1、Designation: D 4487 90 (Reapproved 2008)Standard Test Methods forAnalysis of Calcium Borosilicate1This standard is issued under the fixed designation D 4487; 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.1. Scope1.1 These test methods cover the analysis of the pigmentcommercially known as calcium borosilicate.1.2 The test methods appear in the f
3、ollowing order:Test Methods SectionsSilicon Dioxide (SiO2) 6-9Iron Oxide (Fe2O3) 10-13Boron Trioxide (B2O3) 17-20Calcium Oxide (CaO) 21-23Moisture and Volatile Matter 24Water of Hydration 25 to 26Coarse Particles 27Oil Absorption 281.3 Individual specimens may be used for the direct deter-minations
4、of SiO2,B2O3, and CaO. SiO2and Fe2O3should beremoved before the determination of the B2O3and CaO.1.4 The values stated in SI units are to be regarded as thestandard. The values given in parentheses are for informationonly.1.5 This standard does not purport to address all of thesafety concerns, if an
5、y, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D 185 Test Methods for Coarse Particles in Pigment
6、sD 280 Test Methods for Hygroscopic Moisture (and OtherMatter Volatile Under the Test Conditions) in PigmentsD 281 Test Method for Oil Absorption of Pigments bySpatula Rub-outD 1193 Specification for Reagent Water3. Significance and Use3.1 These test methods compile in one place, recommendedprocedur
7、es for analysis of the pigment known commercially ascalcium borosilicate. This pigment is used extensively in paintsand the composition is important to the user and producer.4. Reagents4.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended
8、 thatall reagents shall conform to the specifications of the Commit-tee on Analytical Reagents of the American Chemical Societywhere 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 l
9、essening theaccuracy of the determination.4.2 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean reagent water conformingto Type II of Specification D 1193.4.3 Concentration of Acids and Ammonium HydroxideWhen acids and ammonium hydroxide are specified by nameo
10、r chemical formula only, it should be understood that concen-trated reagents of the following specific gravity are intended:Hydrochloric acid (HCl) 1.19Nitric acid, (HNO3) 1.42Sulfuric acid (H2SO4) 1.84Ammonium hydroxide (NH4OH) 0.905. Preparation of Samples5.1 Thoroughly mix and comminute the sampl
11、e beforetaking portions for analysis.SILICON DIOXIDE6. Apparatus6.1 Evaporating Casserole, 250-mL capacity.6.2 Hot Plate.6.3 Porcelain Filtering Crucible, medium porosity, 30-mLcapacity.6.4 Drying Oven, maintained at 100 6 5C.6.5 Muffle Furnace.1These test methods are under the jurisdiction of ASTM
12、Committee D01 onPaint and Related Coatings, Materials, and Applications and are the directresponsibility of Subcommittee D01.31 on Pigment Specifications.Current edition approved Nov. 1, 2008. Published November 2008. Originallyapproved in 1985. Last previous edition approved in 2003 as D 4487 90 (2
13、003).2For referenced ASTM standards, 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.3Reagent Chemicals, American Chemical Society Specificat
14、ions, AmericanChemical Society, 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,
15、 Inc. (USPC), Rockville,MD.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.7. Reagents7.1 Hydrochloric Acid (1+1).7.2 Hydrochloric Acid (1+19).7.3 Hydrochloric Acid (1+99).8. Procedure8.1 Introduce a 1-g specimen, weighed to the near
16、est 0.1 mginto an evaporating casserole. Add 50 mL of HCl (1+1) andthoroughly mix.8.2 Place the casserole on a hot plate and evaporate care-fully to dryness.8.3 Place the casserole in the oven at 100C for 2 h. Do notallow the oven temperature to exceed 105C at any time.Remove the casserole and allow
17、 to cool for 10 min.8.4 Completely wet the residue with 25 mL of HCl (1+1)and cover the casserole with a watch glass. Warm just toboiling on a hot plate and maintain for 10 min.8.5 Add 25 mL of water, free any material from the sides ofthe casserole with a stirring rod, and immediately filter throug
18、ha tared porcelain crucible of medium porosity.8.6 Wash the residue with two 5-mL portions of hot HCl(1+19), one 5-mL portion of hot HCl (1+99), and finally withtwo 5-mL portions of hot water. Save the combined filtrates forthe determination of iron oxide (Sections 10-12).8.7 Place the crucible cont
19、aining the precipitate in themuffle furnace from 600 to 800C and heat to constant weight(64 mg). Cool in a desiccator and weigh.9. Calculation9.1 Calculate the percent of SiO2, A, as follows:A 5 R/S1100! (1)where:R = weight of residue, g, andS1= weight of original specimen, g.IRON OXIDE10. Apparatus
20、10.1 Volumetric Flasks, 250-mL and 1000-mL capacity.10.2 Buret, 10-mL capacity.11. Reagents11.1 Potassium Iodate (0.01878 N)Dry 1.0 g of KIO3at120C for2hinadrying oven. After cooling, weigh 0.6700 gand dissolve it in 100 mL of water. Dilute the solution to 1 Lin a volumetric flask. 1 mL = 0.001500 g
21、 Fe2O3.11.2 Potassium Iodide (KI)Iodate free.11.3 Starch Indicator SolutionMake a homogeneouspaste of 10 g of soluble starch in cold water. Add to this 1 L ofboiling water, stir rapidly, and cool. Salicylic acid (1.25 g/L)may be added to preserve the indicator. If long storage isrequired, the soluti
22、on should be kept in a refrigerator at 4 to10C. Prepare fresh indicator when the end point of thetitration from blue to colorless fails to be sharp.11.4 Sulfuric acid (H2SO4) (1+18).11.5 Sodium Thiosulfate, Standard Solution (0.025 N)Dissolve 1.5 g of sodium thiosulfate (Na2S2O35H2O) in 50 mLof wate
23、r and dilute to 250 mL. Standardize as follows: Pipet 10mL of the KIO3solution into each of three 150-mL beakers.Dilute each to 100 mL with water, add2gofKIand5mLofH2SO4(1+18), and dissolve the KI with stirring. Titrate theliberated iodine with 0.025 N Na2S2O3solution until the colorof the solution
24、becomes pale yellow. Add 2 mL of starchindicator and continue the titration dropwise until the colorchanges from blue to colorless.I 5 1mLNa2S2O35 0.01500/V1gFe2O3(2)where:I = iron oxide equivalent of Na2S2O3solution,V1=Na2S2O3required for titrations, mean, mL, and0.01500 = (10.00 mL KIO3) 3 (0.0015
25、00 g Fe2O3/mLKIO3).12. Procedure12.1 Dilute the solution obtained from the procedure in 8.6to 100 mL with water. Add 10 mL of HCl and 5 g KI. Dissolvethe KI with stirring.12.2 Titrate with 0.025 N Na2S2O3solution until the colorbecomes a pale yellow. Add 2 mL of starch indicator solutionand continue
26、 the titration until the color changes from blue tocolorless.13. Calculation13.1 Calculate the percent of iron oxide, D, as follows:D 5 I 3 V2!/S1100! (3)where:V2=Na2S2O3solution required for titration, mL, andS1= weight of original specimen, g.SOLUTION OF PIGMENT FOR THEDETERMINATION OF BORON TRIOX
27、IDE ANDCALCIUM OXIDE14. Apparatus14.1 Boiling Flask300-mL capacity with ground glassconnection.14.2 Bchner Funnel, 56-mm diameter.14.3 Filter Paper, 55-mm diameter.414.4 Filter Flask, 250-mL capacity.14.5 Hot Plate/Stirrer.14.6 pH Meter.14.7 Reflux Condenser, with ground glass connection, watercoole
28、d.14.8 Sintered Glass Crucible, 50-mL capacity, mediumporosity.14.9 Volumetric Flask, 250-mL capacity.15. Reagents15.1 Hydrochloric Acid (1+1).15.2 Hydrochloric Acid (1+25).4The sole source of supply of Whatman No. 50 Filter Paper, known to thecommittee at this time is Whatman, Inc. If you are aware
29、 of alternative suppliers,please provide this information to ASTM International Headquarters. Your com-ments will receive careful consideration at a meeting of the responsible technicalcommittee,1which you may attend.D 4487 90 (2008)215.3 Nitric Acid (1+1).15.4 Potassium Hydroxide, pellets.15.5 Pota
30、ssium Hydroxide Solution, 28 g/L.16. Procedure16.1 Introduce 2.5 g of sample, weighed to 0.1 mg, into the300-mL boiling flask.16.2 Add 50 mL of HCl (1+1) and 2 drops HNO3(1+1).Place a magnetic stirring bar in the flask, connect the refluxcondenser to the flask, and reflux for 1 h on the hotplate wit
31、hconstant stirring.16.3 Remove the hotplate and place an ice bath under theflask. After the solution has cooled, wash the condenser downwith a small amount of water (10 mL) and remove from theflask.16.4 Filter the mixture through a Bchner funnel equippedwith filter paper4into a 250-mL filter flask.
32、Wash the boilingflask with several 5-mL portions of hot water to transfer all thematerial to the filter.16.5 Cool the filtrate in an ice bath to a temperature ofapproximately 10C, add 15 g of KOH pellets and swirl todissolve them. Using the pH meter, neutralize the solution to apH from 6.0 to 7.0, a
33、dding first KOH pellets and finally eitherKOH (28 g/L) or HCl (1+25). Be careful not to add appreciablyto the volume of the solution, nor to exceed a pH of 7.0.16.6 After neutralizing the solution, warm it gently on a hotplate to coagulate the iron precipitate. Filter off the ironprecipitate with a
34、medium-porosity sintered glass filter into aclean 250-mL filter flask.16.7 Replace the sintered glass crucible on the original filterflask and add 10 mL of water. Dissolve the iron precipitate bythe dropwise addition of HCl (1+1) and constant stirring. Filterwith suction and wash the crucible with t
35、wo 5-mL portions ofhot water. Swirl the acidic solution around in the flask todissolve any iron precipitate adhering to the sides of the flask.16.8 Repeat the neutralization step (16.5) and filter thesolution through the sintered glass crucible into the flaskcontaining the first filtrate (16.7).16.9
36、 Wash the flask used in the neutralization with two5-mL portions of water, and then wash the precipitate in thecrucible.16.10 Transfer the filtrate quantitatively to a 250-mL volu-metric flask and dilute to volume. Use this filtrate for thedetermination of boron trioxide (Sections 17-19) and calcium
37、oxide (Sections 20-22).BORON TRIOXIDE17. Apparatus17.1 pH Meter.17.2 Buret, 25-mL capacity.17.3 Volumetric Flasks, 1000-mL and 100-mL capacity.17.4 Drying Oven, maintained at 105 6 2C.18. Reagents18.1 Hydrochloric Acid (1+19).18.2 Mannitol.18.3 Phenolphthalein Indicator Solution Dissolve 0.10 gpheno
38、lphthalein in 50 mL of ethyl alcohol. Dilute to 100 mLwith water.18.4 Thymol Blue Indicator Solution Dissolve 0.1 g ofthymol blue in 50 mL of 0.01 N sodium hydroxide. Dilute to100 mL with ethyl alcohol.18.5 Mixed Indicator SolutionMix 25 mL of thymol blueindicator solution with 75 mL of phenolphthal
39、ein indicatorsolution. Adjust the pH from 6.0 to 7.0 on a pH meter witheither HCl (1+19) or NaOH (0.1 N).18.6 Potassium Hydrogen Phthalate (KHP)Acidimetricstandard.18.7 Sodium Hydroxide, Standard Solution (0.1 N)Dissolve 4.0 g of NaOH pellets in 100 mL of water and diluteto 1 L in a volumetric flask
40、. Standardize as follows: Dry 2.0 gofKHPfor2hat105C in the oven and cool. Weigh 1.6420g and dissolve in 50 mL of water. Transfer quantitatively to a100-mL volumetric flask and dilute to volume with water (1mL = 0.002800 g B2O3). Pipet 25 mL of the KHP solution intoeach of three 150-mL beakers. Add 3
41、 drops of phenolphthaleinindicator and titrate with 0.1 N NaOH until the color changesfrom colorless to red.B 5 1 mL NaOH 5 0.07000/V3gB2O3(4)where:B =B2O3equivalent of NaOH solution,V3= NaOH used in standardization titrations, mean,mL, and0.07000 = (25.00 mL KHP) 3 (0.002800 g B2O3/mLKHP).19. Proce
42、dure19.1 Pipet 50 mL of the filtrate from the procedure in 16.10,which has been diluted to volume, into each of two 150-mLbeakers.19.2 With the pH meter, adjust the pH of each solution to6.0 using either HCl (1+19) or 0.1 N NaOH. Add 10 g ofmannitol and dilute to 100 mL with water.19.3 Add 1 mL of m
43、ixed indicator solution and titrate with0.1 N NaOH. The end point is when the color changes fromyellow to dark violet.20. Calculation20.1 Calculate the percent of boron trioxide, E, as follows:E 5 B 3 V4/S2500! (5)where:V4= NaOH used in titrations, mean, mL, andS2= weight of original specimen, g.CAL
44、CIUM OXIDE21. Apparatus21.1 Buret, 25-mL capacity.21.2 Volumetric Flasks, 500-mL and 1000-mL capacity.21.3 Reagents.21.4 Ammonium Hydroxide (1+4).21.5 Buffer SolutionDissolve 33.75 g of ammonium chlo-ride in 285 mL of NH4OH, add 5 mL of concentratedammonium sulfide, and dilute to 500 mL with water.D
45、 4487 90 (2008)321.6 Calcium StandardDry7gofcalcium carbonate(CaCO3) at 105C for 2 h. Weigh 6.2461 g of the dried CaCO3into a 500-mL flask. Slowly add HCl (1+1) until all the CaCO3has dissolved. Add 200 mL of water and boil for a few minutesto expel CO2. Cool and adjust the pH from 5 to 6 by addingN
46、H4OH (1+4) or HCl (1+1). Transfer solution to a 1000-mLvolumetric flask and dilute to volume. 1 mL = 0.003500 gCaO.21.7 Sodium Carbonate (0.2 %)Dissolve2gNa2CO3inwater and dilute to 1 L.21.8 Sodium Carbonate (10 g/L)Dissolve 10 g Na2CO3inwater and dilute to 1 L.21.9 Eriochrome Black T Indicator Solu
47、tionDissolve 1.0g of Eriochrome Black T in 30 mL of 0.2 % sodium carbonate(Na2CO3) solution. Dilute to 100 mL with isopropanol. Adjustthe pH to 9.0 with Na2CO3solution (10 g/L). Indicator shelflife: 2 months.21.10 EDTA, Standard Solution (0.17 N)Weigh 63.3 g ofdisodium ethylenediamine tetraacetate (
48、EDTA) and 0.1 gmagnesium chloride (MgCl2), and dissolve in 500 mL ofNaOH (20 g/L) solution and dilute to 1 L with water.Standardize as follows: Pipet 50 mL of calcium standard intoeach of three 150-mL beakers. Add 15 mL of buffer solutionand 3 to 4 drops of indicator solution to each beaker. Titrate
49、immediately with EDTA solution (0.17 N) until the colorchanges from red to a definite blue.C 5 1 mL EDTA 5 0.1750/V5g CaO (6)where:C = CaO equivalent of EDTA solution,V5= EDTA required for titrations, mean, mL, and0.1750 = (50 mL Ca Standard) 3 (0.003500 g CaO/mL).22. Procedure22.1 Pipet 50 mL of the filtrate from the procedure in 15.10into each of two 150-mL beakers. Add 25 mL of buffer and 3to 4 drops of indicator solution to each beaker.22.2 Immediately titrate with EDTA until the color changesfrom red to a definite blue.23. Calculation23.1 C
