1、Designation: D4042 93 (Reapproved 2014)Standard Test Method forSampling and Testing for Ash and Total Iron in Steel MillDispersions of Rolling Oils1This standard is issued under the fixed designation D4042; the number immediately following the designation indicates the year oforiginal adoption or, i
2、n the case of revision, the year of last revision. 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 This test method describes a procedure for sampling andtesting dispersions of roll
3、ing 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 phenomenon such as iron separation,fat-emulsion separation, and so forth, do not contribute toanalytical error
4、 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 purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of th
5、e 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 and 7.2. Referenced Documents2.1 ASTM Standards:2D482 Test Method for Ash from Petroleum ProductsD1068
6、 Test Methods for Iron in WaterD1193 Specification for Reagent WaterD2795 Test Methods for Analysis of Coal and Coke Ash(Withdrawn 2001)3E50 Practices for Apparatus, Reagents, and Safety Consid-erations for Chemical Analysis of Metals, Ores, andRelated MaterialsE832 Specification for Laboratory Filt
7、er Papers3. 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 water froman operating mill coolant system.3.2 The collected sample and disposable bag are analyzed
8、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 MethodD482).3.2.2 Total iron content is determined by digesting the ironin the ashed sample and
9、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 are determined separately and are subtracted from thevalues of bag and sample to obtain the values
10、for the samplealone.NOTE 1There are a number of alternative methods available fordetermining total iron in an ashed solution such as Test Methods D2795and D1068.4. Significance and Use4.1 The life cycle and cleanliness of a recirculating steelmill rolling oil dispersion is affected by the amount of
11、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 difficultto prevent adherence of iron containing sludge to the samplecontainer. Thus, the accuracy of a tota
12、l 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 content is still anessential part of the procedure for obtaining a total ironanalysis. Generally, th
13、e 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 test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products, Liquid Fuels, and Lubricants and is the direct respon
14、sibility ofSubcommittee D02.L0.04 on Metal Deformation Fluids and Lubricants.Current edition approved May 1, 2014. Published July 2014. Originally approvedin 1981. Last previous edition approved in 2009 as D4042 93 (2009). DOI:10.1520/D4042-93R14.2For referenced ASTM standards, visit the ASTM websit
15、e, 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.3The last approved version of this historical standard is referenced onwww.astm.org.Copyright ASTM International,
16、100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States15.1.1 Disposable Plastic (Polyethylene) Sampling Bags4177and 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 ma
17、kes a suitable holder.5.1.3 Sampling Cup and Handle.NOTE 3Ahockey 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 nu
18、mber of identified sample bags 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
19、samples from the same location 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. I
20、f so, record complete details on 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 forsh
21、ipment and can be substituted for 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 i
22、n an electric furnace. Donot use 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
23、 through.6.1.3 Oven, capable of maintaining a temperature of 105 62C (221 6 4F).6.1.4 Analytical Balance, 200-g capacity, accurate to0.1 mg.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 1470
24、F) for 10 min or more. Cool at 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 containe
25、rand place it, still tied, in the 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) over
26、night or until the moisture has 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 E832, Type II.6.2.5 Place
27、the beaker or evaporating dish 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 sampleco
28、ntinues to burn at a uniform and 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
29、sample from the furnaceand cool 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
30、the heating,cooling, and weighing 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)inapre
31、weighed evaporating dish (6.2.1) 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 WB2.4Sampling bags (with wires) can be found in most common laboratory supplycatalogues.FIG. 1 Possible Ho
32、lding Fixture and Assembly SystemD4042 93 (2014)2NOTE 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
33、. Also, the weight of the 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 originals
34、ample, as follows:Ash, % 5 WS22 WB2!/WS12 WB1! 3100 (1)where:WS2= ash from sample and bag, g,WB2= ash from empty bag, gWS1= 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
35、 Apparatus:7.1.1 Analytical 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
36、 thatall reagents shall conform to the specifications of the Commit-tee on Analytical Reagents of the American Chemical Society,where such specifications are available.5Other grades may beused, provided it is first ascertained that the reagent is ofsufficiently high purity to permit its use without
37、lessening theaccuracy of the determination.7.2.2 Purity of WaterUnless otherwise indicated, refer-ences to water shall be understood to mean reagent water asdefined in Specification D1193, Type II.7.2.3 Hydrochloric Acid (HCL) (36 %). (WarningPoison. Causes severe burns. Harmful or fatal if swallowe
38、d orinhaled.)7.2.4 Iron Standard Solution (1 mL = 0.10 mg Fe)Makein accordance with Practices E50, 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
39、 the 100-mLbeaker. Cover 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.N
40、OTE 9Prior to use, all 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
41、 Chloride Solution (saturated)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
42、.020 N)Transfer 1.0 g 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 Sulfona
43、te Indicator Solution(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 undisso
44、lved tin metal should 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
45、concentrated sulfuric acid (95%) (WarningPoison. May cause skin irritation. Harmful or fatal ifswallowed), stirring the solution during addition of the acid.Cool the solution to room temperature. Carefully add 150 mLof phosphoric acid (86 %) (WarningCauses skin irritation.Do not get in eyes, on skin
46、, or on clothing) 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
47、6.2.6, 6.2.7, 6.2.8, 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 andtra
48、nsfer each to individual 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 boilin
49、g and add stannous 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 withfreshly boiled and cooled distilled water. To each solution add5Reagent Chemicals, American Chemical So
