1、Designation: D 4042 93 (Reapproved 2003)e1An American National StandardTest Method forSampling and Testing for Ash and Total Iron in Steel MillDispersions of Rolling Oils1This standard is issued under the fixed designation D 4042; the number immediately following the designation indicates the year o
2、foriginal adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.e1NOTEWarning notes were editorially moved into the standard text in
3、June 2003.1. Scope1.1 This test method describes a procedure for sampling andtesting dispersions of rolling oils in water from operating steelrolling mills for determination of ash and total iron content. Itspurpose is to provide a test method such that a representativesample may be taken and phenom
4、enon such as iron separation,fat-emulsion separation, and so forth, do not contribute toanalytical error in determination of ash and total iron.1.2 The values stated in SI units are to be regarded as thestandard. The values given in parentheses are for informationonly.1.3 This standard does not purp
5、ort to address all of thesafety concerns, if any, 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. For specificwarning statements, see Sections
6、6 and 7.2. Referenced Documents2.1 ASTM Standards:D 482 Test Method for Ash from Petroleum Products2D 1068 Test Methods for Iron in Water3D 1193 Specification for Reagent Water3D 2795 Test Method for Analysis of Coal and Coke Ash4E 50 Practices for Apparatus, Reagents, and Safety Consid-erations for
7、 Chemical Analysis of Metals, Ores, andRelated Materials5E 832 Specification for Laboratory Filter Papers63. Summary of Test Method3.1 Polyethylene disposable sample bags in a suitable hold-ing device are used to collect representative samples ofnonhomogeneous dispersions of rolling mill oils in wat
8、er froman operating mill coolant system.3.2 The collected sample and disposable bag are analyzed asone for ash and total iron.3.2.1 Ash content is determined gravimetrically by evapo-rating all water from the sample bag before heating the residueand bag in a muffle furnace to a constant weight (Test
9、 MethodD 482).3.2.2 Total iron content is determined by digesting the ironin the ashed sample and bag in an acidified solution. The ironin the solution is reduced with stannous chloride and titratedwith standardized potassium dichromate.3.2.3 The ash and total iron contributed by a sample bagalone a
10、re determined separately and are subtracted from thevalues of bag and sample to obtain the values for the samplealone.NOTE 1There are a number of alternative methods available fordetermining total iron in an ashed solution such as Test Methods D 2795and D 1068.4. Significance and Use4.1 The life cyc
11、le and cleanliness of a recirculating steelmill rolling oil dispersion is affected by the amount of ironpresent. This iron consists mainly of iron from acid picklingresidues and iron from attrition of the steel sheet or rolls duringcold rolling. In sampling rolling oils for total iron it is difficul
12、tto prevent adherence of iron containing sludge to the samplecontainer. Thus, the accuracy of a total iron determination froman aliquot sample is suspect. This practice provides a means forensuring that all iron contained in a sample is included in theanalysis.4.2 Although less significant, the ash
13、content is still anessential part of the procedure for obtaining a total ironanalysis. Generally, the ash will be mostly iron, and in manycases, could be used as a substitute for total iron in determiningwhen to change the dispersion.5. Sampling5.1 Apparatus:1This practice is under the jurisdiction
14、of ASTM Committee D02 on PetroleumProducts and Lubricants and is the direct responsibility of Subcommittee D02.L0 onIndustrial Lubricants (Joint ASTM-ASLE).Current edition approved May 10, 2003. Published July 2003. Originallyapproved in 1981. Last previous edition approved in 1998 as D 4042 93 (199
15、8).2Annual Book of ASTM Standards, Vol 05.01.3Annual Book of ASTM Standards, Vol 11.01.4Discontinued. See 2000 Annual Book of ASTM Standards, Vol 05.05.5Annual Book of ASTM Standards, Vol 03.05.6Annual Book of ASTM Standards, Vol 14.04.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C70
16、0, West Conshohocken, PA 19428-2959, United States.5.1.1 Disposable Plastic (Polyethylene) Sampling Bags7177 and 473 cm3(6 and 16 oz) complete with closure wire.5.1.2 Holding Fixture.NOTE 2A plastic baby bottle holder with an open 177-cm3(6-oz)sampling bag inserted makes a suitable holder.5.1.3 Samp
17、ling Cup and Handle.NOTE 3A hockey stick or similar formed apparatus of steel, plastic, orwood with or without a separate cup can be used to hold the holdingfixture or the fixture itself can be attached to the handle (see Fig. 1).5.2 Sampling Procedure:5.2.1 Weigh a number of identified sample bags
18、on ananalytical balance to the nearest 0.1 mg. Record the weight ofeach as WB1.5.2.2 Using a different, preweighed, identified plastic dis-posable sampling bag for each sample, remove samples fromthe mill only while the coolant is circulating and the millrunning. Take samples from the same location
19、between thesecond and third stand whenever possible. Fill the bag approxi-mately two thirds full to allow for tying of the bag.NOTE 4Occasionally, due to mill configuration or other reasons, itmay be advisable to obtain the sample from other points in the millsystem. If so, record complete details o
20、n location and time of sampling.5.2.3 Tie and seal each sample with the wire provided inanother disposable plastic sampling bag 473 cm3(16 oz) toprevent loss of material in transit. Individual rigid plasticbottles of suitable size are also satisfactory containers forshipment and can be substituted f
21、or the outer 473-cm3(16-oz)plastic bag.5.2.4 Take extreme care not to soil the exterior of thesampling bag with the dispersion or any foreign material.6. Ash Content6.1 Apparatus:6.1.1 Borosilicate-Glass Beaker, 400-mL, or EvaporatingDish, 350-mL, designed for ashing in an electric furnace. Donot us
22、e platinum crucibles because of the tendency to alloywith metallic iron.6.1.2 Electric Muffle Furnace, capable of maintaining atemperature of 775 6 25C (1427 6 45F), preferably havingsuitable apertures at the front and rear that allow a slow naturaldraft of air to pass through.6.1.3 Oven, capable of
23、 maintaining a temperature of 105 62C (221 6 4F).6.1.4 Analytical Balance, 200-g capacity, accurate to 0.1mg.6.1.5 Top-Loading Balance, 600-g minimum capacity, ac-curate to 0.01 g.6.2 Procedure:6.2.1 Heat the empty beaker or evaporating dish at 700 to800C (1240 to 1470F) for 10 min or more. Cool at
24、roomtemperature in a suitable container (Note 5) and weigh on ananalytical balance to the nearest 0.1 mg.NOTE 5The container in which the beaker or evaporating dish iscooled should not contain a desiccating agent.6.2.2 Remove the bagged sample from its carrier containerand place it, still tied, in t
25、he dish. Remove the wire and weighthe bag with sample on a top loading balance to the nearest0.01 g. Subtract the weight of the beaker or evaporating dishand record the weight in grams as WS1.6.2.3 Place the beaker or dish, sample, and bag in an ovenat 105C (221F) overnight or until the moisture has
26、 beenevaporated from the sample.6.2.4 Cover the beaker or evaporating dish with ashlessfilter paper (Note 6) to prevent loss due to spatter. Add thisfilter paper to the sample prior to ashing.NOTE 6Filter paper should conform to Specification E 832, Type II.6.2.5 Place the beaker or evaporating dish
27、 containing thedried sample, bag, and filter paper in the muffle furnace.Carefully heat the beaker or evaporating dish and sample byprogressively advancing it into the muffle furnace where it willeventually ignite.6.2.5.1 Maintain at such a temperature that the samplecontinues to burn at a uniform a
28、nd moderate rate, leaving onlyash and carbon when burning ceases. (WarningFumes fromburning polyethylene are hazardous.)6.2.6 Heat the residue in the muffle furnace at 775 6 25C(1427 6 45F) until all carbonaceous material has disappeared.6.2.7 Remove the dish and ashed sample from the furnaceand coo
29、l in a suitable container to room temperature. Weigh ona 200-g analytical balance to the nearest 0.1 mg.6.2.8 Reheat the dish to 775 6 25C (1427 6 45F) in themuffle furnace for 30 min, and cool to room temperature in asuitable container and reweigh, as in 6.2.6. Repeat the heating,cooling, and weigh
30、ing until consecutive weighings differ bynot more than 0.5 mg.6.2.9 Subtract the weight of the evaporating dish (6.2.1) andrecord the final ash weight as WS2.6.2.10 Place a new, empty polyethylene bag trimmed to theweight of the original sample bag 60.01 g (5.2.2) in apreweighed evaporating dish (6.
31、2.1) and reduce to ash follow-ing the procedure described by 6.2.4, 6.2.5, 6.2.6, 6.2.7, and6.2.8.6.2.11 Record the final ash weight in grams to the nearest0.1 mg as WB2.7Sampling bags (with wires) can be found in most common laboratory supplycatalogues.FIG. 1 Possible Holding Fixture and Assembly S
32、ystemD 4042 93 (2003)e12NOTE 7In repeat tests for duplicate samples or separate samples, if allsample bags used are from the same source and are of the same size, anaverage weight from three or more bags can be used for WB1. This avoidshaving to preweigh all bags as in 5.2.2. Also, the weight of the
33、 ashedempty bag WB2can be used in subsequent calculations for ash determi-nation. This avoids having to ash one sample bag for each duplicate orseparate sample.6.3 Calculation of Percent AshCalculate the weight of ashfor the dispersion sample as a percentage of the originalsample, as follows:Ash, %
34、5 WS22 WB2!/WS12 WB1! 3 100 (1)where:WS2= ash from sample and bag, g,WB2= ash from empty bag, g,WS1= sample and bag, g, andWB1= bag, g.NOTE 8Both the ash from the sample bag and the ash from the emptybag are to be used for subsequent total iron determination.7. Iron Content7.1 Apparatus:7.1.1 Analyt
35、ical Balance, 200-g capacity, accurate to 0.1mg.7.1.2 Beakers, 400-mL, borosilicate glass, Griffin form.7.1.3 Buret, 50-mL with 0.1-mL graduations.7.2 Reagents:7.2.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents shall
36、 conform to the specifications of the Commit-tee on Analytical Reagents of the American Chemical Society,where such specifications are available.8Other grades may beused, provided it is first ascertained that the reagent is ofsufficiently high purity to permit its use without lessening theaccuracy o
37、f the determination.7.2.2 Purity of WaterUnless otherwise indicated, refer-ences to water shall be understood to mean reagent water asdefined in Specification D 1193, Type II.7.2.3 Hydrochloric Acid (HCL) (36 %). (WarningPoison. Causes severe burns. Harmful or fatal if swallowed orinhaled.)7.2.4 Iro
38、n Standard Solution (1 mL = 0.10 mg Fe)Makein accordance with Practices E 50, iron, standard solution, or asfollows: Transfer 1.000 g of NBS Standard 55e (ingot iron) orequivalent to a 100-mL beaker (Note 9). Dilute 10 mL of HClwith 10 mL of distilled water. Add this solution to the 100-mLbeaker. Co
39、ver and heat below the boiling temperature todissolve the iron. Cool the solution and transfer quantitativelyto a 1-L volumetric flask. Cool to room temperature and diluteto 1-L volume with distilled water. Mix thoroughly. Onemillilitre of standard iron solution = 1 mg of iron.NOTE 9Prior to use, al
40、l beakers and glassware must be cleaned asfollows: Add approximately14 the total volume of HCl to beaker or otherglassware. Cover loosely and heat to boiling under a fume hood. Maintainboiling for approximately 10 min. Cool and rinse thoroughly with distilledwater.7.2.5 Mercuric Chloride Solution (s
41、aturated)Add 100 gof mercuric chloride (HgCl2) to 1000 mL of hot distilled waterand mix thoroughly. Allow to stand 12 to 24 h to obtain asaturated solution at room temperature. (WarningPoison.May cause skin irritation. Harmful or fatal if swallowed.)7.2.6 Potassium Dichromate (0.020 N)Transfer 1.0 g
42、 ofpotassium dichromate (K2Cr2O7) to a 1-L volumetric flask.Dissolve in distilled water and dilute volume to 1 L. Allow tostand 12 to 24 h prior to standardization and use. Standardizein accordance with Annex A1. (WarningCauses skin irrita-tion.)7.2.7 Sodium Diphenylamine Sulfonate Indicator Solutio
43、n(2 g/L)Dissolve1gofsodium diphenylamine sulfonate in500 mL of distilled water.7.2.8 Stannous Chloride (15 g/L)Dissolve 7.5 g of stan-nous chloride (SnCl22H2O) in 150 mL of HCI (36%). Whensolution is complete, dilute to 500 mL with distilled water andadd5goftinmetal. Some undissolved tin metal shoul
44、d bepresent at all times to maintain the stannous chloride in thereduced state. (WarningCauses skin irritation.)7.2.9 Sulfuric-Phosphoric Acid Mixture (150 mLH2SO4+ 150 mL H3PO4+ 700 mL H2O)Transfer 700 mL ofdistilled water to a 1-L borosilicate-glass beaker. Slowly add150 mL of concentrated sulfuri
45、c acid (95%) (WarningPoison. May cause skin irritation. Harmful or fatal if swal-lowed), stirring the solution during addition of the acid. Coolthe solution to room temperature. Carefully add 150 mL ofphosphoric acid (86 %) (WarningCauses skin irritation. Donot get in eyes, on skin, or on clothing)
46、and mix thoroughly.7.3 Procedure:7.3.1 Obtain ashed samples of (1) oil sample and polyeth-ylene bag (6.2.7) and (2) new empty polyethylene-sample bag(6.2.9) in original evaporating dishes or beakers.NOTE 10If total iron analysis only is desired, (no percent ashdetermination) Steps 6.2.6, 6.2.7, 6.2.
47、8, 6.2.10, and 6.3.1 may beeliminated in the ash content procedure.7.3.2 Add 10 mL of HCl to the ashed samples (1) and (2).Cover and heat slowly below the boiling point to digest toeffect the solution of all iron present.7.3.3 Cool the samples (1) and (2) to room temperature andtransfer each to indi
48、vidual 400-mL beakers. Rinse the originalevaporating dish or beaker with HCl and add the rinse to therespective beaker.7.3.4 Cover the beakers loosely and digest by heating nearboiling for 5 min.7.3.5 Rinse the cover and sides of the beakers with distilledwater, heat to near boiling and add stannous
49、 chloride solutiondropwise until the solution changes from yellow to colorless.Add one drop in excess. Cover and just bring to a boil.7.3.6 Cool to room temperature. Rinse the cover and sidesof the beakers with freshly boiled distilled water. Add 10 mL ofHgCl2solution to each and allow to stand for 3 to 5 min.7.3.7 To each beaker add 20 mL of sulfuric-phosphoric acidmixture. Dilute each solution to approximately 300 mL with8Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For suggestions on
