Asme V 2013.pdf - 5

--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---
INTENTIONALLY LEFT BLANK
544
Copyright ASME International (BPVC)
Provided by IHS under license with ASME pe.class Licensee=PDVSA - Pequiven site 9/9986712014, User=Gil, Eliecer
No reproduction or networking permitted without license from IHS Not for Resale, 07/23/2013 06:23:05 MDT
2013 SECTION V ARTICLE 24, SD-129
STANDARD TEST METHOD FOR SULFUR IN PETROLEUM

PRODUCTS (GENERAL BOMB METHOD)
SD-129
(Identical with ASTM Specification D 129-00 (R2005)

(This specification is available in SI Units only.)
--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---
545
ARTICLE 24, SD-129 2013 SECTION V
STANDARD TEST METHOD FOR

SULFUR IN PETROLEUM PRODUCTS
(GENERAL BOMB METHOD)
SD-129
[Identical with ASTM D 129-00 (R2005)]

(This specification is available in SI Units only.)
1. Scope D 1552 Test Method for Sulfur in Petroleum Products

1.1 This test method covers the determination of sulfur (High-Temperature Method)
in petroleum products, including lubricating oils containing D 6299 Practice for Applying Statistical Quality Assurance
additives, additive concentrates, and lubricating greases Techniques to Evaluate Analytical Measurement System
that cannot be burned completely in a wick lamp. The test
Performance
method is applicable to any petroleum product sufficiently
low in volatility that it can be weighed accurately in an E 144 Practice for Safe Use of Oxygen Combustion Bombs
open sample boat and containing at least 0.1% sulfur.
NOTE 1 — This test method is not applicable to samples containing 3. Summary of Test Method
elements that give residues, other than barium sulfate, which are insoluble
in dilute hydrochloric acid and would interfere in the precipitation step. 3.1 The sample is oxidized by combustion in a bomb
These interfering elements include iron, aluminum, calcium, silicon, and containing oxygen under pressure. The sulfur, as sulfate
lead which are sometimes present in greases, lube oil additives, or additive in the bomb washings, is determined gravimetrically as
oils. Other acid insoluble materials that interfere are silica, molybdenum barium sulfate.
disulfide, asbestos, mica, etc. The test method is not applicable to used
oils containing wear metals, and lead or silicates from contamination. 3.2 Warning — Strict adherence to all of the provi-
Samples that are excluded can be analyzed by Test Method D 1552. sions prescribed hereafter ensures against explosive rup-
1.2 This standard does not purport to address all of ture of the bomb, or a blow-out, provided the bomb is of
--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---
the safety concerns, if any, associated with its use. It is proper design and construction and in good mechanical
the responsibility of the user of this standard to establish condition. It is desirable, however, that the bomb be
appropriate safety and health practices and determine the enclosed in a shield of steel plate at least 13 mm thick,
applicability of regulatory limitations prior to use. See 3.2 or equivalent protection be provided against unforseeable
for specific precautionary directions incorporated in the contingencies.
test method.
2. Referenced Documents 4. Apparatus and Materials

2.1 ASTM Standards: 4.1 Bomb, having a capacity of not less than 300 mL,
D 1193 Specification for Reagent Water so constructed that it will not leak during the test and that
546
quantitative recovery of the liquids from the bomb may stable and representative of the samples of interest. These
be achieved readily. The inner surface of the bomb may QC samples can be used to check the validity of the testing
be made of stainless steel or any other material that will process as described in Section 10.
not be affected by the combustion process or products.
Materials used in the bomb assembly, such as the head
gasket and lead-wire insulation, shall be resistant to heat 6. Procedure
and chemical action, and shall not undergo any reaction 6.1 Preparation of Bomb and Sample — Cut a piece of
that will affect the sulfur content of the liquid in the bomb. firing wire 100 mm in length. Coil the middle section
4.2 Sample Cup, platinum, 24 mm in outside diameter (about 20 mm) and attach the free ends to the terminals.
at the bottom, 27 mm in outside diameter at the top, 12 mm Arrange the coil so that it will be above and to one side
in height outside, and weighing 10 to 11 g. of the sample cup. Insert between two loops of the coil a
wisp of cotton or nylon thread of such length that one end
4.3 Firing Wire, platinum, No. 26 B & S gage, 0.41 mm will extend into the sample cup. Place about 5 mL of
(16 thou), 27 SWG, or equivalent. (Warning — The switch Na2CO3 solution in the bomb (Note 2) and rotate the bomb
in the ignition circuit shall be of a type which remains in such a manner that the interior surface is moistened by
open, except when held in closed position by the operator.) the solution. Introduce into the sample cup the quantities
4.4 Ignition Circuit, capable of supplying sufficient cur- of sample and white oil (Note 3 and Note 4) specified in
rent to ignite the cotton wicking or nylon thread without the following table, weighing the sample to the nearest
melting the wire. The current shall be drawn from a step- 0.2 mg (when white oil is used, stir the mixture with a
down transformer or from a suitable battery. short length of quartz rod and allow the rod to remain in
the sample cup during the combustion).
4.5 Cotton Wicking or Nylon Sewing Thread, white.
NOTE 2 — After repeated use of the bomb for sulfur determinations, a
film may be noticed on the inner surface. This dullness can be removed
5. Reagents and Materials by periodic polishing of the bomb. A satisfactory method for doing this
5.1 Purity of Reagents — Reagent grade chemicals shall is to rotate the bomb in a lathe at about 300 rpm and polish the inside
surface with emery polishing papers Grit No. 2⁄0, or equivalent paper,
be used in all tests. Unless otherwise indicated, it is coated with a light machine oil to prevent cutting, and then with a paste
intended that all reagents shall conform to the specifications of grit-free chromic oxide and water. This procedure will remove all but
--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---
of the Committee on Analytical Reagents of the American very deep pits and put a high polish on the surface. Before the bomb is
Chemical Society, where such specifications are available. used it shall be washed with soap and water to remove oil or paste left
Other grades may be used, provided it is first ascertained from the polishing operation.
that the reagent is of sufficiently high purity to permit its 6.1.1 Warning — Do not use more than 1.0 g total
use without lessening the accuracy of the determination. of sample and white oil or other low sulfur combustible
5.2 Purity of Water — Unless otherwise indicated, refer- material or more than 0.8 g if the IP 12 bomb is used.
ences to water shall mean water as defined by Type II or Weight of Weight of
III of Specification D 1193. Sulfur Content, % Sample, g White Oil, g
5 or under 0.6 to 0.8 0.0
5.3 Barium Chloride Solution (85 g/litre) — Dissolve Over 5 0.3 to 0.4 0.3 to 0.4
100 g of barium chloride dihydrate (BaCl2 W 2H2O) in
distilled water and dilute to 1 liter. NOTE 3 — Use of sample weights containing over 20 mg of chlorine
5.4 Bromine Water (saturated). may cause corrosion of the bomb. To avoid this, it is recommended that
for samples containing over 2% chlorine, the sample weight be based on
5.5 Hydrochloric Acid (sp gr 1.19) — Concentrated the chlorine content as given in the following table:
hydrochloric acid (HCl). Weight of Weight of
5.6 Oxygen, free of combustible material and sulfur Chlorine Content, % Sample, g White Oil, g
compounds, available at a pressure of 41 kgf/cm2 (40 atm). 2 to 5 0.4 0.4
Over 5 to 10 0.2 0.6
5.7 Sodium Carbonate Solution (50 g/litre) — Dissolve Over 10 to 20 0.1 0.7
135 g of sodium carbonate decahydrate (Na2CO3 W 10H2O) Over 20 to 50 0.05 0.7
or its equivalent weight in distilled water and dilute to
1 litre. NOTE 4 — If the sample is not readily miscible with white oil, some
other low sulfur combustible diluent may be substituted. However, the
5.8 White Oil, USP, or Liquid Paraffin, BP, or equiv- combined weight of sample and nonvolatile diluent shall not exceed 1.0 g
alent. or more than 0.8 g if the IP 12 bomb is used.
5.9 Quality Control (QC) Samples, preferably are por- 6.2 Addition of Oxygen — Place the sample cup in posi-
tions of one or more liquid petroleum materials that are tion and arrange the cotton wisp or nylon thread so that
547
the end dips into the sample. Assemble the bomb and or dropwise. Stir the solution during the addition and for
tighten the cover securely. (Warning — Do not add oxygen 2 min thereafter. Cover the beaker with a fluted watch
or ignite the sample if the bomb has been jarred, dropped, glass and continue boiling slowly until the solution has
or tilted.) Admit oxygen slowly (to avoid blowing the oil evaporated to a volume approximately 75 mL as indicated
from the cup) until a pressure is reached as indicated in by a mark on the beaker. Remove the beaker from the hot
the following table: plate (or other source of heat) and allow it to cool for 1 hr
before filtering. Filter the supernatant liquid through an
Capacity of Minimum Gage Maximum Gage ashless, quantitative filter paper (Note 5). Wash the precipi-
Bomb, ml Pressure,A kgf/cm2 (atm) Pressure,A kgf/cm2 (atm) tate with water, first by decantation and then on the filter,
300 to 350 39 (38) 41 (40) until free from chloride. Transfer the paper and precipitate
350 to 400 36 (35) 38 (37) to a weighed crucible and dry (Note 6) at a low heat until
400 to 450 31 (30) 33 (32)
the moisture has evaporated. Char the paper completely
450 to 500 28 (27) 30 (29)
without igniting it, and finally ignite at a bright red heat
A
The minimum pressures are specified to provide sufficient oxygen for until the residue is white in color. After ignition is com-
complete combustion and the maximum pressures represent a safety plete, allow the crucible to cool at room temperature, and
requirement. weigh.
6.3 Combustion — Immerse the bomb in a cold distilled- NOTE 5 — A weighed porcelain filter crucible (Selas type) of 5 to 9-␮m
water bath. Connect the terminals to the open electrical porosity may be used in place of the filter paper. In this case the precipitate
is washed free of chloride and then dried to constant weight at 500 ±25°C.
--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---
circuit. Close the circuit to ignite the sample. (Warning —

Do not go near the bomb until at least 20 s after firing.) NOTE 6 — A satisfactory means of drying, charring, and igniting the
Remove the bomb from the bath after immersion for at paper and precipitate is to place the crucible containing the wet filter
paper in a cold electric muffle furnace and to turn on the current. Drying,
least 10 min. Release the pressure at a slow, uniform rate
charring, and ignition usually will occur at the desired rate.
such that the operation requires not less than 1 min. Open
the bomb and examine the contents. If traces of unburned 6.6 Blank — Make a blank determination whenever new
oil or sooty deposits are found, discard the determination reagents, white oil, or other low-sulfur combustible mate-
and thoroughly clean the bomb before again putting it in rial are used. When running a blank on white oil, use 0.3
use (Note 2). to 0.4 g and follow the normal procedure.
6.4 Collection of Sulfur Solution — Rinse the interior
of the bomb, the oil cup, and the inner surface of the bomb
cover with a fine jet of water, and collect the washings in 7. Calculation
a 600-mL beaker having a mark to indicate 75 mL. Remove 7.1 Calculate the sulfur content of the sample as
any precipitate in the bomb by means of a rubber police- follows:
man. Wash the base of the terminals until the washings
are neutral to the indicator methyl red. Add 10 mL of Sulfur, weight percent p (P − B)13.73/W (1)
saturated bromine water to the washings in the beaker.
where:
(The volume of the washings is normally in excess of
300 mL.) Place the sample cup in a 50-mL beaker. Add P p grams of BaSO4 obtained from sample,
5 mL of saturated bromine water, 2 mL of HCl, and enough B p grams of BaSO4 obtained from blank, and
water just to cover the cup. Heat the contents of the beaker W p grams of sample used.
to just below its boiling point for 3 or 4 min and add to
the beaker containing the bomb washings. Wash the sample
cup and the 50-mL beaker thoroughly with water. Remove 8. Report
any precipitate in the cup by means of a rubber policeman.
Add the washings from the cup and the 50-mL beaker, 8.1 Report the results of the test to the nearest 0.01%.
and the precipitate, if any, to the bomb washings in the
600-mL beaker. Do not filter any of the washings, since
filtering would remove any sulfur present as insoluble 9. Precision and Bias
material. 9.1 The precision of this test is not known to have been
6.5 Determination of Sulfur — Evaporate the combined obtained in accordance with currently accepted guidelines.
washings to 200 mL on a hot plate or other source of heat. 9.1.1 Repeatability — The difference between two
Adjust the heat to maintain slow boiling of the solution test results, obtained by the same operator with the same
and add 10 mL of the BaCl2 solution, either in a fine stream apparatus under constant operating conditions on identical
548
test material, would in the long run, in the normal and (a) Results of duplicate tests should not differ by more than the follow-
correct operation of the test method, exceed the following ing amounts:
Repeatability Reproducibility
values only in one case in twenty:
0.016 x + 0.06 0.037 x + 0.13
9.1.2 Reproducibility — The difference between two where x is the mean of duplicate test results.
single and independent results obtained by different opera- (b) These precision values were obtained in 1960 by statistical exami-
tors working in different laboratories on identical test mate- nation of interlaboratory test results. No limits have been established for
rial would, in the long run, in the normal and correct additive concentrates.
operation of the test method, exceed the following values 9.2 Bias — Results obtained in one laboratory by Test
only in one case in twenty: Method D 129 on NIST Standard Reference Material Nos.
1620A, 1621C, and 1662B were found to be 0.05 mass %
Sulfur, higher than the accepted reference values.
Weight % Repeatability Reproducibility
0.1 to 0.5 0.04 0.05
0.5 to 1.0 0.06 0.09 10. Quality Control
1.0 to 1.5 0.08 0.15 10.1 Confirm the performance of the instrument or the
1.5 to 2.0 0.12 0.25
2.0 to 5.0 0.18 0.27
test procedure by analyzing a QC sample (see 5.9).
10.1.1 When QC/Quality Assurance (QA) protocols
are already established in the testing facility, these may be
NOTE 7 — The precision shown in the above table does not apply to used to confirm the reliability of the test result.
samples containing over 2% chlorine because an added restriction on the
amount of sample which can be ignited is imposed. 10.1.2 When there is no QC/QA protocol established
in the testing facility, Appendix X1 can be used as the
NOTE 8 — This test method has been cooperatively tested only in the QC/QA system.
range of 0.1 to 5.0% sulfur.
NOTE 9 — The following information on the precision of this method 11. Keywords
has been developed by the Institute of Petroleum (London): 11.1 bomb; sulfur
--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---
549
APPENDIX
(Nonmandatory Information)
X1. QUALITY CONTROL on the criticality of the quality being measured, the demon-
strated stability of the testing process, and customer
X1.1 Confirm the performance of the instrument or the
requirements. Generally, a QC sample is analyzed each
test procedure by analyzing a quality control (QC) sample.
testing day with routine samples. The QC frequency should
X1.2 Prior to monitoring the measurement process, the be increased if a large number of samples are routinely
user of the test method needs to determine the average analyzed. However, when it is demonstrated that the testing
is under statistical control, the QC testing frequency may
value and control limits of the QC sample (see Practice
be reduced. The QC sample precision should be checked
D 6299 and MNL 7).
against the ASTM method precision to ensure data quality.
X1.3 Record the QC results and analyze by control X1.5 It is recommended that, if possible, the type of
charts or other statistically equivalent techniques to ascer- QC sample that is regularly tested be representative of the
tain the statistical control status of the total testing process material routinely analyzed. An ample supply of QC sam-
(see Practice D 6299 and MNL 7). Any out-of-control data ple material should be available for the intended period
should trigger investigation for root cause(s). of use, and must be homogenous and stable under the
anticipated storage conditions. See Practice D 6299 and
X1.4 In the absence of explicit requirements given in MNL 7 for further guidance on QC and control charting
the test method, the frequency of QC testing is dependent techniques.
--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---
550
STANDARD TEST METHOD FOR SULFATE ION IN WATER
SD-516
--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---
(Identical with ASTM Specification D 516-07.)
551
STANDARD TEST METHOD FOR SULFATE ION IN

WATER
SD-516
(Identical with ASTM D 516-07)
1. Scope E 60 Practice for Analyss of Metals, Ores, and Related

1.1 This turbidimetric test method covers the determi- Materials by Molecular Absorption Spectrometry
nation of sulfate in water in the range from 5 mg/L to E 275 Practice for Describing and Measuring Performance
40 mg/L of sulfate ion (SO4− −). of Ultraviolet and Visible pectrophotometers
1.2 This test method was used successfully with drink-
ing, ground, and surface waters. It is the user’s responsibil- 3. Terminology
ity to ensure the validity of this test method for waters of
3.1 Definitions — For definitions of terms used in this
untested matrices.
test method, refer to Terminology D 1129.
1.3 Former gravimetric and volumetric test methods
have been discontinued. Refer to Appendix X1 for histori-
cal information. 4. Summary of Test Method
4.1 Sulfate ion is converted to a barium sulfate suspen-
1.4 This standard does not purport to address the safety sion under controlled conditions. A solution containing
concerns, if any, associated with its use. It is the responsi- glycerin and sodium chloride is added to stabilize the sus-
bility of the user of this standard to establish appropriate pension and minimize interferences. The resulting turbidity
safety and health practices and determine the applicability is determined by a nephelometer, spectrophotometer, or
of regulatory limitations prior to use. photoelectric colorimeter and compared to a curve prepared
from standard sulfate solutions.
2. Referenced Documents
5. Significance and Use
2.1 ASTM Standards:
5.1 The determination of sulfate is important because
D 1066 Practice for Sampling Steam it has been reported that when this ion is present in excess
of about 250 mg/L in drinking water, it causes a cathartic
D 1129 Terminology Relating to Water
action (especially in children) in the presence of sodium
D 1192 Guide for Equipment for Sampling Water and and magnesium, and gives a bad taste to the water.
Steam in Closed Conduits
D 1193 Specification for Reagent Water 6. Interferences
D 2777 Practice for Determination of Precision and Bias 6.1 Insoluble suspended matter in the sample must be
of Applicable Methods of Committee D19 on Water removed. Dark colors that can not be compensated for in
the procedure interfere with the measurement of suspended
D 3370 Practices for Sampling Water from Closed Con- barium sulfate (BaSO4).
duits
6.2 Polyphosphates as low as 1 mg/L will inhibit barium
D 5847 Practice for Writing Quality Control Specifications sulfate precipitation causing a negative interference. Phos-
for Standard Test Methods of Water Analysis phonates present in low concentrations, depending on the
552
--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---

type of phosphonate, will also cause a negative interfer- of the test method. Type II water was specified at the time
ence. Silica in excess of 500 mg/L may precipitate along of round robin testing of this test method.
with the barium sulfate causing a positive interference.
8.3 Barium Chloride — Crystals of barium chloride
Chloride in excess of 5000 mg/L will cause a negative
(BaCl2W2H2O) screened to 20 to 30 mesh. To prepare in
interference. Aluminum, polymers, and large quantities of
the laboratory, spread crystals over a large watch glass,
organic material present in the test sample may cause the
desiccate for 24 h, screen to remove any crystals that are
barium sulfate to precipitate nonuniformly. In the presence
not 20 to 30 mesh, and store in a clean, dry jar.
of organic matter certain bacteria may reduce sulfate to
sulfide. To minimize the action of sulfate reducing bacteria, 8.4 Conditioning Reagent — Place 30 mL of concen-
samples should be refrigerated at 4°C when the presence trated hydrochloric acid (HCl, sp gr 1.19), 300 mL reagent
of such bacteria is suspected. water, 100 mL 95% ethanol or isopropanol and 75 g sodium
chloride (NaCl) in a container. Add 50 mL glycerol and
6.3 Although other ions normally found in water do mix.
not appear to interfere, the formation of the barium sulfate
suspension is very critical. Determinations that are in doubt 8.5 Sulfate Solution, Standard (1 mL p 0.100 mg
may be checked by a gravimetric method in some cases, SO4− −) — Dissolve 0.1479 g of anhydrous sodium sulfate
or by the procedure suggested in Note 2. (Na2SO4) in water, and dilute with water to 1 L in a volu-
metric flask. A purchased stock solution of adequate purity
is also acceptable.
7. Apparatus
7.1 Photometer — One of the following which are 9. Sampling
given in order of preference. 9.1 Collect the sample in accordance with Practice
7.1.1 Nephelometer or turbidimeter; D 1066, Specification D 1192, and Practices D 3370, as
applicable.
7.1.2 Spectrophotometer for use at 420 nm with light
path of 4 cm to 5 cm;
7.1.3 Filter photometer with a violet filter having a 10. Calibration
maximum near 420 nm and a light path of 4 cm to 5 cm. 10.1 Follow the procedure given in Section 11, using
appropriate amounts of the standard sulfate solution pre-
7.2 Stopwatch, if the magnetic stirrer is not equipped
pared in accordance with 8.5 and prepare a calibration
with an accurate timer.
curve showing sulfate ion content in milligrams per litre
7.3 Measuring Spoon, capacity 0.2 mL to 0.3 mL. plotted against the corresponding photometer readings
(Note 1). Prepare standards by diluting with water 0.0, 5.0,
7.4 Filter photometers and photometric practices pre-
10.0, 15.0, 20.0, 30.0, and 40.0 mL of standard sulfate
scribed in this test method shall conform to Practice E 60;
solution to 100-mL volumes in volumetric flasks. These
spectrophotometer practices shall conform to Practice
solutions will have sulfate ion concentrations of 0.0, 5.0,
E 275.
10.0, 15.0, 20.0, 30.0, and 40.0 mg/L (ppm), respectively.
--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---
NOTE 1: A separate calibration curve must be prepared for each photome-
ter and a new curve must be prepared if it is necessary to change the
8. Reagents
cell, lamp, or filter, or if any other alterations of instrument or reagents
8.1 Purity of Reagents — Reagent grade chemicals are made. Check the curve with each series of tests by running two or
shall be used in all tests. Unless otherwise indicated, it is more solutions of known sulfate concentrations.
intended that all reagents shall conform to the specifications
of the Committee on Analytical Reagents of the American
Chemical Society. Other grades may be used, provided it 11. Procedure
is first ascertained that the reagent is of sufficiently high 11.1 Filter the sample if it is turbid through a 0.45-␮m
purity to permit its use without lessening the accuracy of membrane and adjust the temperature to between 15°C
the determination. and 30°C.
8.2 Purity of Water — Unless otherwise indicated, 11.2 Pipette into a 250-mL beaker 100 mL or less of
reference to water shall be understood to mean reagent the clear sample containing between 0.5 mg and 4 mg of
water conforming to Specification D 1193, Type I. Other sulfate ion (Note 2). Dilute to 100 mL with water if
reagent water types may be used provided it is first ascer- required, and add 5.0 mL of conditioning reagent (Note 1).
tained that the water is of sufficiently high purity to permit NOTE 2: The solubility of BaSO4 is such that difficulty may be experi-
its use without adversely affecting the precision and bias enced in the determination of sulfate concentrations below about 5 mg/L
553
TABLE 1 TABLE 2
OVERALL (ST) AND SINGLE-OPERATOR (SO) OVERALL (ST) AND SINGLE-OPERATOR (SO)
STANDARD DEVIATIONS AGAINST MEAN STANDARD DEVIATIONS AGAINST MEAN
CONCENTRATION FOR INTERLABORATORY RECOVERY CONCENTRATION FOR INTERLABORATORY RECOVERY
OF SULFATE FROM REAGENT WATERA OF SULFATE FROM DRINKING, GROUND, AND
SURFACE WATERA
Mean Concentration (x–), Standard Deviation, mg/L
mg/L ST SO Mean Concentration (–x), Standard Deviation, mg/L
mg/L ST SO
6.6 0.5 0.1
20.4 1.0 0.4 6.9 0.7 0.5
63.7 2.5 1.3 20.2 2.2 1.8
63.3 4.5 1.6
NOTE:
A
The test method is linear to 40 mg/L. Testing at the 63.9 level was NOTE:
accomplished through dilution as described in 11.2. A
The test method is linear to 40 mg/L. Testing at the 63.9 level was
accomplished through dilution as described in 11.2.
(ppm). This can be overcome by concentrating the sample or by adding

5 mL of standard sulfate solution (1 mL p 0.100 mg SO4− −) to the
sample before diluting to 100 mL. This will add 0.5 mg SO4 to the TABLE 3
sample, which must be subtracted from the final result. DETERMINATION OF BIASA
11.3 Mix in the stirring apparatus. Statistically
Significant
11.4 While the solution is being stirred, add a measured Amount Amount at 5%
spoonful of BaCl2 crystals (0.3 g) and begin timing imme- Added, Found, Level (at
diately. mg/L mg/L ±Bias ±% Bias ±0.05)
11.5 Stir exactly 1.0 min at constant speed. Reagent water 20.8 20.4 -0.4 -1.9 % no
63.9A 63.7A -0.2 -0.2 % no
NOTE 3: The stirring should be at a constant rate in all determinations. 7.0 6.6 -0.4 -5.3 % no
--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---
The use of a magnetic stirrer has been found satisfactory for this purpose. Drinking, ground 20.8 20.2 -0.6 -2.7 % no
and surface water 63.9A 63.3A -0.6 -0.9 % no
11.6 Immediately after the stirring period has ended, 7.0 6.9 -0.1 -1.8 % no
pour solution into the cell and measure the turbidity at
30-s intervals for 4 min. Record the maximum reading NOTE:
A
obtained in the 4-min period. The test method is linear to 40 mg/L. Testing at the 63.9 level was
11.7 If the sample contains color or turbidity, run a
sample blank using the procedure 11.2 through 11.6 with-
out the addition of the barium chloride.
and Table 2 for drinking, ground, and surface waters.
11.8 If interferences are suspected, dilute the sample
13.2.1 Seven laboratories participated in the round
with an equal volume of water, and determine the sulfate
robin at three levels in triplicate, making a total of 21
concentration again. If the value so determined is one-half
observations at each level for reagent water and for matrix
that in the undiluted sample, interferences may be assumed
water (drinking, ground, and surface water).
to be absent.
13.3 Recoveries of known amounts of sulfate from
reagent water and drinking, ground, and surface waters are
12. Calculation as shown in Table 3.
12.1 Convert the photometer readings obtained with
13.3.1 A table for estimating the bias of the test
the sample to milligrams per litre sulfate ion (SO4− −) by
method through its applicable concentration range can be
use of the calibration curve described in Section 10. found in Table 4.
13.3.2 These collaborative test data were obtained on
13. Precision and Bias reagent grade water and natural waters. For other matrices,
13.1 The precision and bias data presented in this test these data may not apply.
method meet the requirements of Practice D 2777–86.
13.4 Precision and bias for this test method conforms
13.2 The overall and single-operator precision of the to Practice D 2777–86, which was in place at the time of
test method, within its designated range, varies with the collaborative testing. Under the allowances made in 1.4 of
quantity being tested according to Table 1 for reagent water D 2777–06, these precision and bias data do meet existing
554
TABLE 4 of the batch run to ensure contamination was not a problem

MEAN SULFATE RECOVERY AGAINST during the batch analysis.
CONCENTRATION ADDED WITH OVERALL STANDARD
DEVIATION SHOWN FOR INTERLABORATORY 14.1.2 An instrument check standard should be ana-
EXPERIMENTAL RECOVERY OF SULFATE FROM lyzed at a minimum frequency of 10% throughout the batch
REAGENT WATER AND DRINKING, GROUND, AND analysis. The value of the instrument check standard should
SURFACE WATERA fall between 80% and 120% of the true value.
Mean Sulfate Recovery (–x), mg/L 14.1.3 Two method blanks should be prepared ensur-
Sulfate Added,
mg/L Reagent Water (ST) Matrix Water (SO) ing that an adequate method blank volume is present for
a minimum of seven repetitive analyses. The standard devi-
7.0 6.6 (0.5) 6.9 (0.7) ation of the method blank is used to determine the minimum
20.8 20.4 (1.0) 20.2 (2.2)
63.9 63.7 (2.5) 63.3 (4.5)
detectable concentration of each sample and control in the
batch.
NOTE:
A
14.1.4 A laboratory control sample should be ana-
The test method is linear to 40 mg/L. Testing at the 63.9 level was
lyzed with each batch of samples at a minimum frequency
of 10%.
14.1.5 If the QC for the sample batch is not within
requirements for interlaboratory studies of Committee D19
the established control limits, reanalyze the samples or
test methods.
qualify the results with the appropriate flags, or both. (See
Practice D 5847.)
14. Quality Control (QC) 14.1.6 Blind control samples should be submitted
14.1 The following quality control information is rec- by an outside agency in order to determine the laboratory
ommended for the determination of sulfate ion in water. performance capabilities.
14.1.1 The instrument should be calibrated using a
minimum of four calibration standards and a calibration
blank. The calibration correlation coefficient shall be equal 15. Keywords
to or greater than 0.990. In addition to the initial calibration 15.1 drinking water; ground water; sulfate; surface
blank, a calibration blank should be analyzed at the end water; turbidimetric
--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---
555
APPENDIX
X1. RATIONALE FOR DISCONTINUATION OF METHODS
X1.1 Gravimetric: X1.2 Volumetric:

X1.1.1 This test method was discontinued in 1988. X1.2.1 This test method was discontinued in 1988.
The test method may be found in the 1988 Annual Book The test method may be found in the 1988 Annual Book
--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---
of ASTM Standards, Vol 11.01. The test method was origi- of ASTM Standards, Vol 11.01. The test method was origi-
nally issued in 1938. nally issued in 1959 as a non-referee method, and made
X1.1.2 This test method covers the determination of the primary method in the 1980 issue of Test Method D 516.
sulfate in water and wastewater. Samples containing from X1.2.2 This test method covers the determination of
20 mg/L to 100 mg/L of sulfate may be analyzed. sulfate in industrial water. Samples containing from 5 mg/L
X1.1.3 Sulfate is precipitated and weighted as bar- to 1000 mg/L of sulfate may be analyzed.
ium sulfate after removal of silica and other insoluble X1.2.3 Sulfate is titrated in an alcoholic solution
matter. under controlled acid conditions with a standard barium
X1.1.4 This test method was discontinued because chloride solution using thorin as the indicator.
there were insufficient laboratories interested in participat- X1.2.4 This test method was discontinued because
ing in another collaborative study to obtain the necessary there were insufficient laboratories interested in participat-
precision and bias as required by Practice D 2777. ing in another collaborative study to obtain the necessary
precision and bias as required by Practice D 2777.
556
STANDARD TEST METHOD FOR CHLORINE IN NEW AND

USED PETROLEUM PRODUCTS (BOMB METHOD)
SD-808
(Identical with ASTM Specification D 808-05.)
--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---
557
STANDARD TEST METHOD FOR

CHLORINE IN NEW AND USED PETROLEUM
PRODUCTS (BOMB METHOD)
SD-808
(Identical with ASTM D 808-05)
1. Scope ensures against explosive rupture of the bomb, or a blow-

1.1 This test method covers the determination of chlo- out, provided the bomb is of proper design and construction
rine in lubricating oils and greases, including new and used and in good mechanical condition. It is desirable, however,
lubricating oils and greases containing additives, and in that the bomb be enclosed in a shield of steel plate at least
additive concentrates. Its range of applicability is 0.1 to 13 mm (1⁄2 in.) thick, or equivalent protection be provided
50% chlorine. The procedure assumes that compounds con- against unforseeable contingencies.] The chlorine com-
taining halogens other than chlorine will not be present. pounds thus liberated are absorbed in a sodium carbonate
solution and the amount of chlorine present is determined
1.2 The preferred units are mass percent. The values gravimetrically by precipitation as silver chloride.
stated in SI units are to be regarded as the standard. The
values given in parentheses are for information only.
4. Significance and Use
1.3 This standard does not purport to address all of 4.1 This test method may be used to measure the level
the safety concerns, if any, associated with its use. It is of chlorine-containing compounds in petroleum products.
the responsibility of the user of this standard to establish This knowledge can be used to predict performance or
appropriate safety and health practices and determine the handling characteristics of the product in question.
applicability of regulatory limitations prior to use. Atten-
tion is called to specific warning statements incorporated 4.2 This test method can also serve as a qualitative tool
in the test method. for the presence or non-detection of chlorine in petroleum
products. In light of the efforts in the industry to prepare
chlorine free products, this test method would provide
2. Referenced Documents information regarding the chlorine levels, if any, in such
2.1 ASTM Standards: products.
D 1193 Specification for Reagent Water

5. Apparatus
D 4057 Practice for Manual Sampling of Petroleum and 5.1 Bomb, having a capacity of not less than 300 mL,
Petroleum Products so constructed that it will not leak during the test, and that
D 6299 Practice for Applying Statistical Quality Assurance quantitative recovery of the liquids from the bomb may
Techniques to Evaluate Analytical Measurement Per- be readily achieved. The inner surface of the bomb may
formance be made of stainless steel or any other material that will
not be affected by the combustion process or products.
3. Summary of Test Method gasket and lead-wire insulation, shall be resistant to heat
3.1 The sample is oxidized by combustion in a bomb and chemical action, and shall not undergo any reaction
containing oxygen under pressure. [Warning — Strict that will affect the chlorine content of the liquid in the
--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---
adherence to all of the provisions prescribed hereinafter bomb.
558
5.2 Sample Cup, platinum, 24 mm in outside diameter TABLE 1

at the bottom, 27 mm in outside diameter at the top, 12 mm QUANTITIES OF SAMPLE AND WHITE OIL
in height outside, and weighing 10 g to 11 g. Chlorine Content, Weight of Weight of White
% Sample, g Oil, g
5.3 Firing Wire, platinum, No. 26 B & S gage 0.41
(16 thou), 27 SWG or equivalent. 2 and under 0.8 0.0
Above 2 to 5, incl 0.4 0.4
5.4 Ignition Circuit, capable of supplying sufficient cur-
Above 5 to 10, incl 0.2 0.6
rent to ignite the nylon thread or cotton wicking without Above 10 to 20, incl 0.1 0.7
melting the wire. Above 20 to 50, incl 0.05 0.7
5.4.1 The switch in the ignition circuit shall be of a
type that remains open, except when held in closed position
by the operator. 7.2 Take care that the sample is thoroughly representa-
tive of the material to be tested and that the portion of the
5.5 Nylon Sewing Thread, or Cotton Wicking, white. sample used for the test is thoroughly representative of the
5.6 Filter Crucible, fritted-glass, 30-mL capacity, whole sample.
medium porosity.
8. Procedure
6. Reagents and Materials 8.1 Preparation of Bomb and Sample — Cut a piece of
6.1 Purity of Reagents — Reagent grade chemicals shall firing wire approximately 100 mm in length. Coil the mid-
be used in all tests. Unless otherwise indicated, it is dle section (about 20 mm) and attach the free ends to the
intended that all reagents shall conform to the specifications terminals. Arrange the coil so that it will be above and to
of the Committee on Analytical Reagents of the American one side of the sample cup. Insert into the coil a nylon
Chemical Society, where such specifications are available. thread, or wisp of cotton, of such length that one end will
Other grades may be used, provided it is first ascertained extend into the sample cup. Place about 5 mL of Na2CO3
that the reagent is of sufficiently high purity to permit its solution in the bomb and by means of a rubber policeman,
use without lessening the accuracy of the determination. wet the interior surface of the bomb, including the head,
as thoroughly as possible. Introduce into the sample cup
6.2 Purity of Water — Unless otherwise indicated, refer-
the quantities of sample and white oil (Note 1) (Warn-
ences to water shall be understood to mean reagent water
ing — Do not use more than 1 g total of sample and white
--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---
as defined by Type II or III of Specification D 1193.

oil or other chlorine free combustible material) specified
6.3 Nitric Acid (1 + 1) — Mix equal volumes of concen- in Table 1 (Warning — Do not add oxygen or ignite the
trated nitric acid (HNO3,sp gr 1.42) and water. sample if the bomb has been jarred, dropped, or tilted),
6.4 Oxygen, free of combustible material and halogen weighing the sample to the nearest 0.2 mg. (When white
compounds, available at a pressure of 41 kgf/cm 2 (40 oil is used, stir the mixture with a short length of quartz
atmos). (Warning — Oxygen vigorously accelerates com- rod and allow the rod to remain in the sample cup during
bustion.) the combustion.)
8.1.1 After repeated use of the bomb for chlorine
6.5 Silver Nitrate Solution (50 g AgNO3/L) — Dissolve
determination, a film may be noticed on the inner surface.
50 g of silver nitrate (AgNO3) in water and dilute to 1 L.
This dullness can be removed by periodic polishing of the
6.6 Sodium Carbonate Solution (50 g Na2CO3/L) — bomb. A satisfactory method for doing this is to rotate the
Dissolve 50 g of anhydrous Na2CO3, 58.5 g of Na2CO3 · bomb in a lathe at about 300 rpm and polish the inside
H2O, or 135 g of Na2CO3 · 10 H2O in water and dilute to with Grit No. 2/0 or equivalent paper coated with a light
1 L. machine oil to prevent cutting, and then with a paste of
6.7 White Oil, refined. grit-free chromic oxide and water. This procedure will
remove all but very deep pits and put a high polish on the
6.8 Quality Control (QC) Samples, preferably are por- surface. Before using the bomb wash it with soap and water
tions of one or more liquid petroleum materials that are to remove oil or paste left from the polishing operation.
stable and representative of the samples of interest. These Bombs with porous or pitted surfaces should never be used
QC samples can be used to check the validity of the testing because of the tendency to retain chlorine from sample to
process as described in Section 10. sample.
8.1.2 When the sample is not readily miscible with
7. Sampling white oil, some other nonvolatile, chlorine-free combusti-
7.1 Take samples in accordance with the instructions ble diluent may be employed in place of white oil. How-
in Practice D 4057. ever, the combined weight of sample and nonvolatile
559
TABLE 2 8.5 Determination of Chlorine — Acidify the solution

GAGE PRESSURE by adding HNO3 (1 + 1) drop by drop until acid to methyl
Minimum Gage Maximum Gage red. Add an excess of 2 mL of the HNO3 solution. Filter
Pressure,A kgf/cm2 Pressure,A kgf/cm2 through a qualitative paper [if the solution is cloudy, the
Capacity of Bomb, mL (atm) (atm) presence of lead chloride (PbCl2) is indicated and the solu-
tion should be brought to a boil before filtering] and collect
300 to 350 39 (38) 41 (40)
350 to 400 36 (35) 38 (37)
in a second 600-mL beaker. Heat the solution to about
400 to 450 31 (30) 33 (32) 60°C (140°F) and, while protecting the solution from strong
450 to 500 28 (27) 30 (29) light, add gradually, while stirring, 5 mL of AgNO3 solu-
--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---
A
The minimum pressures are specified to provide sufficient oxygen
tion. Heat to incipient boiling and retain at this temperature
for complete combustion, and the maximum pressures represent a until the supernatant liquid becomes clear. Test to ensure
safety requirement. complete precipitation by adding a few drops of the AgNO3
solution. If more precipitation takes place, repeat the above
steps which have involved heating, stirring, and addition
diluent shall not exceed 1 g. Some solid additives are of AgNO3, as often as necessary, until the additional drops
relatively insoluble, but may be satisfactorily burned when of AgNO3 produce no turbidity in the clear, supernatant
covered with a layer of white oil. (Warning — Do not liquid. Allow the beaker and contents to stand in a dark
use more than 1 g total of sample and white oil or other place for at least an hour. Filter the precipitate by suction on
chlorine-free combustible material.) a weighed fritted-glass filter crucible. Wash the precipitate
NOTE 1 — The practice of running alternately high and low samples in
with water containing 2 mL of HNO3 (1 + 1)/L. Dry the
chlorine content shall be avoided whenever possible. It is difficult to crucible and precipitate at 110°C for 1 h. Cool in a desicca-
rinse the last traces of chlorine from the walls of the bomb and the tor, and weigh.
tendency for residual chlorine to carry over from sample to sample has
been observed in a number of laboratories. When a sample high in chlorine NOTE 2 — If no precipitate is visible at this stage after addition of silver
has preceded one low in chlorine content, the test on the low-chlorine nitrate, this may be taken as an indication of non-detectable quantities
sample shall be repeated and one or both of the low values thus obtained of chlorine in the test sample above this test method’s detection limit
can be considered suspect if they do not agree within the limits of (0.1 m%). The test can be considered as completed at this stage.
repeatability of this method.
8.6 Blank — Make a blank determination with 0.7 to
8.2 Addition of Oxygen — Place the sample cup in posi- 0.8 g of white oil by following the normal procedure but
tion and arrange the nylon thread, or wisp of cotton, so omitting the sample (Note 3). Repeat this blank whenever
that the end dips into the sample. Assemble the bomb and new batches of reagents or white oil are used. The blank
tighten the cover securely. Admit oxygen (Warning — must not exceed 0.03% chlorine based upon the weight of
Do not add oxygen or ignite the sample if the bomb has the white oil.
been jarred, dropped, or tilted) slowly (to avoid blowing
NOTE 3 — This procedure measures chlorine in the white oil and in the
the oil from the cup) until a pressure is reached as indicated reagents used, as well as that introduced from contamination.
in Table 2.
8.3 Combustion — Immerse the bomb in a cold water
bath. Connect the terminals to the open electrical circuit. 9. Calculation
Close the circuit to ignite the sample. Remove the bomb 9.1 Calculate the chlorine content of the sample as
from the bath after immersion for at least 10 min. Release follows:
the pressure at a slow, uniform rate such that the operation
Chlorine, mass % p [(P − B) ⴛ 24.74]/W (1)
requires not less than 1 min. Open the bomb and examine
the contents. If traces of unburned oil or sooty deposits where
are found, discard the determination, and thoroughly clean P p grams of AgCl obtained from the sample
the bomb before again putting it in use (8.1.1). B p grams of AgCl obtained from the blank
8.4 Collection of Chlorine Solution — Rinse the interior W p grams of sample used
of the bomb, the sample cup, and the inner surface of the
bomb cover with a fine jet of water, and collect the wash-
ings in a 600-mL beaker. Scrub the interior of the bomb 10. Quality Control
and the inner surface of the bomb cover with a rubber 10.1 Confirm the performance of the instrument or the
policeman. Wash the base of the terminals until the wash- test procedure by analyzing a QC sample (see 6.8).
ings are neutral to the indicator methyl red. (The volume 10.1.1 When QC/Quality Assurance (QA) protocols
of the washings is normally in excess of 300 mL.) Take are already established in the testing facility, these may be
special care not to lose any wash water. used to confirm the reliability of the test result.
560
10.1.2 When there is no QC/QA protocol established Chlorine, % Repeatability

in the testing facility, Appendix X1 can be used as the 0.1 to 1.9 0.07
QC/QA system. 2.0 to 5.0 0.15
Above 5.0 3% of amount present
11. Report 12.2.2 Reproducibility — The difference between two

11.1 Report the results to the nearest 0.1 m%. single and independent results obtained by different opera-
tors working in different laboratories on identical test mate-
11.2 If there is absence of a visible precipitate in 8.5, rial would, in the long run, in the normal and correct
report the results as non-detectable above the detection operation of the test method exceed the following values
limits (0.1 m%) of this test method. only in one case in twenty:
Chlorine, % Reproducibility
12. Precision and Bias 0.1 to 1.9 0.10
12.1 The precision of this test method is not known to 2.0 to 5.0 0.30
have been obtained in accordance with currently accepted Above 5.0 5% of amount present
guidelines (for example, in Committee D02 Research
Report RR:D02-1007, Manual on Determining Precision 12.3 Bias:
Data for ASTM Methods on Petroleum Products and Lubri- 12.3.1 Cooperative data indicate that deviations of
cants). test results from the true chlorine content are of the same
order of magnitude as the reproducibility.
12.2 The precision of this test method as obtained by
statistical examination of interlaboratory test results is as 12.3.2 It is not practicable to specify the bias of this
follows: test method for measuring chlorine because the responsible
12.2.1 Repeatability — The difference between suc- subcommittee, after diligent search, was unable to attract
cessive test results obtained by the same operator with the volunteers for an interlaboratory study.
same apparatus under constant operating conditions on
identical test material would, in the long run, in the normal
and correct operation of the test method exceed the follow- 13. Keywords
ing values only in one case in twenty: 13.1 bomb; chlorine
561
--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---

APPENDIX
X1. QUALITY CONTROL on the criticality of the quality being measured, the demon-
strated stability of the testing process, and customer
X1.1 Confirm the performance of the instrument or the
requirements. Generally, a QC sample is analyzed each
test procedure by analyzing a QC sample.
testing day with routine samples. The QC frequency should
X1.2 Prior to monitoring the measurement process, the be increased if a large number of samples are routinely
user of the method needs to determine the average value analyzed. However, when it is demonstrated that the testing
is under statistical control, the QC testing frequency may
and control limits of the QC sample (see Practice D 6299
be reduced. The QC sample precision should be checked
and MNL 7).
against the ASTM method precision to ensure data quality.
X1.3 Record the QC results and analyze by control X1.5 It is recommended that, if possible, the type of
charts or other statistically equivalent techniques to ascer- QC sample that is regularly tested be representative of the
tain the statistical control status of the total testing process material routinely analyzed. An ample supply of QC sam-
(see Practice D 6299 and MNL 7). Any out-of-control data ple material should be available for the intended period
should trigger investigation for root cause(s). of use, and must be homogenous and stable under the
anticipated storage conditions. See Practice D 6299 and
X1.4 In the absence of explicit requirements given in MNL 7 for further guidance on QC and Control Charting
the test method, the frequency of QC testing is dependent techniques.
--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---
562
2013 SECTION V ARTICLE 24, SE-165
STANDARD PRACTICE FOR LIQUID PENETRANT

EXAMINATION FOR GENERAL INDUSTRY
SE-165
(Identical with ASTM Specification E 165-09.)

--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,
563
ARTICLE 24, SE-165 2013 SECTION V
STANDARD PRACTICE FOR

LIQUID PENETRANT EXAMINATION FOR GENERAL
INDUSTRY
SE-165
(Identical with ASTM Specification E 165-09)
1. Scope 1.4 The values stated in inch-pound units are to be

1.1 This practice covers procedures for penetrant exam- regarded as the standard. SI units are provided for informa-
ination of materials. Penetrant testing is a nondestructive tion only.
testing method for detecting discontinuities that are open
1.5 This standard does not purport to address all of
to the surface such as cracks, seams, laps, cold shuts,
the safety concerns, if any, associated with its use. It is
shrinkage, laminations, through leaks, or lack of fusion
the responsibility of the user of this standard to establish
and are applicable to in-process, final, and maintenance
appropriate safety and health practices and determine the
testing. It can be effectively used in the examination of
applicability of regulatory limitations prior to use.
nonporous, metallic materials, ferrous and nonferrous met-
--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---
als, and of nonmetallic materials such as glazed or fully

densified ceramics, as well as certain nonporous plastics, 2. Referenced Documents
and glass. 2.1 ASTM Standards:
1.2 This practice also provides a reference: D 129 Test Method for Sulfur in Petroleum Products (Gen-
1.2.1 By which a liquid penetrant examination pro- eral Bomb Method)
cess recommended or required by individual organizations
can be reviewed to ascertain its applicability and com- D 516 Practice for Testing Thermal Conductivity Detectors
pleteness. Used in Gas Chromatography
1.2.2 For use in the preparation of process specifica- D 808 Test Method for Chlorine in New and Used Petro-
tions dealing with the liquid penetrant testing of parts and leum Products (Bomb Method)
materials. Agreement by the customer requesting penetrant
inspection is strongly recommended. All areas of this prac- D 1193 Specification for Reagent Water
tice may be open to agreement between the cognizant D 1552 Test Method for Sulfur in Petroleum Products
engineering organization and the supplier, or specific direc- (High-Temperature Method)
tion from the cognizant engineering organization.
1.2.3 For use in the organization of the facilities and D 4327 Test Method for Anions in Water in Chemically
personnel concerned with the liquid penetrant testing. Suppressed Ion Chromatography
1.3 This practice does not indicate or suggest criteria E 433 Reference Photographs for Liquid Penetrant
for evaluation of the indications obtained by penetrant Inspection
testing. It should be pointed out, however, that after indica-
E 543 Specification for Agencies Performing Nondestruc-
tions have been found, they must be interpreted or classified
tive Testing
and then evaluated. For this purpose there must be a sepa-
rate code, standard, or a specific agreement to define the E 1208 Test Method for Fluorescent Liquid Penetrant
type, size, location, and direction of indications considered Examination Using the Lipophilic Post-Emulsification
acceptable, and those considered unacceptable. Process
564
E 1209 Test Method for Fluorescent Liquid Penetrant TABLE 1

Examination Using the Water-Washable Process CLASSIFICATION OF PENETRANT EXAMINATION
TYPES AND METHODS
E 1210 Test Method for Fluorescent Liquid Penetrant
Examination Using the Hydrophilic Post-Emulsification Type I — Fluorescent Penetrant Examination
Process Method A — Water-washable (see Test Method E 1209)
Method B — Post-emulsifiable, lipophilic (see Test Method E
E 1219 Test Method for Fluorescent Liquid Penetrant 1208)
Examination Using the Solvent-Removable Process Method C — Solvent removable (see Test Method E 1219)
Method D — Post-emulsifiable, hydrophilic (see Test Method E
E 1220 Test Method for Visible Penetrant Examination 1210)
Using the Solvent-Removable Process Type II — Visible Penetrant Examination
E 1316 Terminology for Nondestructive Examinations Method A — Water-washable (see Test Method E 1418)
Method C — Solvent removable (see Test Method E 1220)
--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---
E 1417 Practice for Liquid Penetrant Testing

E 1418 Test Method for Visible Penetrant Examination NOTE 1: The developer may be omitted by agreement between the
Using the Water-Washable Process contracting parties.
2.2 ASNT Documents: NOTE 2: Fluorescent penetrant examination shall not follow a visible
penetrant examination unless the procedure has been qualified in accor-
SNT-TC-1A Recommended Practice for Nondestructive dance with 10.2, because visible dyes may cause deterioration or quench-
Testing Personnel Qualification and Certification ing of fluorescent dyes.
ANSI/ASNT CP-189 Standard for Qualification and Certi- 4.2 Processing parameters, such as surface precleaning,
fication of Nondestructive Testing Personnel penetration dwell time and excess penetrant removal meth-
2.3 Military Standard: ods, are dependent on the specific materials used, the nature
of the part under examination (that is, size, shape, surface
MIL-STD-410 Nondestructive Testing Personnel Qualifi- condition, alloy), and type of discontinuities expected.
cation and Certification
2.4 APHA Standard: 5. Significance and Use
429 Method for the Examination of Water and Wastewater 5.1 Liquid penetrant examination methods indicate the
presence, location and, to a limited extent, the nature and
2.5 AIA Standard: magnitude of the detected discontinuities. Each of the vari-
NAS-410 Certification and Qualification of Nondestructive ous methods has been designed for specific uses such as
Test Personnel critical service items, volume of parts, portability or local-
2.6 SAE Standards: ized areas of examination. The method selected will depend
accordingly on the design and service requirements of the
AMS 2644 Inspection Material, Penetrant parts or materials being tested.
QPL-AMS-2644 Qualified Products of Inspection Materi-
als, Penetrant 6. Classification of Penetrant Materials and
Methods
3. Terminology 6.1 Liquid penetrant examination methods and types
3.1 The definitions relating to liquid penetrant examina- are classified in accordance with MIL-I-25135 and
tion, which appear in Terminology E 1316, shall apply to AMS 2644 and listed in Table 1.
the terms used in this standard. 6.2 Fluorescent Penetrant Testing (Type 1) — Fluores-
cent penetrant testing utilizes penetrants that fluoresce bril-
4. Summary of Test Method liantly when excited by black light (UVA). The sensitivity
of fluorescent penetrants depends on their ability to be
4.1 Liquid penetrant may consist of visible or fluores-
retained in the various size discontinuities during pro-
cent material. The liquid penetrant is applied evenly over
cessing, then to bleed out into the developer coating and
the surface being examined and allowed to enter open
produce indications that will fluoresce. Fluorescent indica-
discontinuities. After a suitable dwell time, the excess sur-
tions are many times brighter than their surroundings when
face penetrant is removed. A developer is applied to draw
viewed under black light illumination.
the entrapped penetrant out of the discontinuity and stain
the developer. The test surface is then examined to deter- 6.3 Visible Penetrant Testing (Type 2) — Visible pene-
mine the presence or absence of indications. trant testing uses a penetrant that can be seen in visible
565
light. The penetrant is usually red, so that the indications 7.3 Emulsifiers:
produce a definite contrast with the white background of 7.3.1 Lipophilic Emulsifiers are oil-miscible liquids
the developer. Visible penetrant indications must be viewed used to emulsify the post-emulsified penetrant on the sur-
under adequate white light. face of the part, rendering it water-washable. The individ-
ual characteristics of the emulsifier and penetrant, and the
7. Types of Materials geometry/surface roughness of the part material contribute
to determining the emulsification time.
7.1 Liquid penetrant examination materials consist of
fluorescent and visible penetrants, emulsifiers (oil-base and 7.3.2 Hydrophilic Emulsifiers are water-miscible liq-
water-base), removers (water and solvent) and developers uids used to emulsify the excess post-emulsified penetrant
(dry powder, aqueous and nonaqueous). A family of liquid on the surface of the part, rendering it water-washable.
penetrant examination materials consists of the applicable These water-base emulsifiers (detergent-type removers) are
penetrant and emulsifier, as recommended by the manufac- supplied as concentrates to be diluted with water and used
turer. Any liquid penetrant, remover, and developer listed as a dip or spray. The concentration, use, and maintenance
in QPL-25135/QPL-AMS2644 can be used, regardless of shall be in accordance with manufacturer’s recommenda-
the manufacturer. Intermixing of penetrants and emulsifiers tions.
from different manufacturers is prohibited. 7.3.2.1 Hydrophilic emulsifiers function by dis-
placing the excess penetrant film from the surface of the
NOTE 3: Refer to 9.1 for special requirements for sulfur, halogen and
alkali metal content. part through detergent action. The force of the water spray
or air/mechanical agitation in an open dip tank provides
NOTE 4: While approved penetrant materials will not adversely affect the scrubbing action while the detergent displaces the film
common metallic materials, some plastics or rubbers may be swollen or of penetrant from the part surface. The individual charac-
stained by certain penetrants.
terisitics of the emulsifier and penetrant, and the geometry
7.2 Penetrants: and surface roughness of the part material contribute to
7.2.1 Post-Emulsifiable Penetrants are insoluble in determining the emulsification time. Emulsification con-
water and cannot be removed with water rinsing alone. centration shall be monitored weekly using a suitable
They are formulated to be selectively removed from the refractometer.
surface using a separate emulsifier. Properly applied and 7.4 Solvent Removers. Solvent removers function by
given a proper emulsification time, the emulsifier combines dissolving the penetrant, making it possible to wipe the
with the excess surface penetrant to form a water-washable surface clean and free of excess penetrant.
mixture, which can be rinsed from the surface, leaving the
surface free of excessive fluorescent background. Proper 7.5 Developers. Developers form a translucent or white
emulsification time must be experimentally established and absorptive coating that aids in bringing the penetrant out
maintained to ensure that over-emulsification does not of the surface discontinuities through blotting action, thus
occur, resulting in loss of indications. increasing the visibility of the indications.
7.2.2 Water-Washable Penetrants are formulated to 7.5.1 Dry Powder Developers. Dry powder devel-
be directly water-washable from the surface of the test opers are used as supplied, that is, free-flowing, non-caking
part, after a suitable penetrant dwell time. Because the powder (see 8.8.2). Care should be taken not to contaminate
emulsifier is “built-in,” water-washable penetrants can be the developer with fluorescent penetrant, as the contami-
washed out of discontinuities if the rinsing step is too long nant developer specks can appear as penetrant indications.
or too vigorous. It is therefore extremely important to 7.5.2 Aqueous Developers. Aqueous developers are
exercise proper control in the removal of excess surface normally supplied as dry powder particles to be either
penetrant to ensure against overwashing. Some penetrants suspended (water suspendable) or dissolved (water soluble)
are less resistant to overwashing than others, so caution in water. The concentration, use, and maintenance shall
should be exercised. be in accordance with manufacturer’s recommendations.
Water soluble developers shall not be used with Type 2
7.2.3 Solvent-Removable Penetrants are formulated
penetrants or Type 1, Method A penetrants.
so that excess surface penetrant can be removed by wiping
until most of the penetrant has been removed. The NOTE 5: Aqueous developers may cause stripping of indications if not
remaining traces should be removed with the solvent properly applied and controlled. The procedure should be qualified in
remover (see 8.6.4). To prevent removal of penetrant from accordance with 10.2.
discontinuities, care should be taken to avoid the use of 7.5.3 Nonaqueous Wet Developers. Nonaqueous wet
excess solvent. Flushing the surface with solvent to remove developers are supplied as suspensions of developer parti-
the excess penetrant is prohibited as the penetrant indica- cles in a nonaqueous solvent carrier ready for use as sup-
tors could easily be washed away. plied. Nonaqueous, wet developers are sprayed on to form
--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---
566
a thin coating on the surface of the part when dried. The be clean and dry before the penetrant is applied. If only a
thin coating serves as the developing medium. section of a part, such as a weld, including the heat affected
zone is to be examined, all contaminants shall be removed
NOTE 6: This type of developer is intended for application by spray only.
from the area being examined as defined by the contracting
7.5.4 Liquid Film Developers are solutions or colloi- parties. “Clean” is intended to mean that the surface must
dal suspensions of resins/polymer in a suitable carrier. be free of rust, scale, welding flux, weld spatter, grease,
These developers will form a transparent or translucent paint, oily films, dirt, and so forth, that might interfere
coating on the surface of the part. Certain types of film with the penetrant process. All of these contaminants can
developer may be stripped from the part and retained for prevent the penetrant from entering discontinuities (see
record purposes (see 8.8.4). Annex or Cleaning of Parts and Materials).
8.4.1 Drying After Cleaning — It is essential that the
8. Procedure surface of parts be thoroughly dry after cleaning, since any
8.1 The following processing parameters apply to both liquid residue will hinder the entrance of the penetrant.
fluorescent and visible penetrant testing methods. Drying may be accomplished by warming the parts in
drying ovens, with infrared lamps, forced hot air, or expo-
8.2 Temperature Limits — The temperature of the pene- sure to ambient temperature.
trant materials and the surface of the part to be processed
shall be between 40°F and 125°F (4°C and 52°C) or the NOTE 9: Residues from cleaning processes such as strong alkalies, pick-
ling solutions and chromates, in particular, may adversely react with the
procedure must be qualified at the temperature used as
penetrant and reduce its sensitivity and performance.
described in 10.2.
8.5 Penetrant Application — After the part has been
8.3 Examination Sequence — Final penetrant examina-
cleaned, dried, and is within the specified temperature
tion shall be performed after the completion of all opera-
range, the penetrant is applied to the surface to be examined
tions that could cause surface-connected discontinuities or
so that the entire part or area under examination is com-
operations that could expose discontinuities not previously
pletely covered with penetrant. Application methods
open to the surface. Such operations include, but are not
include dipping, brushing, flooding, or spraying. Small
limited to, grinding, welding, straightening, machining, and
parts are quite often placed in suitable baskets and dipped
heat treating. Satisfactory inspection results can usually be
into a tank of penetrant. On larger parts, and those with
obtained on surfaces in the as-welded, as-rolled, as-cast,
complex geometries, penetrant can be applied effectively
as-forged, or ceramics in the densified condition.
--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---
by brushing or spraying. Both conventional and electro-
8.3.1 Surface Treatment — Final penetrant examina- static spray guns are effective means of applying liquid
tion may be performed prior to treatments that can smear penetrants to the part surfaces. Not all penetrant materials
the surface but not by themselves cause surface discontinu- are suitable for electrostatic spray applications, so tests
ities. Such treatments include, but are not limited to, vapor should be conducted prior to use. Electrostatic spray appli-
blasting, deburring, sanding, buffing, sandblasting, or lap- cation can eliminate excess liquid build-up of penetrant on
ping. Performance of final penetrant examination after such the part, minimize overspray, and minimize the amount
surface treatments necessitates that the part(s) be etched of penetrant entering hollow-cored passages which might
to remove smeared metal from the surface prior to testing serve as penetrant reservoirs, causing severe bleedout prob-
unless otherwise agreed by the contracting parties. Note lems during examination. Aerosol sprays are conveniently
that final penetrant examination shall always precede sur- portable and suitable for local application.
face peening.
NOTE 10: With spray applications, it is important that there be proper
NOTE 7: Sand or shot blasting can close discontinuities so extreme ventilation. This is generally accomplished through the use of a properly
care should be taken to avoid masking discontinuities. under certain designed spray booth and exhaust system.
circumstances, however, grit blasting with certain air pressures and/or
8.5.1 Penetrant Dwell Time — After application,
mediums may be acceptable without subsequent etching when agreed by
the contracting parties. allow excess penetrant to drain from the part (care should
be taken to prevent pools of penetrant from forming on
NOTE 8: Surface preparation of structural or electronic ceramics for the part), while allowing for proper penetrant dwell time
penetrant testing by grinding, sand blasting, and etching is not recom- (see Table 2). The length of time the penetrant must remain
mended because of the potential for damage.
on the part to allow proper penetration should be as recom-
8.4 Precleaning — The success of any penetrant exami- mended by the penetrant manufacturer. Table 2, however,
nation procedure is greatly dependent upon the surrounding provides a guide for selection of penetrant dwell times for
surface and discontinuity being free of any contaminant a variety of materials, forms, and types of discontinuity.
(solid or liquid) that might interfere with the penetrant Unless otherwise specified, the dwell time shall not exceed
process. All parts or areas of parts to be examined must the maximum recommended by the manufacturer.
567
TABLE 2
RECOMMENDED MINIMUM DWELL TIMES
Dwell TimesA (minutes)

Type of
Material Form Discontinuity PenetrantB DeveloperC
Aluminum, magnesium, steel, brass castings and welds cold shuts, porosity, lack of fusion, 5 10
and bronze, titanium and high- cracks (all forms)
temperature alloys
wrought materials — extrusions, laps, cracks (all forms) 10 10
forgings, plate
Carbide-tipped tools lack of fusion, porosity, cracks 5 10
Plastic all forms cracks 5 10
Glass all forms cracks 5 10
Ceramic all forms cracks, porosity 5 10
A
For temperature range from 50 to 100°F (10 to 38°C) for fluorescent penetrants and 50 to 125°F (10 to 52°C) for visible penetrant.
B
Maximum penetrant dwell time in accordance with 8.5.2.
C
Development time begins as soon as wet developer coating has dried on surface of parts (recommended minimum). Maximum development
time in accordance with 8.8.6.
8.6 Penetrant Removal emulsifier shall not be agitated while being immersed. After
8.6.1 Water Washable (Method A): application of the emulsifier, the parts shall be drained and
positioned in a manner that prevents the emulsifier from
8.6.1.1 Removal of Excess Penetrants — After the
pooling on the part(s).
required penetrant dwell time, the excess penetrant on the
surface being examined must be removed with water. It 8.6.2.2 Emulsification Time — The emulsification
can be removed manually by a coarse spray or wiping the time begins as soon as the emulsifier is applied. The length
aprt surface with a dampened rag, automatic or of time that the emulsifier is allowed to remain on a part
semi-automatic water-spray equipment, or by water immer- and in contact with the penetrant is dependent on the type
sion. For immersion rinsing, parts are completely immersed of emulsifier employed and the surface roughness. Nominal
in the water bath with air or mechanical agitation. emulsification time should be as recommended by the man-
(a) The temperature of the water shall be maintained ufacturer. The actual emulsification time must be deter-
within the range of 50°F to 100°F (10°C to 38°C). mined experimentally for each specific application. The
(b) Spray-rinse water pressure should not exceed 40 psi surface finish (roughness) of the part is a significant factor
(275 kPa). When hydro-air pressure spray guns are used, in the selection of and in the emulsification time of an
--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---
the air pressure should not exceed 25 psi (172 kPa). emulsifier. Contact time shall be kept to the minimum time
to obtain an acceptable background and shall not exceed
NOTE 11: Overwashing should be avoided. Excessive washing can cause three minutes.
penetrant to be washed out of discontinuities. With fluorescent penetrant
methods perform the rinsing operation under black light so that it can 8.6.2.3 Post Rinsing — Effective post rinsing of the
be determined when the surface penetrant has been adequately removed. emulsified penetrant from the surface can be accomplished
8.6.1.2 Removal by Wiping (Method C) — After using either manual, semi-automated, or automated water
the required penetrant dwell time, the excess penetrant is immersion or spray equipment or combinations thereof.
removed by wiping with a dry, clean, lint-free cloth/towel. 8.6.2.4 Immersion — For immersion post rinsing,
Then use a clean lint-free cloth/towel lightly moistened parts are completely immersed in the water bath with air
with water or solvent to remove the remaining traces of or mechanical agitation. The amount of time the part is in
surface penetrant as determined by examination under the bath should be the minimum required to remove the
black light for fluorescent methods and visible light for emulsified penetrant. In addition, the temperature range of
visible methods. the water should be 50°F to 100°F (10°C to 38°C). Any
8.6.2 Lipophilic Emulsification (Method B): necessary touch-up rinse after an immersion rinse shall
8.6.2.1 Application of Lipophilic Emulsifier — meet the requirements of 8.6.2.5.
After the required penetration dwell time, the excess pene- 8.6.2.5 Spray Post Rinsing — Effective post rins-
trant on the part must be emulsified by immersing or flooding following emulsification can also be accomplished by
ing the parts with the required emulsifier (the emulsifier either manual or automatic water spray rinsing. The water
combines with the excess surface penetrant and makes the temperature shall be between 50°F and 100°F (10°C and
mixture removable by water rinsing). Lipophililc emulsifier 38°C). The water spray pressure shall not exceed 40 psi
shall not be applied by spray or brush and the part or (275 kPa) when manual spray guns are used. When
568
hydro-air pressure spray guns are used, the air pressure emulsify the residual penetrant on part surfaces to render
should not exceed 25 psi (172 kPa). it water-washable. The concentration of the emulsifier for
8.6.2.6 Rinse Effectiveness — If the emulsification spray application should be in accordance with the manu-
and final rinse step is not effective, as evidenced by exces- facturer’s recommendations, but it shall not exceed 5%.
sive residual surface penetrant after emulsification and rins- The water spray pressure should be less than 40 psi
ing, thoroughly reclean and completely reprocess the part. (275 kPa). Contact with the emulsifier shall be kept to the
minimum time to obtain an acceptable background and
8.6.3 Hydrophilic Emulsification (Method D): shall not exceed two minutes. The water temperature shall
8.6.3.1 Application of Hydrophilic Remover — be maintained between 50°F and 100°F (10°C and 38°C).
Following the required penetration dwell time, the parts 8.6.3.6 Post-Rinsing of Hydrophilic Emulsified
may be be prerinsed with water prior to application of the Parts — Effective post-rinsing of emulsified penetrant from
hydrophilic emulsifier. This prerinse allows for the removal the surface can be accomplished using either manual or
of excess surface penetrant from the parts prior to emulsifi- automated water spray, water immersion, or combinations
cation so as to minimize penetrant contamination in the thereof. The total rinse time shall not exceed two minutes
hydrophilic emulsifier bath, thereby extending its life. It regardless of the number of rinse methods used.
is not necessary to prerinse a part if a spray application of
8.6.3.7 Immersion Post-Rinsing — If an agitated
emulsifier is used.
immersion rinse is used, the amount of time the part(s) is
8.6.3.2 Prerinsing Controls — Effective prerinsing (are) in the bath shall be the minimum required to remove
is accomplished by manual, semi-automated, or automated the emulsified penetrant and shall not exceed two minutes.
water spray rinsing of the part(s). The water spray pressure In addition, the temperature range of the water shall be
shall not exceed 40 psi (275 kPa) when manual or hydro within 50°F and 100°F (10°C and 38°C). Be aware that a
air spray guns are used. When hydro-air pressure spray touch-up rinse may be necessary after immersion rinse,
guns are used, the air pressure shall not exceed 25 psi but the total wash time still shall not exceed two minutes.
(172 kPa). Water free of contaminants that could clog spray
--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---
8.6.3.8 Spray Post-Rinsing — Effective post-rins-

nozzles or leave a residue on the part(s) is recommended. ing following emulsification can also be accomplished by
8.6.3.3 Application of Emulsifier — The residual manual, semi-automatic, or automatic water spray. The
surface penetrant on part(s) must be emulsified by immers- water spray pressure shall not exceed 40 psi (275kPa) when
ing the part(s) in an agitated hydrophilic emulsifier bath manual or hydro air spray guns are used. When hydro-air
or by spraying the part(s) with water/emulsifier solutions pressure spray guns are used, the air pressure shall not
thereby rendering the remaining residual surface penetrant exceed 25 psi (172 kPa). The water temperature shall be
water-washable for the final rinse station. The emulsifica- between 50°F and 100°F (10°C and 38°C). The spray rinse
tion time begins as soon as the emulsifier is applied. The time shall be less than two minutes, unless otherwise spec-
length of time that the emulsifier is allowed to remain on ified.
a part and in contact with the penetrant is dependent on 8.6.3.9 Rinse Effectiveness — If the emulsification
the type of emulsifier employed and the surface roughness. and final rinse steps are not effective, as evidenced by
The emulsification time should be determined experimen- excessive residual surface penetrant after emulsification
tally for each specific application. The surface finish and rinsing, thoroughly reclean, and completely reprocess
(roughness of the part is a significant factor in determining the part.
the emulsification time necessary for an emulsifier. Contact 8.6.4 Removal of Solvent-Removable Penetrant
emulsification time should be kept to the least possible (Method C) — After the required penetrant dwell time, the
time consistent with an acceptable background and shall
excess penetrant is removed by wiping with a dry, clean,
not exceed two minutes. lint-free cloth/towel. Then use a clean, lint-free cloth/towel
8.6.3.4 Immersion — For immersion application, lightly moistened with solvent remover to remove the
parts shall be completely immersed in the emulsifier bath. remaining traces of surface penetrant. Gently wiping must
The hydrophilic emulsifier concentration shall be as recom- be used to avoid removing penetrant from any discontinu-
mended by the manufacturer and the bath or part shall be ity. On smooth surfaces, an alternate method of removal
gently agitated by air or mechanically throughout the cycle. can be done by wiping with a clean, dry cloth. Flushing
The minimum time to obtain an acceptable background the surface with solvent following the application of the
shall be used, but the dwell time shall not be more than penetrant and prior to developing is prohibited.
two minutes unless approved by the contracting parties. 8.7 Drying — Regardless of the type and method of
8.6.3.5 Spray Application — For spray applica- penetrant used, drying the surface of the part(s) is necessary
tions, all part surfaces should be evenly and uniformly prior to applying dry or nonaqueous developers or follow-
sprayed with a water/emulsifier solution to effectively ing the application of the aqueous developer. Drying time
569
will vary with the size, nature, and number of parts being surface has been dried, apply nonaqueous wet developer
processed. by spraying in such a manner as to ensure complete part
8.7.1 Drying Parameters — Components shall be air coverage with a thin, even film of developer. The developer
dried at room temperature or in a drying oven. Oven tem- shall be applied in a manner appropriate to the type of
peratures shall not exceed 160°F (71°C). Drying time shall penetrant being used. For visible dye, the developer must
only be that necessary to adequately dry the part. Compo- be applied thickly enough to provide a contrasting back-
nents shall be removed from the oven after drying. Compo- ground. For fluorescent dye, the developer must be applied
nents should not be placed in the oven with pooled water thinly to produce a translucent covering. Dipping or flood-
or pooled aqueous solutions/suspensions. ing parts with nonaqueous developers is prohibited,
because the solvent action of these types of developers can
8.8 Developer Application — There are various modes flush or dissolve the penetrant from within the discontinu-
of effective application of the various types of developers ities.
such as dusting, immersing, flooding or spraying. The
developer form, the part size, configuration, and surface NOTE 12: The vapors from the volatile solvent carrier in the developer
may be hazardous. Proper ventilation should be provided at all times,
roughness will influence the choice of developer appli-
but especially when the developer is applied inside a closed area.
cation.
8.8.4 Liquid Film Developers — Apply by spraying
8.8.1 Dry Powder Developer (Form A) — Dry pow- as recommended by the manufacturer. Spray parts in such
der developers should be applied immediately after the a manner as to ensure complete part coverage of the area
part is dry in such a manner as to ensure complete coverage being examined with a thin, even film of developer.
of the area of interest. Parts can be immersed in a container
8.8.5 Developing Time — The length of time the
of dry developer or in a fluid bed of dry developer. They
developer is to remain on the part prior to inspection shall
can also be dusted with the powder developer through a
be not less than ten minutes. Developing time begins imme-
hand powder bulb or a conventional or electrostatic powder
diately after the application of dry powder developer or as
gun. It is common and effective to apply dry powder in
soon as the wet (aqueous and nonaqueous) developer coat-
an enclosed dust chamber, which creates an effective and
ing is dry (that is, the water or solvent carrier has evaporated
controlled dust cloud. Other means suited to the size and
to dryness). The maximum permitted developing times
geometry of the specimen may be used, provided the pow-
shall be four hours for dry powder developer (Form A),
der is applied evenly over the entire surface being exam-
two hours for aqueous developer (Forms B and C), and
ined. Excess developer powder may be removed by shaking
one hour for nonaqueous developer (Forms D and E).
or tapping the part, or by blowing with low-pressure dry,
clean, compressed air not exceeding 5 psi (34 kPa). Dry 8.9 Inspection — After the applicable development
developers shall not be used with Type II penetrant. time, perform inspection of the parts under visible or ultra-
8.8.2 Aqueous Developers (Forms B and C) — Water violet light as appropriate. It may be helpful to observe
soluble developers (Form B) are prohibited for use with the bleed out during the development time as an aid in
Type 2 penetrants or Type 1, Method A penetrants. Water interpreting indications.
suspendable developers (Form C) can be used with noth 8.9.1 Ultraviolet Light Examination — Examine parts
Type 1 and Type 2 penetrants. Aqueous developers shall tested with Type 1 fluorescent penetrant under black light
be applied to the part immediately after the excess penetrant in a darkened area. Ambient light shall not exceed 2 fc
has been removed and prior to drying. Aqueous developers (21.5 lx). The measurement shall be made with a suitable
shall be prepared and maintained in accordance with the visible light sensor at the inspection surface.
manufacturer’s instructions and applied in such a manner
NOTE 13: Because the fluorescent constituents in the penetrant will
as to ensure complete, even, part coverage. Aqueous devel- eventually fade with direct exposure to ultraviolet light, direct exposure
opers may be applied by spraying, flowing, or immersing of the part under test to ultraviolet light should be minimized when not
the part in a prepared developer bath. Immerse the parts removing excess penetrant or evaluating indications.
only long enough to coat all of the part surfaces with the 8.9.1.1 Black Light Level Control — Black lights
developer since indications may leach out if the parts are shall produce a minimum light intensity of 1000 ␮W/cm2,
left in the bath too long. After the parts are removed from at a distance of 15 in. (38.1 cm). The intensity should be
the developer bath, allow the parts to drain. Drain all excess checked daily to ensure the required output. Reflectors and
developer from recesses and trapped sections to eliminate filters should also be checked daily for cleanliness and
pooling of developer, which can obscure discontinuities. integrity. Cracked or broken ultraviolet filters shall be
Dry the parts in accordance with 8.7. The dried developer replaced immediately. Since a drop in line voltage can
coating appears as a translucent or white coating on the part. cause decreased black light output with consequent incon-
8.8.3 Nonaqueous Wet Developers (Forms D and sistent performance, a constant-voltage transformer should
E) — After the excess penetrant has been removed and the be used when there is evidence of voltage fluctuation.
570 --`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---

NOTE 14: Certain high-intensity black lights may emit unacceptable 9. Special Requirements
amounts of visible light, which can cause fluorescent indications to disap-
pear. Care should be taken to use only bulbs suitable for fluorescent
9.1 Impurities:
penetrant testing purposes. 9.1.1 When using penetrant materials on austenitic
8.9.1.2 Black Light Warm-Up — Unless otherwise stainless steels, titanium, nickel-base or other high-temper-
ature alloys, the need to restrict certain impurities such as
specified by the manufacturer, allow the black light to
sulfur, halogens and alkali metals must be considered.
warm up for a minimum of five minutes prior to use or
These impurities may cause embrittlement or corrosion,
measurement of its intensity.
particularly at elevated temperatures. Any such evaluation
8.9.1.3 Visual Adaptation — Personnel examining should also include consideration of the form in which the
parts after penetrant processing shall be in the darkened impurities are present. Some penetrant materials contain
area for at least one minute before examining parts. Longer significant amounts of these impurities in the form of vola-
times may be necessary under some circumstances. Photo- tile organic solvent that normally evaporate quickly and
chromic or tinted lenses shall not be worn during the pro- usually do not cause problems. Other materials may contain
cessing and examination of parts. impurities, which are not volatile and may react with the
part, particularly in the presence of moisture or elevated
8.9.2 Visible Light Examination— Inspect parts tested
temperatures.
with Type 2 visible penetrant under either natural or artifi-
cial visible light. Proper illumination is required to ensure 9.1.2 Because volatile solvents leave the surface
adequate sensitivity of the examination. A minimum light quickly without reaction under normal examination proce-
intensity at the examination surface of 100 fc (1076 lx) is dures, penetrant materials are normally subjected to an
required. evaporation procedure to remove the solvents before the
materials are analyzed for impurities. The residue from
8.9.3 Housekeeping — Keep the examination area this procedure is then analyzed in accordance with Test
free of interfering debris, including fluorescent residues Method D 1552 or Test Method D 129 decomposition
and objects. followed by Test Method D 516, Method B (Turbidimetric
8.9.4 Indication Verification — For Type 1 inspec- Method) for sulfur. The residue may also be analyzed by
tions only, it is common practice to verify indications by Test Method D 808 or Annex A2 on Methods for Measur-
wiping the indication with a solvent-dampened swab or ing Total Chlorine Content in Combustible Liquid Pene-
brush, allowing the area to dry, and redeveloping the area. trant Materials (for halogens other than fluorine) and Annex
Redevelopment time shall be a minimum of ten minutes, A3 on Method for Measuring Total Fluorine Content in
except nonaqueous redevelopment time should be a mini- Combustible Liquid Penetration Materials (for fluorine).
mum of three minutes. If the indication does not reappear, An alternative procedure, Annex A4 on Determination of
the original indication may be considered false. This proce- Anions by Ion Chromatography, provides a single instru-
dure may be performed up to two times for any given mental technique for rapid sequential measurement of com-
original indication. mon anions such as chloride, fluoride, and sulfate. Alkali
--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---
metals in the residue are determined by flame photometry,

8.9.5 Evaluation — All indications found during atomic absorption spectrophotometry, or ion chromatogra-
inspection shall be evaluated in accordance with acceptance phy (see ASTM D 4327).
criteria as specified. Referenced Photographs of indications
NOTE 15: Some current standards require impurity levels of sulfur and
are noted in E 433.
halogens to not exceed 1% of any one suspect element. This level,
however, may be unacceptable for some applications, so the actual maxi-
8.10 Post Cleaning — Post cleaning is necessary when
mum acceptable impurity level must be decided between supplier and
residual penetrant or developer could interfere with subse- user on a case by case basis.
quent processing or with service requirements. It is particu-
larly important where residual penetrant testing materials 9.2 Elevated-Temperature Testing — Where penetrant
might combine with other factors in service to produce testing is performed on parts that must be maintained at
corrosion and prior to vapor degreasing or heat treating elevated temperature during examination, special penetrant
the part as these processes can bake the developer onto materials and processing techniques may be required. Such
the part. A suitable technique, such as a simple water rinse, examination requires qualification in accordance with 10.2
water spray, machine wash, solvent soak, or ultrasonic and the manufacturer’s recommendations shall be
cleaning may be employed (see Annex A1 for further infor- observed.
mation on post cleaning). It is recommended that if devel-
oper removal is necessary, it should be carried out as 10. Qualification and Requalification
promptly as possible after examination so that the devel- 10.1 Personal Qualification — When required by cus-
oper does not adhere to the part. tomer, all penetrant testing personnel shall be qualified/
571
certified in accordance with a written procedure conform- 10.3 Nondestructive Testing Agency Qualification — If
ing to the applicable edition of recommended Practice a nondestructive testing agency as described in Practice
SNT-TC-1A, ANSI/ASNT CP-189, NAS-410, or E 543 is used to perform the examination, the agency
MIL-STD-410. should meet the requirements of Practice E 543.
10.2 Procedure Qualification — Qualification of proce-
dures using times, conditions, or materials differing from 10.4 Requalification may be required when a change or
those specified in this general practice or for new materials substitution is made in the type of penetrant materials or
may be performed by any of several methods and should in the procedure (see 10.2).
be agreed upon by the contracting parties. A test piece
containing one or more discontinuities of the smallest rele-
vant size is used. When agreed upon by the contracting 11. Keywords
parties, the test piece may contain real or simulated discon-
tinuities, providing it displays the characteristics of the 11.1 fluorescent liquid penetrant testing; hydrophilic
discontinuities encountered in product examination. emulsification; lipophilic emulsification; liquid penetrant
10.2.1 Requalification of the procedure to be used testing; nondestructive testing; solvent removable; visible
may be required when a change is made to the procedure liquid penetrant testing; water-washable; post-emulsified;
or when material substitution is made. black light; ultraviolet light; visible light
572
--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---

ANNEXES
(Mandatory Information)
A1. Cleaning of Parts and Materials A1.1.1.4 Alkaline Cleaning:

(a) Alkaline cleaners are nonflammable water solutions
A1.1 Choice of Cleaning Method
containing specially selected detergents for wetting, pene-
A1.1.1 The choice of a suitable cleaning method is trating, emulsifying, and saponifying various types of soils.
based on such factors as: (1) type of contaminant to be Hot alkaline solutions are also used for rust removal and
removed since no one method removes all contaminants descaling to remove oxide scale which can mask surface
equally well; (2) effect of the cleaning method on the parts; discontinuities. Alkaline cleaner compounds must be used
(3) practicality of the cleaning method for the part (for in accordance with the manufacturers’ recommendations.
example, a large part cannot be put into a small degreaser Parts cleaned by the alkaline cleaning process must be
or ultrasonic cleaner); and (4) specific cleaning require- rinsed completely free of cleaner and thoroughly dried
ments of the purchaser. The following cleaning methods prior to the penetrant inspection process [part temperature
at the time of penetrant application shall not exceed 125°F
are recommended:
(52°C)].
A1.1.1.1 Detergent Cleaning — Detergent clean- (b) Steam cleaning is a modification of the hot-tank
ers are nonflammable water-soluble compounds containing alkaline cleaning method, which can be used for prepara-
specially selected surfactants for wetting, penetrating, tion of large, unwieldy parts. It will remove inorganic soils
emulsifying, and saponifying various types of soils, such and many organic soils from the surface of parts, but may
as grease and oily films, cutting and machining fluids, and not reach to the bottom of deep discontinuities, and a
unpigmented drawing compounds, etc. Detergent cleaners subsequent solvent soak is recommended.
may be alkaline, neutral, or acidic in nature, but must be A1.1.1.5 Ultrasonic Cleaning — This method adds
noncorrosive to the item being inspected. The cleaning ultrasonic agitation to solvent or detergent cleaning to
properties of detergent solutions facilitate complete improve cleaning efficiency and decrease cleaning time. It
removal of soils and contamination from the surface and should be used with water and detergent if the soil to be
void areas, thus preparing them to absorb the penetrant. removed is inorganic (rust, dirt, salts, corrosion products,
Cleaning time should be as recommended by the manufac- etc.), and with organic solvent if the soil to be removed
turer of the cleaning compound. is organic (grease and oily films, etc.). After ultrasonic
cleaning, parts must be rinsed completely free of cleaner,
A1.1.1.2 Solvent Cleaning — There are a variety
thoroughly dried, and cooled to at least 125°F (52°C),
of solvent cleaners that can be effectively utilized to dis- before application of penetrant.
solve such soils as grease and oily films, waxes and seal-
ants, paints, and in general, organic matter. These solvents A1.1.1.6 Paint Removal — Paint films can be
effectively removed by bond release solvent paint remover
--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---
should be residue-free, especially when used as a hand-

wipe solvent or as a dip-tank degreasing solvent. Solvent or disintegrating-type hot-tank alkaline paint strippers. In
cleaners are not recommended for the removal of rust and most cases, the paint film must be completely removed to
scale, welding flux and spatter, and in general, inorganic expose the surface of the metal. Solvent-type paint
soils. Some cleaning solvents are flammable and can be removers can be of the high-viscosity thickened type for
toxic. Observe all manufacturers’ instructions and precau- spray or brush application or can be of low viscosity two-
layer type for dip-tank application. Both types of solvent
tionary notes.
paint removers are generally used at ambient temperatures,
A1.1.1.3 Vapor Degreasing — Vapor degreasing as received. Hot-tank alkaline strippers should be used in
is a preferred method of removing oil or grease-type soils accordance with the manufacturer’s instructions. After
from the surface of parts and from open discontinuities. It paint removal, the parts must be thoroughly rinsed to
will not remove inorganic-type soils (dirt, corrosion, salts, remove all contamination from the void openings, thor-
etc.), and may not remove resinous soils (plastic coatings, oughly dried, and cooled to at least 125°F (52°C) before
varnish, paint, etc.). Because of the short contact time, application of penetrant.
degreasing may not completely clean out deep discontinu- A1.1.1.7 Mechanical Cleaning and Surface Condi-
ities and a subsequent solvent soak is recommended. tioning — Metal-removing processes such as filing,
573
buffing, scraping, mechanical milling, drilling, reaming, A2. Methods for Measuring Total Chlorine Content
grinding, liquid honing, sanding, lathe cutting, tumble or in Combustible Liquid Penetrant Materials
vibratory deburring, and abrasive blasting, including abra- A2.1 Scope and Application
sives such as glass beads, sand, aluminum oxide, ligno-
cellulose pellets, metallic shot, etc., are often used to A2.1.1 These methods cover the determination of
remove such soils as carbon, rust and scale, and foundry chlorine in combustible liquid penetrant materials, liquid
or solid. Its range of applicability is 0.001 to 5% using
adhering sands, as well as to deburr or produce a desired
either of the alternative titrimetric procedures. The proce-
cosmetic effect on the part. These processes may decrease
dures assume that bromine or iodine will not be present.
the effectiveness of the penetrant testing by smearing or
If these elements are present, they will be detected and
peening over metal surfaces and filling discontinuities open
reported as chlorine. The full amount of these elements will
to the surface, especially for soft metals such as aluminum,
not be reported. Chromate interferes with the procedures,
titanium, magnesium, and beryllium alloy.
causing low or nonexistent end points. The method is appli-
A1.1.1.8 Acid Etching — Inhibited acid solutions cable only to materials that are totally combustible.
(pickling solutions) are routinely used for descaling part
A2.2 Summary of Methods
surfaces. Descaling is necessary to remove oxide scale,
which can mask surface discontinuities and prevent pene- A2.2.1 The sample is oxidized by combustion in a
trant from entering. Acid solutions/etchants are also used bomb containing oxygen under pressure (see A2.2.1.1).
routinely to remove smeared metal that peens over surface The chlorine compounds thus liberated are absorbed in a
discontinuities. Such etchants should be used in accordance sodium carbonate solution and the amount of chloride pres-
with the manufacturers’ recommendations. ent is determined titrimetrically either against silver nitrate
with the end point detected potentiometrically (Method A)
NOTE A1.1: Etched parts and materials should be rinsed completely free or coulometrically with the end point detected by current
of etchants, the surface neutralized and thoroughly dried by heat prior flow increase (Method B).
to application of penetrants. Acids and chromates can adversely affect
the fluorescence of fluorescent materials. A2.2.1.1 Safety — Strict adherence to all of the
provisions prescribed hereinafter ensures against explosive
NOTE A1.2 Whenever there is a possibility of hydrogen embrittlement rupture of the bomb, or a blow-out, provided the bomb is
as a result of acid solution/etching, the part should be baked at a suitable of proper design and construction and in good mechanical
temperature for an appropriate time to remove the hydrogen before further condition. It is desirable, however, that the bomb be
processing. After baking, the part shall be cooled to a temperature below
enclosed in a shield of steel plate at least 1⁄2 in. (12.7 mm)
125°F (52°C) before applying penetrants.
thick, or equivalent protection be provided against unfore-
A1.1.1.9 Air Firing of Ceramics — Heating of a seeable contingencies.
ceramic part in a clean, oxidizing atmosphere is an effective
way of removing moisture or light organic soil or both. A2.3 Apparatus
The maximum temperature that will not cause degradation A2.3.1 Bomb, having a capacity of not less than
of the properties of the ceramic should be used. 300 mL, so constructed that it will not leak during the test,
and that quantitative recovery of the liquids from the bomb
A1.2 Post Cleaning may be readily achieved. The inner surface of the bomb
A1.2.1 Removal of Developer — Dry powder devel- may be made of stainless steel or any other material that
oper can be effectively removed with an air blow-off (free will not be affected by the combustion process or products.
of oil) or it can be removed with water rinsing. Wet devel- Materials used in the bomb assembly, such as the head
oper coatings can be removed effectively by water rinsing gasket and leadwire insulation, shall be resistant to heat
or water rinsing with detergent either by hand or with a and chemical action, and shall not undergo any reaction
mechanical assist (scrub brushing, washing machine, etc.). that will affect the chlorine content of the liquid in the
The soluble developer coatings simply dissolve off of the bomb.
part with a water rinse. A2.3.2 Sample Cup, platinum, 24 mm in outside
diameter at the bottom, 27 mm in outside diameter at the
--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---
A1.2.2 Residual penetrant may be removed through

solvent action. Solvent soaking (15 min minimum) and top, 12 mm in height outside and weighing 10 to 11 g,
ultrasonic solvent cleaning (3 min minimum) techniques opaque fused silica, wide-form with an outside diameter
of 29 mm at the top, a height of 19 mm, and a 5-mL
are recommended. In some cases, it is desirable to vapor
capacity (Note A2.1), or nickel (Kawin capsule form), top
degrease, then follow with a solvent soak. The actual time
diameter of 28 mm, 15 mm in height, and 5-mL capacity.
required in the vapor degreaser and solvent soak will
depend on the nature of the part and should be determined NOTE A2.1: Fused silica crucibles are much more economical and longer-
experimentally. lasting than platinum. After each use, they should be scrubbed out with
574
fine, wet emery cloth, heated to dull red heat over a burner, soaked in TABLE A2.1
hot water for 1 h, then dried and stored in a desiccator before reuse. GAGE PRESSURES
A2.3.3 Firing Wire, platinum, approximately No. 26 Gage Pressure, atm (MPa)
B & S gage. Capacity of Bomb, mL minA max
A2.3.4 Ignition Circuit (Note A2.2), capable of sup-
300 to 350 38 (3.85) 40 (4.05)
plying sufficient current to ignite the nylon thread or cotton 350 to 400 35 (3.55) 37 (3.75)
wicking without melting the wire. 400 to 450 30 (3.04) 32 (3.24)
450 to 500 27 (2.74) 29 (2.94)
NOTE A2.2: The switch in the ignition circuit shall be of a type that
A
remains open, except when held in closed position by the operator. The minimum pressures are specified to provide sufficient oxygen
for complete combustion and the maximum pressures present a
A2.3.5 Nylon Sewing Thread, or Cotton Wicking, safety requirement.
white.
A2.4 Purity of Reagents add it to the sample cup by means of a dropper at this time
A2.4.1 Reagent grade chemicals shall be used in all (see Note A2.5 and Note A2.6).
tests. Unless otherwise indicated, it is intended that all
NOTE A2.3: After repeated use of the bomb for chlorine determination,
reagents shall conform to the specifications of the Commit- a film may be noticed on the inner surface. This dullness should be
tee on Analytical Reagents of the American Chemical Soci- removed by periodic polishing of the bomb. A satisfactory method for
ety, where such specifications are available. Other grades doing this is to rotate the bomb in a lathe at about 300 rpm and polish
may be used provided it is first ascertained that the reagent the inside surface with Grit No. 2/0 or equivalent paper coated with a
is of sufficiently high purity to permit its use without less- light machine oil to prevent cutting, and then with a paste of grit-free
chromic oxide and water. This procedure will remove all but very deep
ening the accuracy of the determination. pits and put a high polish on the surface. Before using the bomb, it should
A2.4.2 Unless otherwise indicated, references to be washed with soap and water to remove oil or paste left from the
water shall be understood to mean referee grade reagent polishing operation. Bombs with porous or pitted surfaces should never
be used because of the tendency to retain chlorine from sample to sample.
water conforming to Specification D 1193. It is recommended to not use more than 1 g total of sample and white
A2.5 Decomposition oil or other chlorine-free combustible material.
A2.5.1 Reagents and Materials: NOTE A2.4: If the sample is not readily miscible with white oil, some
other nonvolatile, chlorine-free combustible diluent may be employed in
A2.5.1.1 Oxygen, free of combustible material and
place of white oil. However, the combined weight of sample and nonvola-
halogen compounds, available at a pressure of 40 atm tile diluent shall not exceed 1 g. Some solid additives are relatively
(4.05 MPa). insoluble, but may be satisfactorily burned when covered with a layer
of white oil.
A2.5.1.2 Sodium Carbonate Solution (50 g
Na2CO3/L) — Dissolve 50 g of anhydrous Na2CO3 or 58.5 g NOTE A2.5: The practice of running alternately samples high and low
of Na2CO3 · H2O) or 135 g of Na2CO3 · 10H2O in water in chlorine content should be avoided whenever possible. It is difficult
and dilute to 1 L. to rinse the last traces of chlorine from the walls of the bomb and the
tendency for residual chlorine to carry over from sample to sample has
A2.5.1.3 White Oil, refined. been observed in a number of laboratories. When a sample high in chlorine
has preceded one low in chlorine content, the test on the low-chlorine
A2.5.2 Procedure:
sample should be repeated and one or both of the low values thus obtained
A2.5.2.1 Preparation of Bomb and Sample — Cut should be considered suspect if they do not agree within the limits of
a piece of firing wire approximately 100 mm in length. repeatability of this method.
Coil the middle section (about 20 mm) and attach the free A2.5.2.2 Addition of Oxygen — Place the sample
ends to the terminals. Arrange the coil so that it will be cup in position and arrange the nylon thread, or wisp of
above and to one side of the sample cup. Place 5 mL of cotton so that the end dips into the sample. Assemble the
Na2CO3 solution in the bomb (Note A2.3), place the cover bomb and tighten the cover securely. Admit oxygen (see
on the bomb and vigorously shake for 15 s to distribute Note A2.6) slowly (to avoid blowing the sample from the
the solution over the inside of the bomb. Open the bomb, cup) until a pressure is reached as indicated in Table A2.1.
place the sample-filled sample cup in the terminal holder,
and insert a short length of thread between the firing wire Note A2.6: It is recommended to not add oxygen or ignite the sample if
and the sample. Use of a sample weight containing over the bomb has been jarred, dropped, or tilted.
20 mg of chlorine may cause corrosion of the bomb. The A2.5.2.3 Combustion — Immerse the bomb in a
sample weight should not exceed 0.4 g if the expected cold-water bath. Connect the terminals to the open electri-
chlorine content is 2.5% or above. If the sample is solid, cal circuit. Close the circuit to ignite the sample. Remove
not more than 0.2 g should be used. Use 0.8 g of white the bomb from the bath after immersion for at least ten
oil with solid samples. If white oil will be used (Note A2.4), minutes. Release the pressure at a slow, uniform rate such
575
--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---

that the operation requires not less than 1 min. Open the amount of difference between the present reading and the
bomb and examine the contents. If traces of unburned oil last reading. Continue adding 0.1-mL increments, making
or sooty deposits are found, discard the determination, and readings and determining differences between readings
thoroughly clean the bomb before again putting it in use until a maximum difference between readings is obtained.
(Note A2.3). The total amount of AgNO3 solution required to produce
this maximum differential is the end point. Automatic titra-
A2.6 Analysis, Method A, Potentiometric Titration
tors continuously stir the sample, add titrant, measure the
Procedure
potential difference, calculate the differential, and plot the
A2.6.1 Apparatus:
differential on a chart. The maximum differential is taken
A2.6.1.1 Silver Billet Electrode. at the end point.
A2.6.1.2 Glass Electrode, pH measurement type.
NOTE A2.8: For maximum sensitivity, 0.00282 N AgNO3 solution may
A2.6.1.3 Buret, 25-mL capacity, 0.05-mL gradua- be used with the automatic titrator. This dilute reagent should not be
tions. used with large samples or where chlorine content may be over 0.1%
since these tests will cause end points of 10 mL or higher. The large
A2.6.1.4 Millivolt Meter, or expanded scale pH amount of water used in such titrations reduces the differential between
meter capable of measuring 0 to 220 mV. readings, making the end point very difficult to detect. For chlorine
contents over 1% in samples of 0.8 g or larger, 0.282 N AgNO3 solution
NOTE A2.7: An automatic titrator is highly recommended in place of will be required to avoid exceeding the 10-mL water dilution limit.
items A2.6.1.3 through A2.6.1.4. Repeatability and sensitivity of the
method are much enhanced by the automatic equipment while much A2.6.5 Blank — Make blank determinations with the
tedious effort is avoided. amount of white oil used but omitting the sample. (Liquid
A2.6.2 Reagents and Materials: samples normally require only 0.15 to 0.25 g of white oil
A2.6.2.1 Acetone, chlorine-free. while solids require 0.7 to 0.8 g.) Follow normal procedure,
making two or three test runs to be sure the results are
A2.6.2.2 Methanol, chlorine-free. within the limits of repeatability for the test. Repeat this
A2.6.2.3 Silver Nitrate Solution (0.0282 N) — Dis- blank procedure whenever new batches of reagents or white
solve 4.7910 ± 0.0005 g of silver nitrate (AgNO3) in water oil are used. The purpose of the blank run is to measure
and dilute to 1 L. the chlorine in the white oil, the reagents, and that intro-
A2.6.2.4 Sodium Chloride Solution (0.0282 N) — duced by contamination.
Dry a few grams of sodium chloride (NaCl) for 2 h at A2.6.6 Standardization — Silver nitrate solutions are
130°C to 150°C, weigh out 1.6480 ± 0.0005 g of the dried not permanently stable, so the true activity should be
NaCl, dissolve in water, and dilute to 1 L. checked when the solution is first made up and then periodi-
A2.6.2.5 Sulfuric Acid (1 + 2) — Mix 1 volume cally during the life of the solution. This is done by titration
of concentrated sulfuric acid (H2SO4, sp. gr 1.84) with 2 of a known NaCl solution as follows: Prepare a mixture
volumes of water. of the amounts of the chemicals (Na2CO3 solution, H2SO4
solution, acetone, and methanol) specified for the test. Pipet
A2.6.3 Collection of Chlorine Solution — Remove
in 5.0 mL of 0.0282-N NaCl solution and titrate to the
the sample cup with clean forceps and place in a 400-mL
end point. Prepare and titrate a similar mixture of all the
beaker. Wash down the walls of the bomb shell with a
chemicals except the NaCl solution, thus obtaining a
fine stream of methanol from a wash bottle, and pour the
reagent blank reading. Calculate the normality of the
washings into the beaker. Rinse any residue into the beaker.
AgNO3 solution as follows:
Next, rinse the bomb cover and terminals into the beaker.
Finally, rinse both inside and outside of the sample crucible 5.0 ⴛ NNaCl
NAgNO3 p (A2.1)
into the beaker. Washings should equal but not exceed VA − VB
100 mL. Add methanol to make 100 mL. where:
A2.6.4 Determination of Chlorine — Add 5 mL of NAgNO3 p normality of the AgNO3 solution,
H2SO4 (1:2) to acidify the solution (solution should be NNaCl p normality of the NaCl solution,
acid to litmus and clear of white Na2CO3 precipitate). Add VA p millilitres of AgNO3 solution used for the titra-
100 mL of acetone. Place the electrodes in the solution, tion including the NaCl solution, and
start the stirrer (if mechanical stirrer is to be used), and VB p millilitres of AgNO3 solution used for the titra-
begin titration. If titration is manual, set the pH meter on tion of the reagents only.
the expanded millivolt scale and note the reading. Add
A2.6.7 Calculation — Calculate the chlorine content
exactly 0.1 mL of AgNO3 solution from the buret. Allow a
of the sample as follows:
few seconds stirring; then record the new millivolt reading.
Subtract the second reading from the first. Continue the (VS − VB) ⴛ N ⴛ 3.545
Chlorine, weight % p (A2.2)
titration, noting each amount of AgNO3 solution and the W
--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---
576
where: A2.7.3.3 Glacial Acetic Acid-Nitric Acid Solu-

VS p millilitres of AgNO3 solution used by the sample, tion — A typical ratio is 12.5 to 1 (12.5 parts CH3COOH
VB p millilitres of AgNO3 solution used by the blank, to 1 part HNO3).
N p normality of the AgNO3 solution, and A2.7.3.4 Mix enough gelatin solution and of acetic
W p grams of sample used. acid-nitric acid mixture for one titration. (A typical mixture
A2.6.8 Precision and Accuracy: is 2.5 mL of gelatin solution and 5.4 mL of acetic-nitric
A2.6.8.1 The following criteria should be used for acid mixture.)
judging the acceptability of results: NOTE A2.10: The solution may be premixed in a larger quantity for
A2.6.8.1.1 Repeatability — Results by the same convenience, but may not be useable after 24 h.
analyst should not be considered suspect unless they differ A2.7.3.5 Run at least three blank values and take
by more than 0.006% or 10.5% of the value determined, an average according to the operating manual of the titrator.
whichever is higher. Determine separate blanks for both 5 drops of mineral oil
A2.6.8.1.2 Reproducibility — Results by different and 20 drops of mineral oil.
laboratories should not be considered suspect unless they A2.7.4 Titration:
differ by more than 0.013% or 21.3% of the value detected,
A2.7.4.1 Weigh to the nearest 0.1 g and record
whichever is higher.
the weight of the 100-mL beaker.
A2.6.8.1.3 Accuracy — The average recovery of
A2.7.4.2 Remove the sample crucible from the
the method is 86% to 89% of the actual amount present.
cover assembly support ring using a clean forceps, and,
A2.7 Analysis, Method B, Coulometric Titration using a wash bottle, rinse both the inside and the outside
A2.7.1 Apparatus: with water into the 100-mL beaker.
A2.7.1.1 Coulometric Chloride Titrator. A2.7.4.3 Empty the bomb shell into the 100-mL
A2.7.1.2 Beakers, two, 100-mL, or glazed cruci- beaker. Wash down the sides of the bomb shell with water,
bles (preferably with 11⁄2 in.-outside diameter bottom). using a wash bottle.
A2.7.1.3 Refrigerator. A2.7.4.4 Remove the cover assembly from the
A2.7.2 Reagents: cover assembly support, and, using the wash bottle, rinse
the under side, the platinum wire, and the terminals into
A2.7.2.1 Acetic Acid, Glacial. the same 100-mL beaker. The total amount of washings
A2.7.2.2 Dry Gelatin Mixture. should be 50 ± 1 g.
A2.7.2.3 Nitric Acid. A2.7.4.5 Add specified amounts of gelatin mixture
A2.7.2.4 Sodium Chloride Solution — 100 meq and acetic acid-nitric acid mixture, or gelatin mix-acetic
C/1. Dry a quantity of NaCl for 2 h at 130°C to 150°C. acid-nitric acid mixture, if this was premixed, into the
Weigh out 5.8440 ± 0.0005 g of dried NaCl in a closed 100-mL beaker that contains the 50 g of washings including
container, dissolve in water, and dilute to 1 L. the decomposed sample.
A2.7.3 Reagent Preparation: A2.7.4.6 Titrate using a coulometric titrimeter,
NOTE A2.9: The normal reagent preparation process has been slightly
according to operating manual procedure.
changed, due to the interference from the 50 mL of water required to A2.7.5 Calculations — Calculate the chloride ion
wash the bomb. This modified process eliminates the interference and
does not alter the quality of the titration.
concentration in the sample as follows:
A2.7.3.1 Gelatin Solution — A typical preparation (P − B) ⴛ M

Chlorine, weight % p (A2.3)
is: Add approximately 1 L or hot distilled or deionized W
water to the 6.2 g of dry gelatin mixture contained in one
vial supplied by the equipment manufacturer. Gently heat where:
with continuous mixing until the gelatin is completely dis- P p counter reading obtained with the sample,
solved. B p average counter reading obtained with average of
A2.7.3.2 Divide into aliquots each sufficient for the three blank readings,
one day’s analyses. (Thirty millilitres is enough for approx- M p standardization constant. This is dependent on the
imately eleven titrations.) Keep the remainder in a refriger- instrument range setting in use and the reading
ator, but do not freeze. The solution will keep for about obtained with a known amount of the 100 meq
six months in the refrigerator. When ready to use, immerse of Cl per litre of solution, and
the day’s aliquot in hot water to liquefy the gelatin. W p weight of sample used, g.
--`,,,`,`,``,``,,`,``,`,`,`,``,
577
A2.7.6 Precision and Accuracy: A3.4 Apparatus

A2.7.6.1 Duplicate results by the same operator A3.4.1 Bomb, having a capacity of not less than 300
can be expected to exhibit the following relative standard mL, so constructed that it will not leak during the test, and
deviations: that quantitative recovery of the liquids from the bomb
may be readily achieved. The inner surface of the bomb
Approximate % Chlorine RSD, %
1.0 and above 0.10 may be made of stainless steel or any other material that
0.1 2.5 will not be affected by the combustion process or products.
0.003 5.9 Materials used in the bomb assembly, such as the head
gasket and leadwire insulation, shall be resistant to heat
A2.7.6.2 The method can be expected to report and chemical action, and shall not undergo any reaction
values that vary from the true value by the following that will affect the fluorine content of the liquid in the
amounts: bomb.
0.1% chlorine and above ±2% A3.4.2 Sample Cup, nickel, 20 mm in outside diame-
0.001 to 0.01% chlorine ±9%. ter at the bottom, 28 mm in outside diameter at the top,
and 16 mm in height; or platinum, 24 mm in outside
A2.7.6.3 If bromine is present, 36.5% of the true diameter at the bottom, 27 mm in outside diameter at the
amount will be reported. If iodine is present, 20.7% of the top, 12 mm in height, and weighing 10 to 11 g.
true amount will be reported. Fluorine will not be detected.
A3.4.3 Firing Wire, platinum, approximately No. 26
B & S gage.
A3. Method for Measuring Total Fluorine Content A3.4.4 Ignition Circuit (Note A3.1), capable of sup-
in Combustible Liquid Penetrant Materials plying sufficient current to ignite the nylon thread or cotton
A3.1 Scope and Application wicking without melting the wire.
A3.1.1 This method covers the determination of flu- NOTE A3.1: Caution — The switch in the ignition circuit shall be of
orine in combustible liquid penetrant materials, liquid or a type that remains open, except when held in closed position by the
solid, that do not contain appreciable amounts of interfering operator.
elements, or have any insoluble residue after combustion. A3.4.5 Nylon Sewing Thread, or Cotton Wicking,
Its range of applicability is 1 to 200 000 ppm. white.
A3.1.2 The measure of the fluorine content employs A3.4.6 Funnel, polypropylene (Note A3.2).
the fluoride selective ion electrode. A3.4.7 Volumetric Flask, polypropylene, 100-mL
(Note A3.2).
A3.2 Summary of Method
A3.4.8 Beaker, polypropylene, 150-mL (Note A3.2).
A3.2.1 The sample is oxidized by combustion in a
bomb containing oxygen under pressure (see A3.2.1.1). A3.4.9 Pipet, 100-␮L, Eppendorf-type (Note A3.2).
The fluorine compounds thus liberated are absorbed in a A3.4.10 Magnetic Stirrer and TFE-coated magnetic
sodium citrate solution and the amount of fluorine present is stirring bar.
determined potentiometrically through the use of a fluoride A3.4.11 Fluoride Specific Ion Electrode and suitable
selective ion electrode. reference electrode.
A3.2.1.1 Safety — Strict adherence to all of the A3.4.12 Millivolt Meter capable of measuring to
provisions prescribed hereinafter ensures against explosive 0.1 mV.
rupture of the bomb, or a blow-out, provided the bomb is
NOTE A3.2: Glassware should never be used to handle a fluoride solution
of proper design and construction and in good mechanical
as it will remove fluoride ions from solution or on subsequent use carry
condition. It is desirable, however, that the bomb be fluoride ion from a concentrated solution to one more dilute.
enclosed in a shield of steel plate at least 1⁄2 in. (12.7 mm)
thick, or equivalent protection be provided against unfore- A3.5 Reagents
seeable contingencies. A3.5.1 Purity of Reagents — Reagent grade chemi-
cals shall be used in all tests. Unless otherwise indicated,
A3.3 Interferences it is intended that all reagents shall conform to the specifi-
A3.3.1 Silicon, calcium, aluminum, magnesium, and cations of the Committee on Analytical Reagents of the
other metals forming precipitates with fluoride ion will American Chemical Society, where such specifications are
interfere if they are present in sufficient concentration to available. Other grades may be used, provided it is first
exceed the solubility of their respective fluorides. Insoluble ascertained that the reagent is of sufficiently high purity
residue after combustion will entrain fluorine even if other- to permit its use without lessening the accuracy of the
wise soluble. determination.
--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,
578
A3.5.2 Purity of Water — Unless otherwise indicated, TABLE A3.1

all references to water shall be understood to mean Type I GAGE PRESSURES
reagent water conforming to Specification D 1193. Gage Pressure, atm
A3.5.3 Fluoride Solution, Stock (2000 ppm) — Dis- (MPa)
solve 4.4200 ± 0.0005 g of predried (at 130°C to 150°C Capacity of Bomb, mL minA max
for 1 h, then cooled in a desiccator) sodium fluoride in 300 to 350 38 40
distilled water and dilute to 1 L. 350 to 400 35 37
A3.5.4 Oxygen, free of combustible material and 400 to 450 30 32
450 to 500 27 29
halogen compounds, available at a pressure of 40 atm
A
(4.05 MPa). The minimum pressures are specified to provide sufficient oxygen
A3.5.5 Sodium Citrate Solution — Dissolve 27 g of safety requirement.
sodium citrate dihydrate in water and dilute to 1 L.
A3.5.6 Sodium Hydroxide Solution (5 N) — Dissolve
200 g of sodium hydroxide (NaOH) pellets in water and so that the end dips into the sample. Assemble the bomb and
dilute to 1 L; store in a polyethylene container. tighten the cover securely. Admit oxygen (see Note A3.4)
A3.5.7 Wash Solution (Modified TISAB, Total Ionic slowly (to avoid blowing the sample from the cup) until
--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---
Strength Adjustment Buffer) — To 300 mL of distilled a pressure is reached as indicated in Table A3.1.
water, add 32 mL of glacial acetic acid, 6.6 g of sodium
NOTE A3.4: Caution — It is recommended to not add oxygen or ignite
citrate dihydrate, and 32.15 g of sodium chloride. Stir to the sample if the bomb has been jarred, dropped, or tilted.
dissolve and then adjust the pH to 5.3 using 5 N NaOH
solution. Cool and dilute to 1 L. A3.6.3 Combustion — Immerse the bomb in a cold-
water bath. Connect the terminals to the open electrical
A3.5.8 White Oil, refined. circuit. Close the circuit to ignite the sample. Remove the
A3.6 Decomposition Procedure bomb from the bath after immersion for at least 10 min.
A3.6.1 Preparation of Bomb and Sample — Cut a Release the pressure at a slow, uniform rate such that the
piece of firing wire approximately 100 mm in length. Coil operation requires not less than 1 min. Open the bomb and
the middle section (about 20 mm) and attach the free ends examine the contents. If traces of unburned oil or sooty
to the terminals. Arrange the coil so that it will be above deposits are found, discard the determination, and thor-
and to one side of the sample cup. Place 10 mL of sodium oughly clean the bomb before again putting it in use.
citrate solution in the bomb, place the cover on the bomb, A3.6.4 Collection of Fluorine Solution — Remove
and vigorously shake for 15 s to distribute the solution the sample cup with clean forceps and rinse with wash
over the inside of the bomb. Open the bomb, place the solution into a 100-mL volumetric flask. Rinse the walls
sample-filled sample cup in the terminal holder, and insert of the bomb shell with a fine stream of wash solution from
a short length of thread between the firing wire and the a wash bottle, and add the washings to the flask. Next,
sample. The sample weight used should not exceed 1 g. rinse the bomb cover and terminals into the volumetric
If the sample is a solid, add a few drops of white oil at flask. Finally, add wash solution to bring the contents of
this time to ensure ignition of the sample. the flask to the line.
NOTE A3.3: Use of sample weights containing over 20 mg of chlorine A3.7 Procedure
may cause corrosion of the bomb. To avoid this it is recommended that
A3.7.1 Ascertain the slope (millivolts per ten-fold
the following table: change in concentration) of the electrode as described by
Sample the manufacturer.
Chlorine Weight, White Oil
A3.7.2 Obtain a blank solution by performing the
Content, % g Weight, g
procedure without a sample.
2 to 5 0.4 0.4
5 to 10 0.2 0.6 A3.7.3 Immerse the fluoride and reference electrodes
10 to 20 0.1 0.7 in solutions and obtain the equilibrium reading to 0.1 mV.
20 to 50 0.05 0.7 (The condition of the electrode determines the length of
time necessary to reach equilibrium. This may be as little
Do not use more than 1 g total of sample and white oil or as 5 min or as much as 20 min.)
other fluorine-free combustible material. A3.7.4 Add 100 ␮L of stock fluoride solution and
A3.6.2 Addition of Oxygen — Place the sample cup obtain the reading after the same length of time necessary
in position and arrange the nylon thread, or wisp of cotton for A3.7.3.
579
A3.8 Calculation are separated on the basis of their relative affinities for a
A3.8.1 Calculate the fluorine content of the sample low capacity, strongly basic anion exchanger (guard and
as follows: separator column). The separated anions are directed onto
a strongly acidic cation exchanger (suppressor column)
2 ⴛ 10−4 2 ⴛ 10−4 where they are converted to their highly conductive acid
Fluorine, ppm p
冤 10⌬E /S − 1 10⌬E /S − 1冥
−
1
ⴛ 10
2 6
(A3.1) form and the carbonate-bicarbonate eluant is converted to
W weakly conductive carbonic acid. The separated anions in
their acid form are measured by conductivity. They are
where: identified on the basis of retention time as compared to
⌬E1 p millivolt change in sample solution on addition standards. Quantitation is by measurement of peak area or
of 100 ␮L of stock fluoride solution, peak height. Blanks are prepared and analyzed in a similar
⌬E2 p millivolt change in blank solution on addition of fashion.
100 ␮L of the stock fluoride solution, A4.2.2 Interferences — Any substance that has a
S p slope of fluoride electrode as determined in retention time coinciding with that of any anion to be
A3.7.1, and determined will interfere. For example, relatively high con-
W p grams of sample. centrations of low-molecular-weight organic acids interfere
A3.9 Precision and Bias with the determination of chloride and fluoride. A high
A3.9.1 Repeatability — The results of two determina- concentration of any one ion also interferes with the resolu-
tions by the same analyst should not be considered suspect tion of others. Sample dilution overcomes many interfer-
unless they differ by more than 1.1 ppm (0.00011%) or ences. To resolve uncertainties of identification or
8.0% of the amount detected, whichever is greater. quantitation use the method of known additions. Spurious
peaks may result from contaminants in reagent water, glass-
A3.9.2 Reproducibility — The results of two determi-
ware, or sample processing apparatus. Because small sam-
nations by different laboratories should not be considered
ple volumes are used, scrupulously avoid contamination.
suspect unless they differ by 6.7 ppm or 129.0% of the
amount detected, whichever is greater. A4.2.3 Minimum Detectable Concentration — The
minimum detectable concentration of an anion is a function
A3.9.3 Bias — The average recovery of the method
of sample size and conductivity scale used. Generally,
is 62% to 64% of the amount actually present although 83%
minimum detectable concentrations are in the range of
to 85% recoveries can be expected with proper technique.
0.05 mg/L for F− and 0.1 mg/L for Br−, Cl−, NO3−, NO2−,
PO43−, and SO42− with a 100-␮L sample loop and a 10-
A4. Determination of Anions by Ion ␮mho full-scale setting on the conductivity detector. Simi-
Chromatography With Conductivity lar values may be achieved by using a higher scale setting
Measurement and an electronic integrator.
A4.1 Scope and Application
A4.3 Apparatus
A4.1.1 This method is condensed from ASTM proce-
A4.3.1 Bomb, having a capacity of not less than
dures and APHA Method 429 and optimized for the analy-
300 mL, so constructed that it will not leak during the test,
sis of detrimental substances in organic based materials.
and that quantitative recovery of the liquids from the bomb
It provides a single instrumental technique for rapid,
may be readily achieved. The inner surface of the bomb
sequential measurement of common anions such as bro-
may be made of stainless steel or any other material that
mide, chloride, fluoride, nitrate, nitrite, phosphate, and
will not be affected by the combustion process or products.
sulfate.
A4.2 Summary of Method gasket and leadwire insulation, shall be resistant to heat
A4.2.1 The material must be put in the form of an and chemical action, and shall not undergo any reaction
aqueous solution before analysis can be attempted. The that will affect the chlorine content of the liquid in the
sample is oxidized by combustion in a bomb containing bomb.
oxygen under pressure. The products liberated are absorbed A4.3.2 Sample Cup, platinum, 24 mm in outside
in the eluant present in the bomb at the time of ignition. diameter at the bottom, 27 mm in outside diameter at the
This solution is washed from the bomb, filtered, and diluted top, 12 mm in height outside, and weighing 10 to 11 g;
to a known volume. opaque fused silica, wide-form with an outside diameter
A4.2.1.1 A filtered aliquot of sample is injected of 29 mm at the top, a height of 19 mm, and a 5-mL
into a stream of carbonate-bicarbonate eluant and passed capacity (Note A4.1), or nickel (Kawin capsule form), top
through a series of ion exchangers. The anions of interest diameter of 28 mm, 15 mm in height, and 5-mL capacity.
--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---
580
NOTE A4.1: Fused silica crucibles are much more economical and longer A4.4.4 Regenerant Solution 1, H2SO4, 1 N, use this
lasting than platinum. After each use, they should be scrubbed out with regenerant when suppressor is not a continuously regener-
fine, wet emery cloth, heated to dull red heat over a burner, soaked in
hot water for 1 h then dried and stored in a desiccator before reuse.
ated one.
A4.3.3 Firing Wire, platinum, approximately No. 26 A4.4.5 Regenerant Solution 2, H2SO4, 0.025 N, dilute
B and S gage. 2.8 mL conc H2SO4 to 4 L or 100 mL regenerant solution
1 to 4 L. Use this regenerant with continuous regeneration
A4.3.4 Ignition Circuit (Note A4.2), capable of sup- fiber suppressor system.
plying sufficient current to ignite the nylon thread or cotton
wicking without melting the wire. A4.4.6 Standard Anion Solutions, 100 mg/L, prepare
a series of standard anion solutions by weighing the indi-
NOTE A4.2: The switch in the ignition circuit shall be of a type that cated amount of salt, dried to a constant weight at 105°C,
remains open, except when held in closed position by the operator. to 1000 mL. Store in plastic bottles in a refrigerator; these
A4.3.5 Nylon Sewing Thread, or Cotton Wicking, solutions are stable for at least one month.
white. Amount,
Anion Salt g/L
A4.3.6 Ion Chromatograph, including an injection
valve, a sample loop, guard, separator, and suppressor col- Cl− NaCl 1.6485
F− NaF 2.2100
umns, a temperature-compensated small-volume conduc- Br− NaBr 1.2876
tivity cell (6 ␮L or less), and a strip chart recorder capable NO3− NaNO3 1.3707
of full-scale response of 2 s or less. An electronic peak NO2− NaNO2 1.4998
integrator is optional. The ion chromatograph shall be capa- PO43− KH2PO4 1.4330
ble of delivering 2 to 5 mL eluant/min at a pressure of SO42− K2SO4 1.8141
1400 to 6900 kPa. A4.4.7 Combined Working Standard Solution, High
A4.3.7 Anion Separator Column, with styrene Range — Combine 10 mL of the Cl−, F−, NO3−, NO2−, and
divinyl-benzene-based low-capacity pellicular PO43− standard anion solutions, 1 mL of the Br−, and 100
anion-exchange resin capable of resolving Br−, Cl−, F−, mL of the SO42− standard solutions, dilute to 1000 mL,
NO3−, NO2−, PO43−, and SO42−; 4 ⴛ 250 mm. and store in a plastic bottle protected from light; contains
A4.3.8 Guard Column, identical to separator column 10 mg/L each of Cl−, F−, NO3−, NO2−, and PO43−, 1 mg
except 4 ⴛ 50 mm, to protect separator column from Br−/L, and 100 mg SO42−/L. Prepare fresh daily.
fouling by particulates or organics. A4.4.8 Combined Working Standard Solution, Low
A4.3.9 Suppressor Column, high-capacity cation- Range — Dilute 100 mL combined working standard solu-
exchange resin capable of converting eluant and separated tion, high range, to 1000 mL and store in a plastic bottle
anions to their acid forms. protected from light; contains 1.0 mg/L each Cl−, F−, NO3−,
NO2−, and PO43−, 0.1 mg Br−/L, and 10 mg SO42−/L. Pre-
A4.3.10 Syringe, minimum capacity of 2 mL and pare fresh daily.
equipped with a male pressure fitting.
A4.4.9 Alternative Combined Working Standard
A4.4 Reagents Solutions — Prepare appropriate combinations according
A4.4.1 Purity of Reagents — Reagent grade chemi- to anion concentration to be determined. If NO2− and PO43−
cals shall be used in all tests. Unless otherwise indicated, are not included, the combined working standard is stable
it is intended that all reagents shall conform to the specifi- for one month.
--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---
cations of the Committee on Analytical Reagents of the
A4.5 Decomposition Procedure
American Chemical Society, where such specifications are
available. Other grades may be used provided it is first A4.5.1 Preparation of Bomb and Sample — Cut a
ascertained that the reagent has sufficiently high purity piece of firing wire approximately 100 mm in length. Coil
to permit its use without lessening the accuracy of the the middle section (about 20 mm) and attach the free ends
determination. to the terminals. Arrange the coil so that it will be above
and to one side of the sample cup. Place 5 mL of Na2CO3/
A4.4.2 Deionized or Distilled Water, free from inter- NaHCO3 solution in the bomb, place the cover on the bomb,
ferences at the minimum detection limit of each constituent and vigorously shake for 15 s to distribute the solution over
and filtered through a 0.2-␮m membrane filter to avoid the inside of the bomb. Open the bomb, place the sample-
plugging columns. filled sample cup in the terminal holder, and insert a short
A4.4.3 Eluant Solution, sodium bicarbonate-sodium length of thread between the firing wire and the sample.
carbonate, 0.003M NaHCO3− 0.0024M Na2CO3: dissolve The sample weight used should not exceed 1 g. If the
1.008 g NaHCO3 and 1.0176 g Na2CO3 in water and dilute sample is a solid, add a few drops of white oil at this time
to 4 L. to ensure ignition of the sample.
581
TABLE A4.1 FIG. A4.1 TYPICAL ANION PROFILE

GAGE PRESSURES
Gage Pressures, atm
Capacity of Bomb, mL minA max
300 to 350 38 40
--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---
350 to 400 35 37
400 to 450 30 32
450 to 500 27 29
A
The minimum pressures are specified to provide sufficient oxygen
safety requirement.
NOTE A4.3: Use of sample weights containing over 20 mg of chlorine

may cause corrosion of the bomb. To avoid this it is recommended that
the following:
Chlorine Sample
Content, Weight, White Oil
% g Weight, g A4.6 Procedure
2 to 5 0.4 0.4 A4.6.1 System Equilibration — Turn on ion chroma-
5 to 10 0.2 0.6 tograph and adjust eluant flow rate to approximate the
10 to 20 0.1 0.7 separation achieved in Fig. A4.1 (2 to 3 mL/min). Adjust
20 to 50 0.05 0.7 detector to desired setting (usually 10 ␮mho) and let system
CAUTION: Do not use more than 1 g total of sample and white oil come to equilibrium (15 to 20 min). A stable base line
or other fluorine-free combustible material. indicates equilibrium conditions. Adjust detector offset to
zero-out eluant conductivity; with the fiber suppressor
A4.5.2 Addition of Oxygen — Place the sample cup adjust the regeneration flow rate to maintain stability, usu-
in position and arrange the nylon thread, or wisp of cotton ally 2.5 to 3 mL/min.
so that the end dips into the sample. Assemble the bomb and
tighten the cover securely. Admit oxygen (see Note A4.4) A4.6.1.1 Set up the ion chromatograph in accor-
slowly (to avoid blowing the sample from the cup) until dance with the manufacturer’s instructions.
a pressure is reached as indicated in Table A4.1. A4.6.2 Calibration — Inject standards containing a
single anion or a mixture and determine approximate reten-
NOTE A4.4: It is recommended to not add oxygen or ignite the sample
if the bomb has been jarred, dropped, or tilted. tion times. Observed times vary with conditions but if
standard eluant and anion separator column are used, reten-
A4.5.3 Combustion — Immerse the bomb in a cold- tion always in the order F−, Cl−, NO2−, PO43−, Br−, NO3−,
water bath. Connect the terminals to the open electrical and SO42−. Inject at least three different concentrations for
circuit. Close the circuit to ignite the sample. Remove the each anion to be measured and construct a calibration curve
bomb from the bath after immersion for at least 10 min. by plotting peak height or area against concentration on
Release the pressure at a slow, uniform rate such that the linear graph paper. Recalibrate whenever the detector set-
operation requires not less than 1 min. Open the bomb and ting is changed. With a system requiring suppressor regen-
examine the contents. If traces of unburned oil or sooty eration, NO2− interaction with the suppressor may lead to
deposits are found, discard the determination, and thor- erroneous NO2− results; make this determination only when
oughly clean the bomb before again putting it in use. the suppressor is at the same stage of exhaustion as during
A4.5.4 Collection of Solution — Remove the sample standardization or recalibrate frequently. In this type of
cup with clean forceps and rinse with deionized water and system the water dip (see Note A4.4) may shift slightly
filter the washings into a 100-mL volumetric flask. Rinse during suppressor exhaustion and with a fast run column
the walls of the bomb shell with a fine stream of deionized this may lead to slight interference for F− or Cl−. To elimi-
water from a wash bottle, and add the washings through nate this interference, analyze standards that bracket the
the filter paper to the flask. Next, rinse the bomb cover expected result or eliminate the water dip by diluting the
and terminals and add the washings through the filter into sample with eluant or by adding concentrated eluant to the
the volumetric flask. Finally, add deionized water to bring sample to give the same HCO3−/CO32− concentration as in
the contents of the flask to the line. Use aliquots of this the eluant. If sample adjustments are made, adjust standards
solution for the ion chromatography (IC) analysis. and blanks identically.
582
NOTE A4.5: Water dip occurs because water conductivity in sample is TABLE A4.2
less than eluant conductivity (eluant is diluted by water). PRECISION AND ACCURACY OBSERVED FOR ANIONS
A4.6.2.1 If linearity is established for a given AT VARIOUS CONCENTRATION LEVELS IN REAGENT
detector setting, it is acceptable to calibrate with a single WATER
standard. Record the peak height or area and retention time Single-
to permit calculation of the calibration factor, F. Amount Amount Overall Operator Significant
Added, Found, Precision, Precision, Bias 95%
A4.6.3 Sample Analysis — Remove sample particu- Anion mg/L mg/L mg/L mg/L Level
lates, if necessary, by filtering through a prewashed
0.2-␮m-pore-diam membrane filter. Using a prewashed F− 0.48 0.49 0.05 0.03 No
syringe of 1 to 10 mL capacity equipped with a male luer F− 4.84 4.64 0.52 0.46 No
Cl 0.76 0.86 0.38 0.11 No
fitting inject sample or standard. Inject enough sample to Cl− 17 17.2 0.82 0.43 No
flush sample loop several times: for 0.1 mL sample loop Cl 455 471 46 13 No
inject at least 1 mL. Switch ion chromatograph from load NO2 0.45 0.09 0.09 0.04 Yes, neg
to inject mode and record peak heights and retention times NO2 21.8 19.4 1.9 1.3 Yes, neg
on strip chart recorder. After the last peak (SO42−) has Br− 0.25 0.25 0.04 0.02 No
Br− 13.7 12.9 1.0 0.6 No
appeared and the conductivity signal has returned to base PO43− 0.18 0.10 0.06 0.03 Yes, neg
line, another sample can be injected. PO43− 0.49 0.34 0.15 0.17 Yes, neg
A4.6.4 Regeneration — For systems without fiber NO3− 0.50 0.33 0.16 0.03 No
NO3− 15.1 14.8 1.15 0.9 No
suppressor regenerate with 1 N H2SO4 in accordance with SO42− 0.51 0.52 0.07 0.03 No
the manufacturer’s instructions when the conductivity base SO42− 43.7 43.5 2.5 2.2 No
line exceeds 300 ␮mho when the suppressor column is
on line.
A4.7 Calculation H p peak height or area,
--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---
A4.7.1 Calculate concentration of each anion, in F p response factor − concentration of standard/

mg/L, by referring to the appropriate calibration curve. height (or area) of standard, and
Alternatively, when the response is shown to be linear, use D p dilution factor for those samples requiring
the following equation: dilution.
CpHⴛFⴛD (A4.1) A4.8 Precision and Bias

A4.8.1 Samples of reagent water to which were
where: added the common anions were analyzed in 15 laboratories
C p mg anion/L, with the results shown in Table A4.2.
583
ARTICLE 25 2013 SECTION V
ARTICLE 25
MAGNETIC PARTICLE STANDARDS
--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---
584

Asme V 2013.pdf - 5

Uploaded by

Copyright:

Available Formats

You might also like

Asme V 2013.pdf - 5

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Asme V 2013.pdf - 5

Uploaded by

Copyright:

Available Formats

--`,,,`,`,``,``,,`,``,`,`,`,``,`-`-`,,`,,`,`,,`---

INTENTIONALLY LEFT BLANK

STANDARD TEST METHOD FOR SULFUR IN PETROLEUM

(Identical with ASTM Specification D 129-00 (R2005)

STANDARD TEST METHOD FOR

[Identical with ASTM D 129-00 (R2005)]

1. Scope D 1552 Test Method for Sulfur in Petroleum Products

2. Referenced Documents 4. Apparatus and Materials

circuit. Close the circuit to ignite the sample. (Warning —

STANDARD TEST METHOD FOR SULFATE ION IN WATER

(Identical with ASTM Specification D 516-07.)

STANDARD TEST METHOD FOR SULFATE ION IN

(Identical with ASTM D 516-07)

1. Scope E 60 Practice for Analyss of Metals, Ores, and Related

Copyright ASME International (BPVC)

(ppm). This can be overcome by concentrating the sample or by adding

TABLE 4 of the batch run to ensure contamination was not a problem

X1. RATIONALE FOR DISCONTINUATION OF METHODS

X1.1 Gravimetric: X1.2 Volumetric:

STANDARD TEST METHOD FOR CHLORINE IN NEW AND

(Identical with ASTM Specification D 808-05.)

STANDARD TEST METHOD FOR

(Identical with ASTM D 808-05)

1. Scope ensures against explosive rupture of the bomb, or a blow-

D 1193 Speciﬁcation for Reagent Water

adherence to all of the provisions prescribed hereinafter bomb.

5.2 Sample Cup, platinum, 24 mm in outside diameter TABLE 1

as deﬁned by Type II or III of Speciﬁcation D 1193.

TABLE 2 8.5 Determination of Chlorine — Acidify the solution

10.1.2 When there is no QC/QA protocol established Chlorine, % Repeatability

11. Report 12.2.2 Reproducibility — The difference between two

Copyright ASME International (BPVC)

STANDARD PRACTICE FOR LIQUID PENETRANT

(Identical with ASTM Specification E 165-09.)

STANDARD PRACTICE FOR

(Identical with ASTM Speciﬁcation E 165-09)

1. Scope 1.4 The values stated in inch-pound units are to be

als, and of nonmetallic materials such as glazed or fully

E 1209 Test Method for Fluorescent Liquid Penetrant TABLE 1

E 1417 Practice for Liquid Penetrant Testing

Dwell TimesA (minutes)

8.6.3.8 Spray Post-Rinsing — Effective post-rins-

Copyright ASME International (BPVC)

metals in the residue are determined by ﬂame photometry,

Copyright ASME International (BPVC)

A1. Cleaning of Parts and Materials A1.1.1.4 Alkaline Cleaning:

should be residue-free, especially when used as a hand-

A1.2.2 Residual penetrant may be removed through

Copyright ASME International (BPVC)

where: A2.7.3.3 Glacial Acetic Acid-Nitric Acid Solu-

A2.7.3.1 Gelatin Solution — A typical preparation (P − B) ⴛ M

A2.7.6 Precision and Accuracy: A3.4 Apparatus

A3.5.2 Purity of Water — Unless otherwise indicated, TABLE A3.1

TABLE A4.1 FIG. A4.1 TYPICAL ANION PROFILE

NOTE A4.3: Use of sample weights containing over 20 mg of chlorine

A4.7.1 Calculate concentration of each anion, in F p response factor − concentration of standard/

CpHⴛFⴛD (A4.1) A4.8 Precision and Bias

You might also like