(fp cceonton 0-0 Standard Test Methods for rsa rene AS etn py AST Chemical Analysis of Titanium and Titanium Alloys’ This sandare insu wder the fied designation E120; the number immediatly fallowing the designation indicts the year of rial adoption rm he ae evi the ya fat ein. A umber im prethencs nats the Yeast Feapprval. A Speci epaln (india an eto cate sine the as eison or repro This sandard has boo eprovd fer we by egenis ofthe Daportmont of Defense Cons the Deb Index of Speceatons ond ‘Standards for he spec year tse which has ber adopted bythe Deparment of Defense 1, Scope 1.1. These test methods cover procedures for the chemical analysis of titanium and titanium alloys containing the following elements in the concentration ranges listed: Blemeat Concetaion Rage, % Alurinumn 110 Grione om 10 Gromum ans te 20 Columbor basis Coreer Door wea Irom 0s te 20 Magnus on ie1e Manganese 008 ¥6 20 Molybdenum 00s ve 3 Nitoser 9005 20 Oxrsen Bits oas0 Paar 51016025, Stoon bans 030 Tesla 281030 Te 028 610 Tengen Sans io 10 Varad 051020 Bicone 191620 1.2. The test methods in this standard are contained in the sections indicated as follows: Sections 1 Quolinal (Grevimetrie) Test Method? fou (Clone by he Gravimetie Test Meth? Ben Conver (Copezone (Photometric) Test Metis on Dietyhithioerbamate (Photorsinc) Test Method nea Manganee: Penodate (Photometric) Tet Method Ben Mabybeenese "Thos aaie-Extraction(Photomei) Tet Method S106 ‘Thonyanate 242 Buonyethouy) Eine! (Photometric) Test 631072, ‘Metnee Duinegen hy the Dianon- Thon Text Metka? Dow Pallas by the Nitav-2-Napbio! (Protomer) Test er Method Vanadium by he Pots Permanganate(Tivimetic) Test 91 097 Method iconn by the Mande Acid (Gravieetic) Tet Method 98 0 [06 13 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appro- priate safety and health practices and determine the applica- "Tess tes methods are ueder the junc of ASTM Commitee E-t on ‘Anica Chem le Metals, Ores, and Related Materials and are the dec. ‘aponialty of Schonemite EDO on, Zr, W. Mo, Ta, Mb HE ‘Cureet editon approved Jan. 10,1996. Pebshed Mach 1936, Originally pubes E 120-56, Last previos edition 120-89. >The ex metho are bexed of the methods developed by the Parson Methods of Analyse of the Mecongcal Aviary Commits on Tian, Ordeence Corp, US Army, and publhed in ir Bullet Te bility of regulatory limitations prior to use. 2, Referenced Documents 2.1 ASTM Standards: E 29 Practice for Using Significant Digits in Test Data 10 Determine Conformance With Specifications? E 50 Practices for Apparatus, Reagents, and Safety Pre- cautions for Chemical Analysis of Metals! E $9 Practice for Sampling Steel and Iron for Determina- tion of Chemical Composition E 60 Practice for Photometric and Spectrophotometric Methods for Chemical Analysis of Metals* E 173 Practice for Conducting interlaboratory Studies of Methods for Chemical Analysis of Metals* 3. Significance and Use 3.1. These test methods for the chemical analysis of metals and alloys are primarily intended to test such materials for compliance with compositional specifications. [tis assumed that all who use these test methods will be trained analysts capable of performing common laboratory procedures skill fully and safely 1 i expected that work will be performed in 4 properly equipped laboratory 4, Apparatus, Reagents, and Photometric Practice 4.1 Apparatus and reagents required for each determina- tion are listed in separate sections preceding the procedure, ‘The apparatus, standard solutions, and certain reagents used in more than One procedure are relerred to by number and shall conform to the requirements prescribed in Practices E50, except that photometers shall conform to the require ‘ments prescribed in Practice E 60. 5. Hazards 5.1 For hazards to be observed in these test methods, teference shall be made to Practices E 50. 6, Sampling 6.1 No standardized sampling procedures are available, but the principles of Practice E 59 should be used as 2 guide to obtain representative samples, bearing in mind that with preseat melting practices titanium metal and titanium-base alloys may show greater inhomogencities than are usually found in steels, 6.2 The sample used for the chloride determination shall, not be subjected to any physical or mechanical process that breaks down ot opens up significant portions of cells of the > anal Book of ASTM Standards, Wo 14.02 Anal Book of ASTM Standards, Vol 03.08) & 120 titanium sponge, or causes a localized heating of the sponge sample. Avoid briquetting, compacting, drilling, or combina tion thereof, of the titanium sponge to obtain « laboratory sample for analysis of chloride, 7. Rounding Calculated Values 7.1 Calculated values shall be rounded to the desired number of places in accordance with the rounding test ‘method given in 3.4 and 3.5 of Practice E 28. ALUMINUM BY THE 8-QUINOLINOL (GRAVIMETRIC) TEST METHOD 8. Scope 8.1 This test_method covers the determination of alu- ‘minum in titanium and titanium alloys in concentrations from 110 8 %. 9. Summary of Test Method 9.1 The sample is dissolved in hydrochloric and nitric acids and treated with sodium hydroxide to precipitate titanium and other metals, Aluminum in the filtrate is precipitated with 8-quinolinol in the presence of hydrogen peroxide, dried, and weighed. 10, Interferences 10.1 The elements ordinarily present do not interfere if their concentrations are under the maximum limits shown in. i 11. Reagents, 11.1 &-Quinolinof Solution (25 g/L)—Reagent No. 130 11.2 Sodium Hydroxide Solution A (300 e/L}—Prepare a solution as described for Reagent No. 146, but use 300 g instead of the specified weight 11.3 Sodium Hydroxide Solution B (100 g/L)—Reagent No. 146, 11.4 Tartaric Acid Solution (250 g/L) —Prepare a solution as described for Reagent No, 116, but use 250 g instead of the specified weight. 12, Procedure 12.1. Transfer a |.0-g sample, weighed to the nearest 1 mg, to a.400-mL. beaker. 12.2 Carry a reagent blank through the entire procedure, using the same amounts of all reagents with the sample omitted 123 Add 100 mL. of HCI (141), and heat gently until dissolution is complete. Add HNO, dropwise until the titanium is oxidized, and then boil gently to expel oxides of nitrogen. 12.4 Cool, nearly neutralize (Note 1) with NaOH Solution ‘A, and pour the solution slowly, with stirring, into a 600-mL beaker containing 150 mL of hot NaOH Solution B. Boil for | min while stirring constantly, and cool to room tempera- ture in a running water bath, Nore 1—Once the solation is made alkaline it must be carried through the procedure without delay until i acidified to Timmus 36 directed in 126, 125 Transfer to a S00-mL volumetric flask, dilute to volume, and mix. Immediately transfer, without rinsing, to a dry 600-mL beaker, Filter through a dry 18,5-cm fluted filter paper into a dry 250-mL volumetric flask, discard the first 50 mL, and collect 250 mL of the filtrate 12.6 ‘Transfer to a 600-mL beaker and acidify to litmus with HCI (141). Add 25 mL of tartaric acid solution and adjust to pH 8.0 using NHJOH and pH test paper. Add 10 mL of HO; (30 %) and heat to 50 to 60°C. While mechan- ically stirring, add 3.5 mL of 8-quinolinol solution for each 5 ‘mg of aluminum present, plus 5 mL in excess. Add 5 mL of NH,OH and continue stirring for 10 min 12.7 Allow the precipitate to settic. Filter through a weighed medium-porosity fiitted-glass crucible. Test for completeness of precipitation by the addition of S mL of 8-quinolinol solution to the filtrate. Wash the precipitate four times with warm NH,OH (1+99). Dry at 139°C for 12 hh. Cool in a desiceator and weigh as alurninum quinolinate. 13. Calculation 13.1, Calculate the peroentage of aluminum as follows: Aluminum, % = (4 ~ BY x 0.0887 x 100/C where: A= grams of aluminum quinotinate found in the aliquot used, grams of aluminum quinolinate in the blank, and (C= grams of sample represented in the 250-mL aliquot. 414, Precision and Bias 14.1. Precision—Seven laboratories cooperated in testing this test method on samples of Ti6A1-28n-42r-2Mo and Tiel3V-11Cr-3Al, and obtained the data summarized in Table t 14.2 Bias—No centfied reference materials suitable for testing this test method were available when the interlaboratory testing program was conducted. The user of this test method is encouraged to employ accented reference materials, if available, to determine the bias of this test method as applied in a specific laboratory. (CHLORIDE BY THE GRAVIMETRIC TEST METHOD 15. Scope 15.1 This test method covers the determination of cilo- ride in titanium sponge in the range from 0,02 10 1 %. ‘TABLE 1 Precision Data for Aluminum by the 8-Quinotin! (Gavimetrc) Method ‘arin Fore, % by Labealey NO™ ‘est waewna r z 3 ‘ 5 z 7 (i Therion bse aay, 2Sraz-aMo on $a bok Bon OF 60 61st See GS Gs S85 (2) Tanuae-paa aay, 130-116 a 318 ate 3238 an 3m a3) ma * och samp ane once on each fo ya on Dee,h & 120 16, Summary of Test Method 16.1 The sample is dissolved in dilute hydrofluoric acid ‘and oxidized with nitric acid. The chloride is precipitated With silver nitrate and weighed as silver chloride. 17. Interferences 17.1 Blements normally present in titanium sponge do not interfere, 18. Apparatus 18.1 Filtering Crucibles, Sritted-glass, fine-porosity, 30- ‘mL, conforming to the requirements for Apparatus No. 2 18.2 Plastic Beakers, 400 oF 600-mL. 18.3 Plastic Graduated Cylinder, 25-maL. 19. Reagents 19.1 Borie Acid (HBO). 19.2 Silver Nitrate Solution (5.8 g/L\—Dissolve 5.8 g of silver nitrate (AgNO) in water and dilute to | L. 19.3 Silver Nitrate Wash Solution (0.05 p/L)—Dissolve 0.05 g of silver nitrate (ARNO) in J L of water 20. Procedure 20.1 Transfer 20 mL. of HF and SQ mL of water to a plastic beaker and mix. Weigh 5 g of the sample to the nearest |_mg. Transfer 1 to 2 g of the sample, in small portions, to the dilute HF solution. (Soe 6.2 for guidelines for handling the sample.) Add $ mL. of HNO, and then add the remainder of the sample in small portions. Afterall of the metal has been added, allow to stand until dissolution is ‘complete Note 2—Dissolution of the sample is usually complete in $ min, ‘with «colores solution beng obiained. I the solution i not colores, SAU TINO, dropwise until the color disappears 20.2 Carry a reagent blank through all steps of the procedure. 203 Add 5 g of HBO; to the solution, transfer to a 400-mL glass beaker, and dilute to 200 mL. Stir and heat gently until the HBO, dissolves. With stirring, slowly add 10 mL of the AgNO; solution. Heat to approximately 60°C and maintain at this temperature untii the supernatant liquid clears. Test for completeness of precipitation by adding a few ‘drops of the AgNO, solution. If additional precipitate forms, add an additional § mL. of AgNO, solution and repeat the above operation, Allow to stand in a dark place for 2b. 20.4 Filter, using a low-ash, fine-textured, paper, and wash thoroughly with the AgNO, wash solution. Dissolve the precipitate by pouring 50 mI of NH,OH (1+!) in 10-mL increments through the filter, collecting the filtrate in the original beaker. If necessary, pour the NH,OH through a second time to dissolve the silver chloride (Note 3). Wash the paper thoroughly with water. [Nove 3—Residua titanium hydroxide om the paper should not be confised with aver chloride 205 Make the filtrate slightly acid with HNO, using methyl orange indicator. Add 5 raL. of the AgNO; solution and stir to coagulate the precipitate. Check for complete precipitation as described in 20.3. Allow to stand in a dark place for 2 h, Filter through a weighed fritted-glass crucible, Police the beaker and stirring rod and wash thoroughly with the AgNO, wash solution. Finally, wash twice with water, 20.6 Dry the crucible and contents at 130 to 150°C to constant weight (approximately 2 h). Cool in a desiccator and weigh 21, Cateul 21.1 Calculate the percentage of chloride as follows: Chloride, % = [(A = B) x 0.2474/C] x 100 where: A= grams of AgC\ from the sample, B = grams of AgCi from reagent biank, and C = grams of sample used. 22, Precision and Bias 22.1. This test method was originally approved for publi- cation before the inclusion of precision and bias statements within standards was mandated. The original interlaboratory test data for this test method are no longer available. The user is cautioned to verify by the use of reference materials, if available, that the precision and bias of this test method are adequate for the contemplated use. COPPER BY CUPRIZONE (PHOTOMETRIC) TEST METHOD. 23, Scope 23.1 This test method covers the determination of copper in concentrations from 0.4 to 1.1 %. 24, Summary of Test Method 24.1 Ammonium citrate is added to the sample solution, and the pH adjusted to about 8.5. Cuprizone is added to form a blue-colored complex with cupric copper. Photo ‘metric measurement is made at approximately 600 nm, 25, Concentration Range 25,1 The recommended concentration range is from 0.05, 0 0.3 mg of copper/100 mL of solution using a 1-em cell. [Nore 4—This test method hes been written for cells having a Im light path. Ces having other dimensions may be used, provided suitable fcjustments ean he made in the amounts of cample and reagent used 26. Stability of Color 26.1 The color develops in 20 min and is stable for 1 h. 27, Interferences 27.1 The elements ordinarily present do not interfere When more than 1% of nickel or cobalt is present, the addition of ethanol stabilizes the color. 2. Reagents 28.1 Ammonium Citrate Solution (500 g/L)—Dissolve 500 g of ammonium citrate in hot water, cool, and dilute to 1h. 28.2 Copper, Standard Solution (\ ml. = 0.01 mg Cu}— Transfer 0.2000 g of copper (purity: 99.95 % min) to a 250-mL beaker, and cover. Dissolve in 15 mL of water and 3 mL of HNOs. When dissolution is complete, gently boil out nitrogen oxide fumes. Cool, transfer to a I-L volumetric flask, dilute to volume, and mix. Transfer $0.0 mL to @ J-L.4) & 120 volumetric flask, dilute to volume, and mix. 28.3 Deionized Water—Deionized water is used ‘throughout this test method. 28.4 Dicyclohexanone Oxaiyldihydrazone (Cuprizone) So- Audion (4 g/L of ethanol (1+ 1))—Dissolve 4 g of cuprizone in hot ethanol (1+1), cool, and dilute to 1 L with ethanol (1+1). 28.5 Ethanol (1+1)—Mix 1 volume of ethanol (95 %) with T volume of water. 28.6 Fluoboric Acid (48 0 50 %) (HBF,). 29, Preparation of Calibration Curve 29.1. Calibration Solutions —Transfer 5.00, 10:00, 20.00, and 30.00 mL of copper solution (1 mL = 0.01 mg Cu) t0 four 100-mL beakers, and dilute to approximately 30 mL. (Proceed a5 directed in 29.3.) 29.2 Reference Solution—Transfer 30 mL. of water to @ 100-raL beaker, (Proceed as directed in 29.3.) 29.3 Color Development—Add 10 mL of ammonium citrate solution and adjust to a pH of $ to 9 with NH.OH. Cool to room temperature, and transfer the solution to a 100-mL volumetric ask. Add 10 mL of cuprizone solution imix, dilute to volume with water (Note 5), and mix again. ‘Allow the solution to stand 20 min. Nore $—if more than 1% of nickel of cobalt it present in the sari a $0 mt of ethanol (95°%) afer the 10 mt of cuprizene Solution: then dilute wo volume with water, and mis again, This dition ef ethanol should be made to the cubation and reference soltions a: wells to the test soluon, Tae eal increases the saaiy ofthe Color sgnicanly in the presence of wick and eobal, but is nat eceuay it the als of commercial tam alloys 29.4 Photometry 29.4.1 Muliple-Cell Photometer—Measure the cell cor- rection using absorption cells with a 1-em light path and 2 light band centered at approximately 600 nm. Using the test cell, lake the photometric readings of the calibration solu- tions. 29.42 Single-Cell Photometer—Transfer a suitable por- tion of the reference solution 10 an absorption cell with ‘em light path and adjust the photometer to the initial setting, using alight band centered at approximately 600 nm. While’ maintaining this adjustment, take the photometric readings ofthe calibration solutions. 29.5. Calibration Curve—Plot the net photometric read- ings of the calibration solutions against milligrams of copper per 100 ml. of solution 30, Procedure 30.1 Test Solution: 30.1.1 Transfer 0.100 g of the sample, weighed 10 the nearest 0.1 mg, to a 100-mL beaker. Add 20 mL of HCI (+1) and 2 mL of HBF,, and heat gently. When dissolution is complete, oxidize by the dropwise addition of HNOs, Cool, transfer to a 100-mL volumetric flask, dilute to volume, and mix. 30.1.2 Transfer @ 20.00-mL aliquot, in duplicate to two 100-mi beakers [Nove 6—Dupliate aliquots are taken inorder to ba to determine the background coor. 30.2 Reference Solution-—Uise deionized water as the reference solution 30.3 Reagent Blank Sotuion—Cary a reagent blank ‘through the entire procedure using the same amounts ofall reagents, with the sarmple omitted 30.4 Color Development—Proceed with one of the dupli« cates as directed in 29.3, 30,5. Background Color Soluion—Proceed with the other duplicate as directed in 29.3 but omit the addition of the ‘cuprizone solution, 30.6 Photomeiry—Take the photometric readings of the reagent blank solution, the background color solution, and the test solution as directed in 29.4 one available 31. Calculation 31.1 Convert the net photometric readings of the reagent, blank solution, background color solution, and test solution to milligrams of copper by means of the calibration curve. Caleulate the percentage of copper as follows: Copper, % = [A = (B + CMD « 10) where: 4 = milligrams of copper found in 100 mL of final test solution, B= reagent blank correction, mg of Cu, C = background color correction, mg of Cu, and D = gcams of sample represented in 100 mL of the final test solution, 32. Precision and Bias 32.1 Precision—Nine laboratories cooperated in testing this test method and obtained the data summarized in Table 2. 32.2 Bias—No certified reference materials suitable for testing this test method were available when the interlab- oratory testing program was conducted, The user of this test ‘method is encouraged to employ accepted reference mate- rials if available, to determine the bias of this test method as applied in a specific laboratory. (COPPER BY THE DIETHYLDITHIOCARBAMATE (PHOTOMETRIC) TEST METHOD 33 Scope 433.1. This test method covers the determination of copper in concentrations from 0.001 to 0.95 %. TABLE 2_ Statistical Information—Copper by Cuprizane (Photometric) Method Test Mae ‘Coops Found. ‘Mepealibiy —_— Reroaucty * (ETS ETS) o Ti aoy ost 0084 057 [ASTI 0289 6% T, Grae Fm) (6A1-5V26n-080u0.7Fe) 2 Tasoy oats, 0.025 oor (ASTI 8283 6 T, Grado F8) (6A1-4V.25n-0.86u0.7Fo) oy TiAoy oar oon 05 |ASTH 8201 6 T,Grae Fs) GAL-AV.250-1 COU0.7Fe)Gh 120 34, Summary of Test Method 34.1 The sample is dissolved in sulfuric and fluoboric acids and oxidized with nitric acid. Ammonium citrate and EDTA are added as complexing agents. The solution is adjusted to pH 8 5, diethyldithiocarbamate is added, and the copper complex extracted with chloroform. Photomeiric ‘measurement is made at approximately 440 nm, 35. Concentration Range 35,1 The recommended concentration range is from 0.005 v0 0.12 mg of copper per 25 mL of solution, using a tem cel Nove. 7—This ret method has been written for cells having a Lem. light pata, Clit having ther dimensions may be used, provided suitable adjustments can be made inthe amounts of sample and reagents used. 36. Stability of Color 36.1 The color is stable for at least 30 min in bright light, ‘or for several hours in diffuse daylight. 37. Interferences 37.1 The clements ordinarily present do not interfere. 38. Reagents 38.1 Ammonium Curate Schution, Purified—~Add 210 ml of NH,OH to 150 mL of water. Add 200 g of citric acid in small portions white stirring and cooling, and dilute to 500 mL, Transfer 100 mL. 10 a 250-mL separatory funnel, make slightly ammoniacal, add 5 mL. of sodium diethyldithio- carbamate solution, ‘and mix. Add $0 mL of chloroform (CHC) and shake for 1% min, Discard the organic phase. 38.2 Chloroform (CHC). 38.3 Copper. Standard Solution (1 mL = 0.01 mg Cuy— ‘Transfer 0.1000 g of copper (purity: 99.95 % min) to a 250-mL. beaker, and cover. Dissolve in 15 mL of water and 2 mL of HNO, When dissolution is complete, gently boil to remove oxides of nitrogen, Cool, transfer to a I-L volumetric flask, dilute to volume, and mix. Transfer 20.00 mL. to a 200-inL volumetric flask, dilute to volume, and mix, 384, Deionized Water—Deionized water is throughout this test method. 38.5 Disodium (Ethylenedinitrilo} Tetraacetate Dihydrate (EDTA) Solution (100 g/L}—Dissoive 10 g of disodium {ethylenedinitrilo) tetraacetate dihydrate in 90 mL. of water, and dilute to 100 mb. 38.6 Fluoborie Acid (48 10 50 %) (HBF,) 38.7 Sodium Diethyldithiocarbamate Solution (1 g/L)— Dissolve 0.10 g of sodium diethyldithiocarbamate in 90 mL of water, and die to 100 mL. Store in an amber bottle. Do ot use & solution that has stood for more than one week. used 39. Preparation of Calibration Curve 39.1. Calibration Solutions, 39.1.1 Transfer 0.50, 1,00, 3.00, 5.00, 8,00, and 12,00 mL. of copper solution (1 ml. = 0.01 mg Cu) to six 100-mL. beakers. Add 25 mL of H,SO, (1+1),0.5 mL of HBF,, and 3 0 5 drops of HNO). 39.12 Add 20 mL of ammonium citrate solution and 10, mL of EDTA solution, Adjust to pH 8.5 with NH,OH. Cool and transfer to 2 250-mL separatory funnel, Proceed as directed in 39.3, 39.2. Reference Solution—Carry a reagent blank through the entire procedure, using the same amounts of all reagents, with the sample omitted, for use as the reference solution. 39.3 Color Development—Add 10.0 mL. of sodium dicthyldithiocarbamate solution and mix. Add 10 mL of, CHC1, and shake for 1% min. Allow the layers to separate, Transfer the CHCl layer to a. 2S-mL_ glass-stoppered volumetric flask. Repeat the CHCI, separations two more times using 5 mL of CHCI, each time, Transfer the CHC}, layers to the 25-mL glassstoppered volumetric flask, Dilute 10 volume with CHT and mix 39.4 Photometry: 39.4.1 Multiple-Cel! Photometer-—Measure the cell cor- rection using absorption cells with a f-cm light path and 2 light band centered at approximately 440 nm. Using the test cell, take the photometric readings of the calibration solu- 39.42 Single-Cell Photometer—Transfer a suitable por- tion of the reference solution to an absorption celi with a lem light path and adjust the photometer to the initial setting, using a light band centered at approximately 440 nm, While maintaining this adjustment, take the photometric readings of the cal solutions 39.4.3 Calibration Curve—Plot the net photometric read- ings of the calibration solutions against milligrams of copper per 25 mL of solution, 40. Procedure 40.1. Test Solution: 40.1.1 Select and weigh @ sample in accordance with the following: “oleae in Sample Copper. Sample Weight Weobt me 001 w 002 ox os ‘nz tous 02m 0s ons oss 0100 et ‘Transfer the sample to a 100-mL beaker. 40.1.2 Add 25 mL of H,SO, (1+4) and 0.5 mL of HBF,, and heat gently. When dissolution is complete, oxi ‘dropwise with HNO, and then add 3 drops in excess. Boil 2 to 3 min to remove oxides of nitrogen, and cool. For samples containing up to 0.1 % Cu, proceed as directed in 39.1.2. 40.1.3 For samples containing 0.1 to 0.55 % Cu, transfer the test solution 19 a 100-mL. volumetric flask, dilute to volume, and mix. Transfer a suitable aliquot toa 100-mL. ‘beaker. A sample solution is shown in the following: Aliguot opps Volume, 01 0035 359 ansto03s 209 Proceed as directed in 39.1.2. 40.2 Reference Solution—Proceed as directed in 39.2. 40.3 Color Development—Proceed as directed in 39.3, 40.4 Phoometry—Take the photometric reading of the test solution as directed in 39.4. 41. Calculation 41.1 Convert the net photometric reading of the test solution to milligrams of copper by means of the calibrationib € 120 curve. Calculate the % of copper as follows: Copper. % = AMEX 10) where: A = milligrams of copper found in 25 mL of final test solution, and B = grams of sample represented in 25 ml. of final test solution, 42. Precision and Bi 42.1. Precision—Nine laboratories cooperated in testing this test method and obtained the data summarized in Table 3 42.2 Bias—No certified reference materials suitable for testing this test method were available when the interlaboratory testing program was conducted. The user of this test method is encouraged to employ accepted reference materials, if available, to determine the bias of this test method as applied in a specific laboratory. MANGANESE BY THE PERIODATE (PHOTOMETRIC) TEST METHOD 43. Scope 43.1 This test method covers the determination of man- ‘ganese in concentrations from 5 to 7500 ppm. 44, Summary of Test Method 44.1 The sample is dissolved in sulfuric and fluoboric acids and oxidized with nitric acid, The solution is diluted to specific volume, additional nitric acid added, and the manganese oxidized to permanganate with potassium periodate, Photometric measurement is made at approxi- mately $25 nm. 45. Concentration Range 45.1 The recommended concentration ranges are from 5 to 250 yg and from 200 to 1000 yg of manganese per 100 mL of solution, using cell depths of 5 and | cm respectively. Nove, 8—This test method fas been writen for eels having $ and tom light paths. Cells having other dimensions may be used, provided suitable adjustments cin be made in the amounts of sample and reagents sed, 46. Stability of Color 46.1 The color is stable for several hours. 47. Interferences 47.1 Provision has been made for the correction of any interfering elements present in titanium and titanium-base alloys. 48, Reagents Nore 9--If deionized water is used, itis necessary to teat the water before preparing. the solutions to make cera that 0 reducing impurities ae present. Treat the water a follows: ad 10 mL of H,S0, 1011 L of water and bring to a boll Add several crystals of potassium ‘eriodate (KO,) tol for 10 min and then cook 48.1 Manganese, Standard Solution A (1 mL = 100 4g, ‘Mn)—Reagent No. 24. 48.2 Manganese. Standard Solution B (I ml. = 10 ne ‘Mn)—Transfer & 20-mL aliquot of manganese Solution A to 2 200-mL volumetric Mask, dilute to volume, and mix. Prepare as needed. 48.3 Potassium Periodate Solution (50 g/L. of HNOs (1+4)}—-Dissolve 25 g of potassium periodate (KIO,) in 400 mL of hot HNOs (1++4), cool, and dilute to 500 mL. with HNO, (1+4). 484 Sodium Nurite (20 g/L}—Dissolve 1 g of sodium nitrite (NaNO;) in water and dilute to $0 mL. Prepare fresh as needed, 49. Preparation of Calibration Curve 49.1, Calibration Solutions, 49.1.1 Transfer 0.5, 2.5, 5.0, 10.0, 15.0, 20.0, and 25.0 mL of manganese Solution B to seven 250-mL beakers, 49.1.2 Transfer 2.0, 2.5, 5.0, 7.5, and 10.0 ml of manga- nese Solution A to five 250-mL beakers. 49.1.3. Add 45 mL of H,SOg(1+4) and adjust the volume of exch solution ta about 60 mi. Proceed as directed in 49.3. 49.2 Reference Solution—Transfer 45 mL of H;SOq (+4) to 2 250-mL beaker and dilute to 60 mL. Proceed as directed in 49.3 49.3 Color Development—Add 10 ml of HNO; and heat, to boiling, Add 15 mL of K1Q, solution and boil gently for 30 min (Note 10), Cool to room temperature, transfer to a 100-mL volumetric flask, dilute to volume, and mix, Nore 10—Avoid loss of volume, as fll cole development may not be obtained 49.4 Photometry—Transfer a suitable portion of the refer- tence solution to an absorption cell with a S-cm light path or a |-om light path, 2s appropriate (see Section 45), and adjust the photometer to the initial setting using 2 light band centered at approximately 525 nm. While maintaining this adjustment, take the photometric readings of the calibration solutions. 49.5 Calibration Curves—Plot the photometric readings of the calibration solutions against micrograms of manganese per 100 mL of solution, 50. Provedure 50.1 Test Solution: ‘TABLE 3 Statistica! Information—Copper by the Diothyithiccarbamate (Photometric) Mothod Cote Fun, apes opr Te: Matra me eer eee ao Tay rod ‘o.c00 ‘0.007 | thos 14, a-v.0.0%2 Go eee ozs oom cow {havstoeaasoscy a al os oss oom (ASTM 8 361 ~ 617, Grade F-8) (earsv.2en0scod 70)ib 120 50.1.1 Select a sample weight in accordance with the following: Sample Manganese, pam wep 5 to 1000 +00 | 580 to 2000 os00 1900 $000 020 9 103800 2400 50.1.2 Transfer the sample, weighed to the nearest 0.1 mg, to a 250-mL. beaker, Add 45 mL of H,S0, (1+4) and 2 mL of HBF,, When dissolution is complete, add HNO, dropwise ‘until the solution is oxidized; then add drop in excess. Boil for2 to 3 min, Cool, and adjust the volume to about 60 mL. 50.2. Reference Solution—Distillod water. 50:3 Reagent Blank Soluion—Carry @ reagent blank through the entire procedure using the seme amount of all reagents, 50.4 Color Development-—Proceed as directed in 49.3. 50.8 Background Color Soluions—To the remainder of the test and reagent blank solutions, after obtaining the photometric readings. add NaNO, solution droprise, while mixing the solution thoroughly, until the permanganate is reduced; then add! drop in excess. Note 1i—Photometic readings should not be postponed und ‘because seoxidation of manganese occurs on sandine 50.6 Photometry—Adjust the photometer to the initial seiting with the reference solution. While maintaining this adjustment, take the photometric readings of the test solu- tion, the reagent blank solution, and the background color solutions. 51. Calculation 51.1 Convert the photometne reading of the test solution to micrograms of manganese, and the photometric readings of the reagent blank and background color solutions to the equivalent micrograms of manganese by means of the calibration curves, Calculate the parts per million of manga- nese as follows: Manganese, ppm = [(A = #) = (C~ D)VE where: 4 = micrograms of manganese found in 100 mL of the final test solution, B = micrograms’ of manganese equivalent found in the background color solution after reducing the permanganate in the final test solution, C = micrograms of manganese equivalent found in 100 mL. of the reagent blank solution, D = micrograms of manganese equivalent found in the Dackground color solution after reducing the permanganate in the final reagent blank solution, and E = grams of sample represented in 100 mL of the final test solution, 52. Precision and 52.1. Precision—Data on this test method was obtained by ‘eleven cooperators. Standard deviation of precision, repeat- ability, and coefficient of variation were graphically calcu- lated as directed in Practice E 173, and were found to be as. shown in Table 4. $22 Bias—The following data indicates that the bias of ‘TABLE 4 Statistical Information— Manganese by the Periedato (Photometric) Method Manganese Preaier. mT Nlanganase—Varion. A 0328 5.08 aa ua) 538 168 358 sa sox aa a3 1382 106 85 13 this test method is satisfactory: (1) the first of the above listed samples (9.4 ppm) is NBS Standard Sample No. 176 (Ti-SA1-2.8$n), with a certified manganese content of 8 pm; and (2) the third sample (524 ppm) has been previ- ously used by another group testing a different periodate photometric method, and its accepted manganese value was 5340 ppm MOLYBDENUM BY THE THIOCYANATE-EXTRACTION PHOTOMETRIC TEST METHOD 53. Scope 53.1 This test method covers the determination of molyb- denum in titanium and titanium alloys in concentrations from 0.0050 to 0.100 %. 54, Summary of Test Method 54.1 After dissolution of the sample in sulfuric, hydro- chloric, and hydrofluoric acids, titanium is oxidized with hhydrogen peroxide, and the solution is evaporated to SO, fumes, The molybdenum thiocyanate complex is developed and then extracted with butyl acetate. Photometric measure- ment is made at approximately 470 nm, 55. Concentration Range 55.1 The recommended concentration range is from $ to 35 ug of molybdenum per 20 ml. of solution, using a 2-em cell. Nore 12—This est method has been writen for cells heving 8 2m ‘ight path, Cells having other dimensions may be wed, provided suitable adjustments can be made in the amounts of semple and reagents use. 56, Stability of Color 56.1 The color develops in | min and is stable for atleast 3h. 57, Interferences 51.1 The elements ordinarily present do not interfere if their concentrations are under the maximum limits shown in ua 58. Reagents 58.1 Butyl Acetate. 582 Civic Acid Soluion (250 g/1)}—Dissolve 125 g of citric acid monohydrate in about 250 mL of water, add 10 mL of H,SO, (1+1), and dilute 19 500 mL. 58.3 Ferrie Sulfate Solution (50 g/L}—Dissolve $ g of fertic sulfate nonahydrate (Fe,(S0,);-9H,0) in 90 mL of HSO, (1+) and dilute to 100 mL with H,S0, (+1) 58.4 Molybdenum, Standard Solution 4 (1 mL = 150 ws Mo}—Dissolve 0.189 g of sodium molybdate dihydrate (Na;MoO,-2H,0) in 100 mL of H,S0, (1449). Transfer to aib E120 500-mL volumetric flask, dilute to volume, and mix. Stan- dardize this stock solution (1 mL = 150 ug Mo) as described for Reagent No. 8A. [Nore 13—An alternative method for preparing molybdeoum Solu ior A (1 mk = 150 ug Mo) is as follows: Transfer 0.150 g of ‘molybdenum metal (purity: 99.8 % min) to a 1SO-mL beaker. Add 40 ‘iL of H,SO, (141), and H,0, dropwise, until dissolution is complete. Evaporate ust to $O, fumes to destroy exces peroxide. Coo, transfer to 44 vol volumetric Mag, dite 0 about 700 mI, coo), lute wo volume, and ain. 385. Molybdenum, Standard Solution B(t mL = 1.5 we ‘Mo}—Using a pipet, transfer 10 mL of molybdenum Solu tion A (I mL = 150 ug Mo) to a I-L volumetnc flask, dilute to volume with H,SO, (1+99), and mix, Do not use a solution that has stood more than 24h. 586 Sodium Thiocyanate Solution (100 g/L}—Reagent No. 137, 58.7 Stannous Chloride Solution (350 g/L)—Dissolve 175 of stannous chloride dihydrate (SnCly+2H,0) and 5 mg of cupric chloride dihydrate (CuCls-2H;0) in 100 mL. of HC) (1+) by warming gently until a clear solution is obtained. Cool, and dilute to 509 mL. 59, Preparation of Calibr 59.1 Calibration Solutions—Using pipets, transfer 2, 5, 10, 15, and 25 mL of molybdenum Solution B (1 mL ="1.3 ug Mo) to 125-mL. Erlenmeyer flasks, add 15 mL of HaSO« (141, and dilute to 60 mL. Proceed as directed in 59.4 59.2 Reference Solution—Water. $93 Reagent Blark—Add {5 mL of H,SO, (141) to a 125-mL Erlenmeyer flask and dilute to 60° mL. Proceed as directed in 59.4 59.4 Color Development: 59.4.1 Add 1 mL of Fe,(SO,)s solution and 10 mL of citric acid sotution, heat for $ min, and cool. 59.42 Transfer to 2 250-mL conical separatory funnel and cool in running water. Add 10 mL. of NaSCN solution and shake 30 5. Add 10 mL of SnCl solution and shake ‘exactly | min, Using a pipet, transfer 20 mL. of butyl acetate to the funnel, shake 30 s, and cool in running water 2 to 3 min, Shake an additional 30 s and allow the phases to separate. Drain off the lower aqueous layer and discard it. 59.43 Add 50 mL. of H,SO, (1+9), 10 mL of NaSCN solution, and 5 mL of SnC, solution. Shake 305, let stand 2 to 3 min, again shake 30 s, and allow the phases to separate. Draw off the aqueous phase and discard it. Transfer the butyl acetate toa dry test tube, stopper the tube, and allow to stand tunil the solution is cleat. 59.5, Phocornetry 59.5.1 Multiple-Cell Photometer—Measure the reagent blank (which includes the cell correction) using absorption cells with a 2.cm light path and a light band centered at approximately 470 nm. Using the test cell, take the photo- metric readings of the calibration solutions. 39.5.2 Single-Cell Photometer—Transfer a suitable por- tion of the reference solution to an absorption cell with a 2-cm light path and adjust the photometer to ihe initial Setting, using a light band centered at approximately 470 nm. While maintaining this adjustment, take the photometric ion Curve readings of the calibration solutions. 39.6 Calibration Curve—Plot the net photometric read- ings of the calibration solutions against micrograms of molybdenum per 20 mL of solution. 60. Procedure 60.1. Test Solution: 60.1.1 Transfer a 1.00-g sample, weighed to the nearest 1 mg, to a 125-mL Erlenmeyer flask. Add 15 mL of HS, (+1), 40 mL of HCl (1+1), and 1 drop of HF. Heat gently until dissolution is complete, Add HzO, dropwise until a permanent yellow color of peroxidized titanium is formed. ‘60.1.2 Ifthe molybdenum content of the sample is from 5 to 35 us, evaporate to fumes, cool, and dilute to 60 ml. Proceed as directed in 60.4, 60.1.3 If the molybdenum content is from 35 to $00 us, transie: the solution to 2 100-mL. volumetric flask, dilute to volume, and mix. Select an aliquot in accordance with the following H.80, Equivalent Sample Mayteecum, ppm Aliquotml (ivi mL Welt r010350 0 as cio 010 500 $ aS 809) ‘Transfer the aliquot to a 125-mL Erlenmeyer flask, and add the indicated amount of H,SO, (141). Evaporate to SO, fumes, cool, and dilute to 60 mL. Procoed as directed in 60. 60.2. Reagent Blank—Carry a reagent blank through the entire procedure using the same amounts ofall reagents but with the sample omitted. 60.3 Reference Solaion—Water. 60.4 Color Development—Proceed as directed in 59.4 60.5 Photometry—Proceed as directed in 59.5. 61. Calculation 61.1 Convert the net photometric readings of the test and reagent blank solutions to micrograms of molybxenum by means of the appropriate calibration curve. Calculate the percentage of molybdenum as follows: Molybdenum, % = (4 ~ BY(C x 10) where: 4 = micrograms of molybdenum found in 20 mL of the final test salution, B = micrograms of molybdenum found in 20 mL of the final eagent blank solution, and © = grams of sample represented in 20 mL ofthe final test solution (62, Precision and Bias 62.1. Precision—Seven laboratories cooperated in testing this test method and obtained the data summarized in Table 5 62.2 Bias—No certified reference materials suitable for testing this test method were available when the interlabo- ratory testing program was conducted. The user of this test method is encouraged {0 employ accepted reference mate- rials, i availabe, to determine the bias ofthis test method as applied in a specific laboratory@h & 120 TABLE 5 Statistical Ioformation—Molybdenum by Thiocyanate Extraction (Photomotric) Method ite Fea 3 Urn Na Lesiereniah i z a 4 . é z (0) Thanken-ae oy A1-4V (ES) 179A, €.005 Me). 2.00) 9002005004003 O08 Boos — 0.008.005 ooek © ones 2) Ti. rates 9.009 0103 © oe ato2 000 0.100 toa Bio Dore ots Osos 7 Each sarge aazed once on each oo day Wench laboratory MOLYBDENUM BY THE THIOCYANATE 242, BUTOXYETHOXY) ETHANOL PHOTOMETRIC TEST ‘METHOD 63. Scape 63.1 This test method covers the determination of molyb- denum in titanium and titanium alloys in concentrations from 0.04 to 5 %. 64, Summary of Test Method 64.1. The sample is dissolved in hydrochloric acid and the solution is oxidized with nitric acid, After adding sulfuric ‘Acid, the solution is evaporated to fumes. A colored complex is formed with molybdenum and thiocyanate in the presence of ferric ions, 242-butoxyethoxy) ethanol, and stannous chloride. Photometric measurement is made at approxi- mately 470 nm. 65. Concentration Range 65.1 The recommended concentration range is from 0.05 to 1.0 mg of molybdenum per 100 mL of solution, using a -em cell [Nove 14—This tet method tus been written for cells having a -cm lightpath. Ces having other dimensions may be used, provided suitable adjusinents can be made in the amounts of sample and reagents used 66. Stability of Color 66,1. The color develops within § min and is stable for 2 h 67. Interferences 67.1 The elements ordinarily present do not interfere if their concentrations are under the maximum limits shown in Mt 68, Reagents 68,1 2-(2-Butoxvethoxy) Ethanol—(Butyl carbitol_ or ieihylene glycol monobutyl ether). 68.2 Ferric Ammonium Sulfate Solution (8.5 g/L.)—Dis- solve 8.5 of ferric ammonium sulfate dodecahydrate (FeNH,(S0,).°12H,0) in 800 mL of water, add 5 mL of HCI, and dilute to TL, 68.3 Molybdenum, Standard Solution A (1 mL = 1.0 mg ‘Mo)—Dissolve 1.840 g of ammonium heptamolybdate tetrahydrate ((NH4)jMOo;Ozq-4H,0) in 10 mL of NH,OH (+6) in a I-L volumetric flask, dilute to volume, and mix. Standardize this solution as described for Reagent No. 8A. Nore 15--An alternative methad for preparing molybdenum Solo tion A (ml = 1.0 mg Mo) is as follows: Prepare solution as described {or Reagent No, $B, but we 1.000 g of molybdenum and 60 mL of HC, instead ofthe specied weighs an volume 68.4 Molybdenum, Standard Solution B() ml. = 0.05 mg ‘Mo)—Using a pipet, transfer 25 mL of molybdenum Solu- tion A (I'L = 10 mg Mo) to a 500ml volumetric ask, dilute to volume, and mix. Do aot use a solution thet has stood more than 24 h. 68.5 Potassium Thiocyanate Solution (50 g/L.)—Dissolve 01g of potassium thiocyanate (KSCN) in water and dilute to TL 68.6 Stannous Chloride Solution (350 g/L.)—Dissolve 175, x of stannous chloride dihydrate (SnCly-2H,0) in 125 mL of HCL. Heat gently until the solution is clear and then slowly add 150 mL of water. Dilute to $00 mL with HCI (1+1), Do ‘not use a solution that has stood more than 5 days. 69, Preparation of Calibration Curve 69.1. Calibration Solutions—Using pipets, transfer 1, 2.5, 10, and 15 mL of molybdenum Solution B(1 mL = 0.05 me Mo) to 150-mL beakers. Add 10 mL. of H;SO, (1+1), and evaporate to SO; fumes, Cool, and transfer’ to 100-mL Yolumetnic flasks with about 40 mL of water. Proceed as directed in 69.4. 69.2 Reference Solution—Water. 69.3 Reagent Blank Solution—Transfer 10 mL. of HsSOx (1+1) toa 150-mL beaker, and evaporate to $O, fumes. Cool and transfer to 100-mL volumetric flask with about 40 mL. of water. Proceed as directed in 69.4. 69.4 Color Develonment—~Add reagents in the following order: 15 mL of 242-butoxy-ethoxy) ethanol, 1 mL of ferric ‘mmonium sulfate solution, $ mL of KSCN solution, and 5 mL of SoC, solution, Dilute to volume, mix, and let stand for $ min. 69.5 Phovometry: 69.5.1 Multiple-Cell Phoiometer—Measure the reagent blank (which includes the cell correction) using absorption cells with a i-cm light path and light band centered at approximately 470 nm. Using the test cell, take the photo- metric readings of the calibration solutions 69.5.2 Single-Cell Photometer—Transfer a suitable por- tion of the reference solution to an absorption cell with a tem light path and adjust the photometer to the initial setting, using a light band centered at approximately 470 nm, While maintaining this adjustment, take the photometric readings of the calibration and reagent blank solutions. 69.6 Calibration Curve—Plot the net photometric read- ings of the calibration solutions against milligrams of molyb= denum per 100 mL of solution, 70. Procedure 70.1 Test Solution: 70.1.1 Select and weigh a sample in accordance with the followingqb & 120 “Teeance ip Sample ‘Siopie Molybdenum, Wegner weigh me 0005 10200, so 5 198 12 4.00 0 2 ‘Transfer it to a 400-mL beaker. Add 80 mL of HCI, warm gently until dissolution is complete, and cool. Transfer, using HCI, to a volumetric flask of the appropriate size (70.1.2), dilute to volume with HCI, and mix 70.1.2 Transfer to a 150-mL beaker an aliquot selected in accordance with the following: Eayivlent Motyadesur, Ditwion, Aliquot Sample % ‘ml Volume ml Wahi 008 we a10 109 0 0300 (ove too20 "00 $ 0380 tg too xo 5 bins C38 to 100 1600 6 030 99k 0200, tee s ans Tos 40 10 3 Baio Add HINO, dropwise until the titanium is oxidized, as indicated by the disappearance of the purple color. Add 10 ral. of H,80, (141) and evaporate to SO, fumes. Cool and transfer 0 « 1O0-mL volumetric ask with about 40 mL of water, Proceed as directed in 70.4. 70.2 Reagent Blank—Carry a reagent blank through the entire procedure using the same amount of reagents but with the sample omitted 70.3 Reference Solution—Water. 70.4 Color Development—Procecd as dirccted in 69.4 105 Photometr)—Proceed as directed in 69.5. 71. Calculation 711 Convert the net photometric readings of the test and reagent blank solutions to milligrams of molybdenum by means of the calibration curve. Calculate the percentage of molybdenum as follows: Molybdenum, = (4 = BY(C x 10) where: A = milligrams of molybdenum found in 100 mL of the final test solution, milligrams of molybdenum found in 100 mL of the final reagent blank solution, and C = grams of sample represented in 100 mL ofthe final test solution B 72, Precision and Bias 72.1 Precision—Eight laboratories cooperated in testing this test method and obtained the data summarized in Table 6. 72.2 Bias—No certified reference materials suitable for testing this test method were available when the interlaboratory testing program was conducted. The user of this standard is encouraged to employ accepted reference TABLE 6 Statistica Information—Molyblenum by Thiocyanato ‘Butoxyethory) Ethanol (Photometic) Method Monee Ropeatabity Rerodvciniy Tet oe Pont pera ae 7) T42No-SFeScr aay 0.19 020 iB Reunowe tie tate materials, if available, to determine the bias of this test method as applied in a specific laboratory. NITROGEN BY THE DISTILLATION-TITRATION TEST ‘METHOD, 73. Scope 73.1 This test method covers the determination of nix trogen in titanium and titanium alloys in concentrations from 0.005 to 20 %. 74, Summary of Test Method 74.1. The sample is dissolved in a mixture of HBF, and HCL, thus converting the nitrides 10 ammonium salts: The NH is distilled from an alkaline solution into HBO, and titrated with standard acid 75. Concentration Range 75.1. This test method is satisfactory for nitrogen in the range from 0.05 to 1.0 mg in the sample used. 76. Interfering Elements 76.1 There are no known interferences, ‘77. Apparatus 71.1 Microdistillation Apparatues—Parnas-Wagner Micro- ‘Kjeldahl, or equivalent (see Fig. 1). 71.2 Microburet, 10 mL. 78, Reagents 78.1 Borie Acid Soluion (10 g/L)—Dissolve 10 g of HyBO, in water and dilute to 1 L. 78.2 Fluoborie Acid (48 10 50 %). 783 Methyl Purple Indicator 78.4 Sodium Hydroxide Solution (40 %)—Dissolve 400 g of NaOH in 600 mL of water. 785 Standard Ammonium Chloride Solution (1 mL. = 0.0001 g nitrogen)—Transfer 0.3820 g of dry NH,Cl toa t-L. ‘volumetric flask and fill tothe mark with water. 78.6 Sulfuric Acid (0.007 N)—Dilute 2 mL of H,SO, to 1 Land transfer 100 ml. of this to a I-1. volumetric ask Dilute to the mark and mix. Obtain the nitrogen equivalent as follows: Transfer 10.0 mL of the standard NIJ,C1 solution toa 125-mL Erlenmeyer flask. Add HBF, and HC, but no titanium, and continue as directed in 78.1, including the determination of blanks. Nitrogen equivalent = 001KC = DY where C = millilitres of H,SO, required to titrate the standard ‘ammonium chloride solution, and D = millilitres of H,S0, required to titrate the blank, 79. Procedure 79.1 If the expected nitrogen content js 0.07 to 0.20 %. ‘transfer 0.50 g of the sample to a 125-mL Erlenmeyer flask. If the expected nitrogen content is less than 0.07 %, use a 1.0+g portion (Note 16). Add 25 mL of HCI (1+1) and 2 to 3 mL of HBF,. Aliow to sland at room temperature until vigorous action ceases. Place on a steam bath (90 to 100°C) and heat until dissolution is complete, or nearly so.A — Vacusmsectad 175k ston ask 12 — Onete roudotom borcllete ask, abot two thr Mi wth water consinrg 410 § mL of WSO, and ‘ontaning a fow gass boas or olng chips to revert Surg CC — Steam rap, dosed ete top wit stopoek and the DaOM wi Stepceck G or uber ubirg and anc camp. (0 — Fura corcaced to fash A with ber ting and stpccck Hore pec clamp. E — Som. Eonar fas £F Condon ocor wih ster condoner tbe FIG. 1 Microdistiiavon Apparatus Nort 16—It is gnod practice o run the lowenitrogen samples frst and the higher ones lat, simlas tothe practice employed in determining ‘catbon by combustion ‘Nore 17-—I0 the case of alloys of titanium that have insoluble resides due 10 refractory nitrides or high-carbon content, proceed as follows: Dovatt, and reserve the solution, Add to the raidue a crystal of| selenium and $ mL of H,$0, (1+1), heat to dense white fumes 10 istolve the residue, ané combine withthe main solution. Ao alternate procedure i 0 filter the residue on a small pape, digest the paper and precipitate with HIP-H,O;-H,S0,, evaporate to dense white fumes Continue heating wo a clear solution, and combine with the main solution 79.2 Cool the solution and, with stopcock J closed, transfer 10 the micro-Kjeldahl apparatus through funnel D and stopcock H (Fig. 1), rinsing with 10 to 15 mL of water While this is being done, the water in B should be at the boiling point, with the source of heat, a bunsen burner, to cone side and stopcock G open. Pour 25 mL of the NaOH solution through funnel D at a slow rate so that two layers form in vacuum-jacketed flask A and then close stopcock #7. ‘Add 10 mL of HBO; solution and 2 drops of methyl purple indicator to the 50-mL Erlenmeyer flask, £, and adjust it under the receiving condenser so that the tip of the outlet is. Just above the solution in the flask. Increase the heat by placing the bunsen burner under flask B and, when boiling occurs, close stopcock G and open stopcock ¥/, forcing the steam into flask A and mixing the two layers. After the initial vigorous action in flask A (no loss of ammonia takes place), raise flask E until the tip of the condenser is below the level of the solution. After the color of the solution in flask E changes to green (about 1 min), continue the distillation for 3.5 min (collecting a distillate of approximately 10 t0 20 mL). Remove the flask E, rinse the tip of the condenser with about mL of water and at the same time remove the source of heat from 8. (The contents in flask 4 will transfer to fannel C, from which they are discarded by opening stop- cock G before the next sample is run.) 79.3 Titrate the distillate with 0.007 N HySO,. using a 10-mi microburet, until the color changes from green to light purple, 79.4 Determine an average blank by carrying all the reagents through the entire procedure before and after a run of samples and averaging the two results. Note 18—No provision has been made for semoviag last races of| nitrogen from the distiled water, since the Diank determinations will ore forthe presence of nitrogen. However, specially purified waters reerable if Danks exceed 0.29 mL. Kis desvable that the analysis be ‘ade i @ room where 90 ammonia or ammonium saith are used or stored. 79.5 Calculation—Caleulate the percentage of nitrogen as Follows: Nitrogen, % = (4 ~ B}C/D] x 100 where: = millilitres of H,SO, required to titrate the sample, B = millilitres of H,SO, required to titrate the blank, C = nitrogen equivalent, and D = grams of sample used.@) & 120 80, Precision and Bias 80.1 This test method was originally approved for publi- cation before the inclusion of precision and bias statements within standards was mandated. The original interlaboratory test data for this test method are no longer available. The user is cautioned to verify by the use of reference materials, if available, usat the precision and bias of this test method are adequate for the contemplated use. PALLADIUM BY THE 1-NITROSO-2-NAPHTHOL (PHOTOMETRIO) TEST METHOD 81. Scope 81.1 This test method covers the determination of palla- dium in concentrations from 0.10 to 0.25 %. Lower concen- {rations may be determined by taking smaller volumes of the calibration solutions and extending the calibration curve. 82, Summary of Test Method 82.1 A portion of the sample solution is evaporated with sulfurie and perchloric acids. A colored complex is formed ‘with the palladium and [-nitroso-2-naphthol and extracted with toluene. Photometric measurement is made at approx- imately 430 nm, 83. Concentration Range 83.1 The recommended concentration range is from 0,002 to 0.050 mg of palladium per 25 mL of solution, using a Lem cel [Nore 19—This test method hus been writen for cells having 1-em light path, Cells having other dimensions may be used, provided suitable ‘adjustments ean be made in the amounts of sample ar reagens use. 84. Stability of Color 84.1 The color is stable for several hours. 85. Interferences 85.1 The elements ordinarily present do not interfere. 86. Reagents 86.1 Citric Aeid Solution (100 g/L)—Reagent No. 129. 86.2 Ferrous Ammonium Sulfate, Crystals (Fe(NHa)e- (80,),-6H,0). 86.3 J-Nitroso-2-Naphuhol (0.5 g/L of ethanol)—Dissolve 0.050 g of L-nitroso-2-naphchot in 100 rol, of ethanol. 86.4 Palladium, Standard Sohuion (1 mL = 002 mg Pd)-Transfer 1.000 g of palladium metal (purty: 99.9 % tio) to a 250-mL tetrafluoroethylene beaker and dissolve in 100 mL of HCl, 2 to 3 mL of HF, and 20 mL of HNO, Transfer the solution to a I-L. volumetric Mask, diluie «0 volume, and mix. Transfer 2000 mL to another 1-L volumetric flask, dilute to volume with HNO, (149), and 86.5 Toluene (CH,CH,). 87. Preparation of Calibration Curve 87.1 Calibration Solutions: 87.1.1 Transfer 5.00, 10.00, 15.00, and 25.00 mL of palladium solution (1 mL = 0.02 mg Pd) to four 150-mL. beakers. 87.1.2 Add 5 mL of H,SO, (141) and 2 mL of HCIO, Evaporate the solution to the first appearance of HCIO, fumes, cool slightly, and wash down the sides of the beaker. Repeat the fuming and washing once, then fume again, and cool. 87.1.3 Transfer the solution to a 100-mL volumetric flask, dilute to volume, and mix. Proceed as directed in 87.3. 87.2 Reference Solution—Transfer § ml. of HySO, (141) and 2 mL of HCIO, to a 150-mL beaker, and proceed as directed in 87.1.2 and 87.1.3. 87.3 Color Development —Transfer 10.00 mL to a 12! iL separatory funnel containing 5 mL of citric acid solu- tion, and, using a pipet, add 1 mL of I-nitroso-2-naphthol solution. Mix and allow the color to develop for 2 h. Add 25.0 mL of toluene and { ml of NH,OH (1+1), shake for 30 5, and allow the layers to separate for 15 min. Discard the aqueous layer, and transfer the toluene layer to a small beaker, which will trap droplets of water on its surface. 87.4 Photometry: 874.1 Multiple-Cell Photometer—Measure the cell cor- rection using absorption cells with a I-cm light path and a light band centered at approximately 430 nm. Using the test call, take the photometric readings of the calibration solu- tions. 87.42 Single-Cell Photometer—Transier a suitable px tion of the reference solution to an absorption cell with a I-cm fight path and adjust the photometer to the initial setting, using a light band centered at approximately 430 nm, While ‘maintaining this adjustment, take the photometric readings of the calibration solutions. 87.5 Calibration Curve—Plot the net photometric read- ings Of the calibration solutions against milligrams of palla- dium per 25 mL of solution. 88. Procedure 88.1 Test Solution, 88.1.1 Transfer a 5.00-g sample, weighed to the nearest 1 mg, to a 400-mL tetrafluorethylene beaker. Add 150 mL of HCl and 2 to 3 mL of HF. When dissolution is complete (except for the palladium), add HNOy dropwise until the titanium is oxidized. Continue adding HNOs, while digesting. the solution on a hot plate, until the palladium is dissolved and the solution is clear; about 10 mL of HNO, is required. 88.1.2 Transfer the solution to a 250-ml. volumetric flask, cilute to volume, and mix, Transfer a 10.00-mL. aliquot to 3 150-mL. beaker. 88.1.3 Proceed as directed in 87.1.2 and 87.1.3. If more than 1 % chromium is present in the sample, add a few ‘crystals of ferrous ammonium sulfate to the test solution contained in the 100-mL volumetric flask. 88.2 Reference Solution—Carry a reagent blank through the entire procedure, using the same amounts ofall reagents, with the sample omitted, for use as the reference solution, 88.3 Color Development~—Proceed as directed in 87.3 88.4 Phoromerry—Take the photometric reading of the test solution as difected in 87.4. 89. Calculation 89.1 Convert the net photometric reading of the test solution to milligrams of palladium by means of the calibra- tion curve, Calculate the percentage of palladium as follows: Palladium, © = 4/(B x 10)hE 120 where: A = milligrams of palladium found in 25 mL of the final test solution, and B = grams of sample represented in solution, mL of the final test 90, Precision and Bias 90.1 Precision—Nine laboratories cooperated in testing this test method and obtained the data summarized in Table 1, 90.2 Bias—No certified reference materials suitable for testing this test method were available when the interla oratory testing program was conducted. The user of this test method is encouraged to employ accepted reference mate- rials, if available, to determine the bias of this test method as applied in a specific taboratory. VANADIUM BY THE POTASSIUM PERMANGANATE (TITRIMETRIO) TEST METHOD 91, Scope 91.1 This test method covers the determination of vana- dium in concentrations from 0.5 to 20 %, 92. Summary of Test Method 92.1 The sample is dissolved in sulfuric and fluoboric ids and the solution oxidized with nitric acid. Am excess of potassium permanganate is added to the cooled solution to ‘eliminate any reducing substances. The vanadium and excess potassium permanganate are reduced with excess ferrous ammonium sulfate and the excess ferrous iron is oxidized with ammonium persulfate. The vanadium is titrated di- rectly with potassium permangenate. 93, Interferences 93:1 The elements ordinarily present in titanium and titanium-base alloys do not interfere if their concentrations are under the maximum limits shown in 1.1 94, Reagents 94,1 Ammonium Persulfate Solution (150 g/L}—Dissolve 15 g of ammonium persulfate (NH,)95,0,) in water and dilute to 100 mL. Prepare fresh as needed. 94.2 Ferrous Ammonium Sulfate Standard Solution (0.08 N)--Prepare as directed for Reagent No. 5, using 19.6 g instead of the specified weight. 94.3 Fluoborie Acid (48 to 50 %) (HBF,). 94.4 Potassium Permanganate Solution (20 g/L)—Dis- solve 2 g of potassium permanganate (KMnO,) in water and dilute 6 100 mL. 94.5 Potassium Permanganate, Standard Solution (0.05 N)—Prepare and standardize as directed for Reagent No. 13, using 1.6 g instead of the specified weight, Calculate the vanadium equivalent in grams per mililite, using Table 2 of Practices E 50 95. Procedure 95.1 Weigh, to the nearest 1 mg, a portion of the sample calculated to contain 10 to 100 mg of vanadium and transfer toa $00-mL. Erlenmeyer flask. Add 100 mL of H,SO, (1+9) and 5 mL of HBF,, Heat gently, to avoid loss of water, untit dissolution is complete (Note 19). Oxidize by the dropwise addition of HNO;, and boil out fumes of nitrogen oxide, Cool the solution Note 19--Excessve loss of water leads to atack on the ask by the UDF. 95.2. Add KMnO, solution dropwise to a slight excess and ‘maintain the pink color for 10 min, 95.3 Add sufficient ferrous ammonium sulfate solution to reduce the excess KMnQ, and all the vanadium, and then add an excess of 5 to 10'mL. Add 15 mL of (NH4):S,0¢ solution to oxidize the excess ferrous iron, and swirl for | min, 95.4 Titrate the vanadium at once with 0.05 W KMnO, solution. Add the final portion of the KMnO, solution dropwise, allowing the color of each drop to fade before adding the next one. The end point is reached when 1 drop produces a pink color that lasts for { min, 96. Caleulation 96.1 Calculate the percentage of vanadium as follows: Vanadium, % = (4 x BY'C] x 100 where: A = millilitres of KMnO, solution required for titration of the sample, B = vanadium equivalent of the KMnO, solution, g/mL, and C = grams of sample used. 97. Precision and Bias 97.1 Precision—Data on this test method were obtained by eight cooperators. Repeatability, standard deviation, and coefficient of variation were graphically calculated as rested in Practice © 173, and were found tobe as shown in Table 97.2 Bias—The following data, obtained by one of the task force members, indicate that the bias ofthis test method. is satisfactory. Analyses of NBS Standard Sample No. 173 (Ti-GAI-4V) showed results within 0.01 % of the certified value of 4.09 % vanadium. On synthetic samples containing the equivalent of 15.60 % vanadium, results within 0.02 % were obtained; on other synthetic samples containing 14.00 % vanadium and 11.20% chromium, results within 0.04 % of the vanadium value were obtained, ZIRCONIUM BY THE MANDELIC ACID (GRAVIMETRIC) TEST METHOD. 98. Scope 98.1 This test method covers the determination of zirco- nium in concentrations from 1.0 to 20%. 99. Summary of Test Method 99.1 The sample is dissolved in hydrochloric acid. Zirco- nium is precipitated with mandelic acid and separated by filtration. The precipitate is ignited to the oxides and weighed, The weight of the precipitate is corrected for the titanium which has been coprecipitated, 100. Interferences 100.1 The elements ordinarily present in titanium and titanium-base alloys, except columbium and tantalum, do not interfere if their concentrations are under the maximumGh © 120 TABLE 7 Statistea!inormation—Paliachum by te t-Nivoso-2-Naphinol (Photometric) Method Paindum Foun ‘Rapley Ropraaacbany sen = Ges, (ae 173) Ta8/035 Pa oy one 9018 0015 ASTM G 097 65 on 9900 - 65, Gases 7 and 6) TABLE 8 Statistical Information—Vanadium by the Potassium Pormanganato (Tirimetne) Test Matnod Sdard on vanaen cemons Satin of naar : Tae ean v3 ost aa as Sos6 oor oa sai Sore oe Be ae limits shown in 1.1. The small amount of hafniure that may be present because of its association with and similar properties to zirconium is determined as zirconium. 101. Reagents 101.1 Hydrogen Peroxide (H,03). 101.2 Mandelic Acid Solution (160 g/L}—Dissolve 160 cof mandelic acid in about 800 mL of water and dilute to 1 L. 101.3 Mandelic Acid Wash Solution—Dissolve 20 2 of mandélic acid in 1 L of HCI (+9). 101.4 Potassium Pyrosulfate (K,S,0>). 101.5 Titanium, Standard Solution’ (mk Ti)—Reagent No. 18. = 05 me 102, Procedure 102.1 Transfer a 1.00-g sample, weighed to the nearest 1 img, to 2 250-mL beaker, and cover. Add 60 mL of HCI, beat gently until dissolution is complete, and cool (Note 20). If the sample contains more than 7 % zirconium, proceed as directed in 102.2; otherwise, proceed directly to 102.3 [Note 20—A clear sample solution is generally obtained. However, if any insoluble matier is visible, it shouldbe assumed tha itis niobium (columbiura) or tantalum (uniess itis known that these elements are absent), and the aralysis should be started again using a method that ‘removes the niobium and tantalum fist. {felobium and tantalum are ‘known fo be absent, the insoluble matter may be due to the presence of insoluble Stanium maleal, siliceous mateal, or palladium in. the sample; in which case the insoluble mater should be separated by filation or centiugation before proceeding with 102.2. 102.2 Transfer the solution to 2 100-mL volumetric flask, rinse the beaker with HCI, dilute to volume with HCL, and mix, Transfer an aliquot 10 a 250-mL beaker in accordance with the following: auiaeat mangle conve, tact youre, mL wei Fold “0 os B3tol7 «© oe 165100 3s 025 102.3 Dilute to 60 mL with HCI, add 10 mL of water, mix, and heat the solution to 80 to 85°C. While maintaining this temperature, add dropwise, while stirring, 50 mL of mandelic acid solution, Digest at 80 to 85°C for at least |b. 1024 Filter using an JI-cm fine filter paper containing filter paper pulp. Immediately wash the beaker and precipi tate with hot mandelic acid wash solution, Scrub the stirring tod and beaker with filter paper moistened with wash solution, and adé the paper to the funnel. Rinse the rod and ‘the beaker after scrubbing and wash the paper and precipi- fate 12 times with hot mandelic acid wash solution using a total volume of about 60 to 75 mL. 102.5 Transfer the paper and precipitate to a weighed platinum crucible and dry. Place the crucible in a muffle Farnace at about 200°C and heat to 950 to 100°C. Maintain at this temperature for 20 min to complete ignition. Cool in a desicator, and weigh. 102.6 Determine the titanium dioxide present in the precipitate as follows: 1026.1 Add 2 of K:S,0, tothe crucible and heat until clear melt is obtained. Cool the crucible, transfer it to a 250-mL beaker, add 35 mL of H,SO, (1+9), and then digest until the melt is dissolved, and cool. Remove the crucible and rinse it with H,SO, ((+9). Trarsfer the solution to a 100-mL volumetric flask, Rinse the beaker, dilute to volume with HSO, (149), and mix 102.62 Transfer about 25 mL. of this solution to a small beaker and use this as the reference solution, To the femaining solution in the Mask, add 5 drops of #is03, and mix, Take the photometric reading at 400 nm, using a I-cmn cell. Convert to milligrams of titanium by means of a calibration curve prepared as directed in 102.6.3, 102.6.3 Prepare the calibration curve as follows: Transfer 1.00, 2.00, 4.00, and 5.00 mL of titanium solution (1 mL = 050 mg Ti) 10 100-mL volumetric flasks, Add approxi- imately 75 mL. of HySO, (+9), 5 drops of H0,, dilute to volume with H,SO, (1+9), and mix. Measure the absorbance of each solution in a 1-cm cell using H,SO, (1+9) as the reference solution. Plot the net photometric Teadings of the calibration solutions against milligrams of titanium per 100 mL of solution. Convert the milligrams of Tito grams of TiO, as follows: mig of Ti x 0.00167 = g of TIO, 103. Calculation 103.1 Calculate the percentage of zirconium as follows: Zirconium, % = [lA ~ B) « 0.7403)/C} x 100 where: A = grams of combined oxides (102.5), B = grams of titanium dioxide (102.6.4), and C = grams of sample represented in the final solution, 104. Precision and Bias 104.1 Precision—Nine laboratories cooperated in testing this test method for Sample |, eight for Samples 2 and 3, and obtained the data summarized in Table 9. 1042 Bias—No certified reference materials suitable for testing this test method were available when the interlaboratory testing program was conducted. The user of this standard is cacouraged 10 employ accepted reference4) € 120 ‘TABLE 9 _Stailsticalnformation—Ziconium by the Mandelic Acid (Gravimettc) Method = ‘con Feud, Repenabity Fegoauctay ee = ee n5) Cnet 1) Atay (6 AYS 8v2500. 75080 7EFeAzH 39 ‘006 O18 (2) TAloy GALSEn529 488 008 000 {Bi Tater at-t2z7} 221 0.08 oa materials, if available, to determine the bias of this test 108, Keywords method as applied in a specific laboratory. 105.1 aluminum; chemical analysis; chloride; copper; manganese; molybdenum; nitrogen; palladium; titanium, vanadium; zirconium Tr Amercan Sole fr Testing and Mates aks no poston repecting the ality of any plat fps assured i connecon wen any tar nto Oe sanded. Uses of is sand wr egress acid tel doerminaton ob val fay wach ute des and the tsk of tingormant of such ha re ety Dar ow repre, ‘nis tana i suec fo roid a any by ib responsi eae caries and mun be eewed vty the yas er ‘nat rvse, etna redpproved or witetawn. Yu! Comments ar vader f rose of fs lanard ofr eddtral anders fc snus ta aceenes 1 ASTM Haauaars. Yous comments wi cave CAEL conideston at Ae oe Espen {acnnce cormntisg, whch you may mtnd If you Tel Dal your Concerts Pave Rt Feed 8a aang You SMES ake out eww known foe ASTM Camas on Starderce, 100 Bar Haroor Orv, West Corchehocten, PA TOAZH