontact ASTM Customer Service 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 t
14、esting 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.Copyright ASTM International, 100 Barr Harbor
15、 Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States15. 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.4Disca
16、rd any skins that do not pass through 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
17、color should be completely destroyed, 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 t
18、he bluecolor, the evidence is strong 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 precipita
19、teestablished the pigment as consisting, 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 w
20、eighed without opening the oven 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
21、 by placing a sample dish containing9.200 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 i
22、n the oven. For a series of specimens, 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 theo
23、ven.NOTE 2The dried pigment is 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
24、the curve to zero time. That portion 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
25、 extrapola-tion corrects for this 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 (Secti
26、on9).MOISTURE BY TOLUENE DISTILLATION9. Procedure9.1 Determine the moisture content in accordance withSections 7 and 8 of Test Method D1208, but using 25 g ofpigment and 200 mL of toluene and adjusting the calculationaccordingly.WATER-SOLUBLE MATTER BY EXTRACTION10. Procedure10.1 Determine whether o
27、r not the pigment is easily wet 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.
28、10.2 Weigh to 1 mg about 2.5 g 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
29、 disperse the pigment thoroughly. 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
30、. 3A) has been found suitable.4Detailed requirements for this sieve are given in Specification E11.D1135 86 (2014)210.3 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 ste
31、ambath. Dry for1hinanoven at 105 6 2C, cool, and weigh.10.4 CalculationCalculate the percent of water-solublematter as follows:Water 2 soluble matter, % 5 grams of residue 3100WATER-SOLUBLE SALTS BY ELECTRICALCONDUCTIVITY11. Procedure11.1 Determine water-soluble salt content in accordancewith Test M
32、ethod D2448.DETECTION OF ACID-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
33、the last trace ofpigment but 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
34、to effectcomplete solution of 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 isevidenc
35、ed by a dull glowing. While being 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
36、residue of less than 3 mg that appears as small blackspecks can be neglected, since quite frequently a small amountof iron is rendered insoluble or a small amount of blue pigmentFIG. 1 Brabender Moisture TesterD1135 86 (2014)3escapes destruction. Ignite the residue and weigh. If apprecia-bly more th
37、an 3 mg are present, extenders should be suspected,and if it is required to know which extenders are present,analyze the residue for silica, barium sulfate, and alumina.NOTE 6If alumina is present, it may appear both with the acid-insoluble and acid-soluble extenders.As a rule, most of it will appea
38、r withthe acid-soluble extenders.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 ammo-nium oxalate monohydrate in warm wate
39、r and dilute to 1 L.15.2 Ammonium 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
40、hydrous iron oxide iscoagulated. 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 solutio
41、n is stillclear, no alumina 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, dri
42、ed, ignited, andweighed as Al2O3.17. 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)
43、.Add 10 mL excess NH4OH. If no precipitate formsimmediately, let stand for a short time in a cool place withoccasional vigorous stirring. Rub the inside of the beaker fromtime to time with a glass rod to initiate crystallization. A whitemicrocrystalline precipitate indicates the presence of magne-si
44、um salts and possibly some alkaline 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 prec
45、ipitate indicates the presence 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 wa
46、ter.Let settle and decant the 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 colo
47、rless,disregarding a slight yellowish 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 ab
48、out 0.05 g of the sample in a 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 im
49、mediately precipitate as a brilliant 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 pigm
