01 ARTICLE 24

LIQUID PENETRANT STANDARDS

SD-129 Standard Test Method for Sulfur in Petroleum Products (General

(ASTkd 129-95) Bomb Method). ,. 445

SD-516 Standard Test Method for Sulfate Ion in Water 449

(ASTM D 516.90)

SD-808 Standard Test Method for Chlorine in New and Used Petroleum
(ASTM D 808.95) Products (Bomb Method). 453

SD-1552 Standard Test Method for Sulfw in Petroleum Products (High-

(ASTM D 1552.95) Temperature Method). 451

SE-165 Standard Test Method for Liquid Penetnnt Examination. 464

(ASTM E 165.95)

444
 STANDARD TEST METHOD FOR SULFUR
IN PEfTROLEUM PRODUCTS
(GENERAL BOMB METHOD)
SD-129

(Identical with ASTM D 129-95)

(This specification is available in SI Units only.)

1. SCOPC E 144 Practice for Safe Use of Oxygen Combustion

Bombs
1.1 This test method covers the determination of
sulfur in petroleum products, including lubricating oils
containing additives, additive concentrates, and Iubricat-
ing greases that cannot be burned completely in a wick 3. Summary of Test Method
lamp. The test method is applicable to any petroleum
product sufficiently low in volatility that it can be 3.1 The sample is oxidized by combustion in a bomb
weighed accurately in an open sample boat and con- containing oxygen under pressure. The sulfnr, as snlfate
taining at least 0.1% sulfur. in the bomb washings, is determined gravimetrically
as barium &fate.
NOTE 1 - This test method is not applicable to samples containing
elements that give residues, other than barium solfate, which are 3.2 Warning - Strict adherence to all of the
insoluble in dilute hydrochloric acid and would interfere in the provisions prescribed hereajier ensures against explo-
precipitation step. These interfering elements include iron. aluminum,
calcium, silicon, and lead which are sometimes present in greases, sive rupture of the bomb, or a blow-out, provided the
lube oil additives, or additive oils. Other acid insoluble materials bomb is of proper design and construction and in good
that interfere are silica, molybdenum disubide, asbestos, mica, etc. mechanical condition. It is desirable, however, that the
The test method is not applicable to used oils containing wear metals,
and lead or silicates from contamination. Samples that are excluded bomb be enclosed in a shield of steel plate at least
can be analyzed by Test Method D 1552. 13 mm thick, or equivalent protection be provided
against unforseeable contingencies.
1.2 This standard does not purport to address all
of the safety concerns, if any, associated with its use.
It is the responsibility of the user of this standard to
establish appropriate safety and health practices and 4. Apparatus and Materials
determine the applicability of regulatory limitations
prior to use. See 3.2 for specific precautionary directions 4.1 Bomb, having a capacity of not less than 300
mL, so constructed that it will not leak during the test
incorporated in the test method.
and that quantitative recovery of the liquids from the
bomb may be achieved readily. The inner surface of
the bomb may be made of stainless steel or any other
material that will not be affected by the combustion
2. Referenced Documents process or products. Materials used in the bomb assem-
2.1 ASTM Standards: bly, such as the head gasket and lead-wire insulation,
D 1193 Specification for Reagent Water shall be resistant to heat and chemical action, and shall
D 1552 Test Method for Sulfur in Petroleum Products not undergo any reaction that will affect the sulfur
(High-Temperature Method) content of the liquid in the bomb.

445
SD-129 2001 SXCTION
4.2 Sample Cup, platinum, 24 mm in outside diameter
at the bottom, 27 mm in outside diameter at the top,
12 mm in height outside, and weighing 10 to 11 g.
4.3 Firing Wire, platinum, No. 26 B & S gage, 0.41
mm (16 thou), 27 SWG, or equivalent,
NOTE 2: Caution - The switch in the ignition circuit shall be of
a type which remains open, except when held in closed position by
the operator.
4.4 Ignition Circuit, capable of supplying sufficient
current to ignite the cotton wicking or nylon thread
without melting the wire. The current shall be drawn
from a step-down transformer or from a suitable battery.
4.5 Cotton Wick@ or Nylon Sewing Thread, white.
5. Reagents and Materials
5.1 Purity of Reagents - Reagent grade chemicals
shall be used in all tests. Unless otherwise indicated,
it is intended that all reagents shall conform to the
specifications of the Committee on Analytical Reagents
of the American Chemical Society, where such specifi-
cations are available. Other grades may be used, pro-
vided it is first ascertained that the reagent is of
sufficiently high purity to permit its use without less-
ening the accuracy of the determination.
5.2 Purity of Water - Unless otherwise indicated,
references to water shall mean water as defined by
Type II or 111 of Specification D 1193.
5.3 Barium Chloride Solution (85 g/litre) -Dissolve
100 g of barium chloride dihydrate (BaQ 2Hz0) in
distilled water and dilute to 1 litre.
5.4 Bromine Water (snturated).
5.5 Hydrochloric Acid (sp gr 1.19) - Concentrated
hydrochloric acid (HCI).
5.6 Oxygen, free of combustible material and sulfur
compounds, available at a pressure of 41 kgf/cm*
(40 atm).
5.7 Sodium Carbonate Solution (50 g/litre) - Dis-
solve 135 g of sodium carbonate decahydrate (Na2C03
10HzO) or its equivalent weight in distilled water
and dilute to 1 litre.
5.8 White Oil, USP, or Liquid Parajjin, BP, or
equivalent.
446
V
6. Procedure
6.1 Preparation of’ Bomb and Sample - Cut a piece
of firing wire 100 mm in length. Coil the middle
section (about 20 mm) and attach the free ends to the
terminals. Arrange the coil so that it will be above
and to one side of the sample cup. Insert between two
loops of the coil a wisp of cotton or nylon thread of
such length that one end will extend into the sample
cup. Place about 5 mL of NazC03 solution in the bomb
(Note 3) and rotate the bomb in such a manner that
the interior surface is moistened by the solution. Intro-
duce into the sample cup the quantities of sample and
white oil (Notes 5 and 6) specified in the following
table, weighing the sample to the nearest 0.2 mg (when
white oil is used, stir the mixture with a short length
of quartz rod and allow the rod to remain in the sample
cup during the combustion).
NOTE 3 -After repeated use of the bomb for sulfur determinations.
a film may be noticed on the inner surface. This dullness can be
removed by periodic polishing of the bomb. A satisfactory method
for doing this is to rotate the bomb in a lathe at about 300 rpm
and polish the inside surface with emery polishing papers Grit No.
‘4. or equivalent paper, coated with a 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 pits and put a high
polish on the surface. Before the bomb is used it shall he washed
with soap and ~ter to remove oil or paste left from the polishing
operation.
NOTE 4: Caution - Do not use more than I.0 g total of sample
and white oil or other law sulfur combustible material or more than
0.8 g if the IP 12 bomb is used.
Weight of Weight of
Sulfur Content, I Sample. g White Oil, g
5 or under 0.6 to 0.8 0.0
Over 5 0.3 to 0.4 0.3 to 0.4
NOTE 5 - Use of sample weights containing over 20 mg of
chlorine 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 the chlorine content as given in the
following table:
Weight of Weight of
Chlorine Content. % Sample, g White Oil, g
2 t” s 0.4 0.4
Over 5 to IO 0.2 0.6
Over IO to 20 0.1 0.7
Over 20 to 50 0.05 0.7
NOTE 6 - If the sample is no, readily miscible with white oil,
some other low sulfur combustible diluent may be substituted.
However, the combined weight of sample and nonvolatile diluent
shall not exceed I.0 g or more than 0.8 g if the IP 12 bomb is used.
6.2 Addition of Oxygen - Place the sample cup in
position and arrange the cotton wisp or nylon thread
so that the end dips into the sample. Assemble the
bomb and tighten the cover securely. (Caution - See
 ARTICII 24 ~ LIQUID
Note 7.) Admit oxygen slowly (to avoid blowing the
oil from the cup) until a pressure is reached as indicated
in the following table:
Capacityof Minimum Gage MaximumGage
Bomb,ml Pressure,”kgflcm’ (atm) Pressures kgflcm’ (atm)
300 to 350 39 (38) 41 (40)
350 to 400 36 (35) 38 (37)
400 to 450 31 (30) 33 (32)
450 to 500 28 (27) 30 (29)
NOTE 7: Caution - Do not add oxygen or ignite the sample if
the bomb has been jarred, dropped,or tilted.
6.3 Combustion - Immerse the bomb in a cold
distilled-water bath. Connect the terminals to the open
electrical circuit. Close the circuit to ignite the sample.
(Caution - See Note 8.) Remove the bomb from the
bath after immersion for at least 10 min. Release the
pressure at a slow, uniform rate such that the operation
requires not less than I min. Open the bomb and
examine the contents. If traces of unburned oil or
sooty deposits are found, discard the determination and
thoroughly clean the bomb before again putting it in
use (Note 3).
NOTE 8: Caution - Da not go near tbe bomb until at least 20 s
after tiring.
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 a 600.mL beaker having a mark to indicate
75 mL. Remove any precipitate in the bomb by means
of a rubber policeman. Wash the base of the terminals
until the washings are neutral to the indicator methyl
red. Add IO mL of saturated bromine water to the
washings in the beaker. (The volume of the washings
is normally in excess of 300 mL.) Place the sample
cup in a 50-mL beaker. Add 5 mL of saturated bromine
water, 2 mL of HCI, and enough water just to cover
the cup. Heat the contents of the beaker 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
any precipitate in the cup by means of a rubber
policeman. Add the washings from the cup and the
50-mL beaker, 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 material.
447
PENRTRANT STANDARDS SD-129
6.5 Determination of Sulfur - Evaporate the com-
bined washings to 200 mL on a hot plate or other
source of heat. Adjust the heat to maintain slow boiling
of the solution and add 10 mL of the BaC12 solution,
either in a fine stream or dropwise. Stir the solution
during the addition and for 2 min thereafter. Cover
the beaker with a fluted watch glass and continue
boiling slowly until the solution has evaporated to a
volume approximately 75 mL as indicated by a mark
on the beaker. Remove the beaker from the hot plate
(or other source of heat) and allow it to cool for 1
hr before filtering. Filter the supernatant liquid through
an ashless, quantitative filter paper (Note 9). Wash the
precipitate with water, first by decantation and then on
the filter, until free from chloride. Transfer the paper
and precipitate to a weighed crucible and dry (Note
10) at a low heat until the moisture has evaporated.
Char the paper completely without igniting it, and
finally ignite at a bright red heat until the residue is
white in color. After ignition is complete, allow the
crucible to cool at room temperature, and weigh.
NOTE 9 - A weighedporcelainhlter crucible (Selas type) of 5
to 9.pm porosity may be used in place of the filter paper. In this
case the precipitateis washed free of chloride and then dried to
constant weight at 500 * 25°C.
NOTE 10 - A satisfactory means of drying, charring, and igniting
the paperand precipitateis to placethe cruciblecontainingthe wet
filter paper in a cold &Uric muffle furnace and m turn on the
current. Drying, charring, and ignition usually will occur at the
desired rate.
6.6 Blank - Make a blank determination whenever
new reagents, white oil, or other low-sulfur combustible
material are used. When running a blank on white oil,
use 0.3 to 0.4 g and follow the normal procedure.
1. Calculation
7.1 Calculate the sulfur content of the sample as
follows:
Sulfur, weight percent = (P - B)13,73/W
where:
P= grams of BaS04 obtained from sample,
B = grams of BaS04 obtained from blank, and
W= grams of sample used.
8. Report
8.1 Report the results of the test to the nearest
0.01%.
SD-129 2001 SECTION V

9. Precision and Bias I.5 10 2.0 0.12 0.25

9.1 The precision of this test is not known to have
been obtained in accordance with currently accepted
guidelines (for example in Committee D-2 Research
Report, “Manual on Determining Precision Data for
ASTM Methods on Petroleum Products and Lubri-
cants”).
9.1.1 Repeatability - The difference between two
test results, obtained by the same operator with the
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 following values only in one case in twenty.
9.1.2 Reproducibility - The difference between
two single and independent results obtained by different
operators working in different laboratories on identical
test material would, in the long run, in the normal and
correct operation of the test method, exceed the follow-
ing values only in one case in twenty:
Sulfur,
Weight % Repeatability Reproducibility
0.1 to 0.5 0.04 0.05
0.5 LO 1.0 0.06 0.09
1.0 to 1.5 0.08 0.15
2.0 to 5.0 0.1R 0.27
NOTE II - The precision shown in the above table does not apply
to samples containing over 2% cblorinc because:an added restriction
on the amount of sample which can be ignited is imposed.
NOTE 12 - This test method has been cooperatively tested only
in the range of 0.1 Lo 5.0% sulfur.
NOTE 13 - ‘Ibe following information on the precision of this
method has been developed by the Institute of Petroleum (London):
(al Results of duplicate tests should not differ by more than Ihe
following amoll”t,s:
Repeatability Reproducibility
0.016 x + 0.06 0.037 x + 0.13
where x is the mean of duplicate tat results.
(bj These precision values were obtained in 1960 by statistical
examination of interlaboratory test results. No limits have been
established for additive concenlrates.
9.2 Bias - Results obtained in one laboratory by
Test Method D 129 on NIST Standard Reference Mate-
rial Nos. 162OA, 1621C, and 3662B were found to be
0.05 mass % higher than the accepted reference values.
10. Keywords
10.1 bomb; sulfur

448
 STANDARD TEST METHOD FOR
SULFATE ION IN WATER
SD-516

(Identical with ASTM D 516.90)

1. scope 3. Terminology
1.1 This turbidimetric test method covers the determi- 3.1 Dejnitions - For definitions of terms used in
nation of sulfate in water in the range from 1 to 40 this test method, refer to Terminology D 1129.
mg/L of sulfate ion (SO;-).

1.2 This test method was used successfully with

4. Summary of Test Method
drinking, ground, and surface waters. It is the user’s
responsibility to ensure the validity of this test method 4.1 Sulfate ion is converted to a barium sulfate
for waters of untested matrices. suspension under controlled conditions. A solntion con-
taining glycerin and sodium chloride is added to stabilize
1.3 Former gravimetric and volumetric test methods the suspension and mini&e interferences. The resulting
have been discontinued. Refer to XAppendix Xl for
turbidity is determined by a nephelometer, spectropho-
historical information.
tometer, or photoelectric calorimeter and compared to
1.4 This standard does not purport to address the a curve prepared from standard sulfate solutions.
safety concerns, if any, associated with its use. It is
the responsibility of the usw of this standard to establish
appropriate safety and health practices and determine 5. Significance and Use
the applicability of regulatory limitations prior to use.
5.1 The determination of sulfate is important because
it has been reported that when this ion is present in
excess of about 250 mg/L in drinking water, it causes
2. Referenced Documents a cathartic action (especially in children) in the presence
of sodium and magnesium, and gives a bad taste to
2.1 ASTM Standards:
the water.
D 1066 Practice for Sampling Steam
D 1129 Terminology Relating to Water
D 1192 Specification for Equipment for Sampling Water
and Steam in Closed Conduits 6. Interferences
D 1193 Specification for Reagent Water 6.1 Insoluble suspended matter in the sample must
D 2777 Practice for Determination of Precision and Bias be removed. Dark colors that can be compensated for
of Applicable Methods of Committee D-19 on Water in the procedure interfere with the measurement of
D 3370 Practices for Sampling Water from Closed Con- suspended barium sulfate (BaSO&
duits
E 60 Practice for Photometric and Spectrophotometric 6.2 Polyphosphates as low as 1 mg/L will inhibit
Methods for the Chemical Analysis of Metals barium sulfate precipitation causing a negative interfer-
E 275 Practice for Describing and Measuring Perform- ence. Phosphonates present in low concentrations, de-
ance of Ultraviolet, Visible, and Near Infrared Spectro- pending on the type of phosphonate, will also cause
photometers a negative interference. Silica in excess of 500 mg/L

449
may precipitate along with the barium sulfate causing
a posit&c interference. Chloride in excess of 5000
mg/L will cause a negative interference. Aluminum,
polymers, and large quantities of organic material pres-
ent in the test sample may cause the barium sulfate
to precipitate nonuniformly. In the presence of organic
matter certain bacteria may reduce sulfate to sulfide.
To minimize the action of sulfate reducing bacteria,
samples should be refrigerated at 4°C when the presence
of such bacteria is suspected.
6.3 Although other ions normally found in water do
not appear to interfere, the formation of the barium
sulfate suspension is very critical. Determinations that
are in doubt may be checked by a gravimetric method
in some cases, or by the procedure suggested in Note 2.
I. Apparatus
7.1 Photometer - One of the following, which are
given in order of preference.
7.1.1 Nephelometer or turbidimeter;
7.1.2 Spectrophotometer for use at 420 nm with
light path of 4 to 5 cm;
7.1.3 Filter photometer with a violet filter having
a maximum near 420 nm and a light path of 4 to 5 cm.
7.2 Stopwatch, if the magnetic stirrer is not equipped
with an accurate timer.
7.3 Measuring Spoon, capacity 0.2 to 0.3 mL.
7.4 Filter photometers and photometric practices pre-
scribed in this test method shall conform to Practice
E 60: spectrophotometer practices shall conform to
Practice E 275.
8. Reagents
8.1 Purity of Reagents - Reagent grade chemicals
shall be used in all tests. Unless otherwise indicated,
it is 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 is first ascertained that the reagent
is of sufficiently high purity to permit its use without
lessening the accuracy of the determination.
8.2 Purity of Water - Unless otherwise indicated,
references to water shall be understood to mean reagent
water conforming to Specification D 1193, Type III.
8.3 Warirrnz Chloride - Crystals of barium chloride
(RaC12 2H,O) screened to 20 to 30 mesh. To prepare
in the laboratory, spread crystals over a large watch
glass, desiccate for 24 h, screen to remove any crystals
that are not 20 to 30 mesh, and store in a clean, dry jar.
8.4 Conditioning Reagent - Place 30 mL of concen-
trated hydrochloric acid (HCl, sp gr 1.19), 300 mL
reagent water, 100 mL 95% ethanol or isopropanol and
75 g sodium chloride (NaCI) in a container. Add 50
mL glycerol and mix.
8.5 Sulfate Solution, Standard (1 mL = 0.100 mg
SOI--) - Dissolve 0.1479 g of anhydrous sodium
sulfate (Na*SO,) in water, and dilute with water to
1 L in a volumetric flask.
9. Sampling
9.1 Collect the sample in accordance with Practice
D 1066, Specification D 1192, and Practices D 3370,
as applicable.
10. Calibration
10.1 Follow the procedure given in Section 11, using
appropriate amounts of the standard sulfate solution
prepared in accordance with 8.5 and prepare a calibration
curve showing sulfate ion content in milligrams per
litre plotted against the corresponding photometer read-
ings (Note 1). Prepare standards by diluting with water
0.0, 2.0, 5.0, 10.0, 15.0, 20.0, 30.0, and 40.0 mL of
standard sulfate solution to 100.mL volumes in volumet-
ric flasks. These solutions will have sulfate ion concen-
trations of 0.0, 2.0, 5.0, 10.0, 15.0, 20.0, 30.0, and
40.0 mg/L (ppm), respectively.
11. Procedure
11.1 Filter the sample if it is turbid, and adjust the
temperature to between 15 and 30°C.
11.2 Pipet into a 250-mL beaker 100 mL or less of
the clear sample containing between 0.5 and 4 mg of
sulfate ion (Note 2). Dilute to 100 mL with water if
required, and add 5.0 mL of conditioning reagent
(Note 1).
 ARTICLE 24 ~ LIQUID PENETRANT STANDARDS SD-516

NOTE 2 - The solubility of EtaSO is such that difficulty may be TABLE 1

experienced in the detemkation of sulfate concentrations below
OVERALL C.7,) AND SINGLE-OPERATOR C&J
about 5 mg/L (ppm). This can be overcome by concentrating the
sample or by adding 5 mL of standard sulfate solution (I mL = STANDARD DEVIATIONS AGAINST MEAN
0.100 mg SOIm -) to the sample before diluting to IOU ml. This CONCENTRATION FOR INTERLABORATORY
will add 0.5 mg SQ to the sample, which must be subtracted from RECOVERY OF SULFATE FROM REAGENT WATER”
the final result.
StandardDeviation,mg/L
Mean Concentration (K),
11.3 Mix in the stirring apparatus.
mu/L ST S”
11.4 While the solution is being stirred, add a 6.6 0.5 0.1
measured spoonful of BaC12 crystals (0.3 g) and begin 20.4 1.0 0.4
timing immediately. 63.7 2.5 1.3

A Thetest methodis linearto 40 mg/L. Testingat the 63.9 levelwas

11.5 Stir exactly 1.0 min at constant speed. accomplishedthrough dilution as describedin 11.2.
NOTE 3 - The stirring should be at a constant rate in all determina-
tions. The use of a magnetic stirrer has keen found satisfactory for
this purpose.

11.6 Immediately after the stirring period has ended, TABLE 2

pour solution into the cell and measure the turbidity OVERALL C.9,) AND SINGLE-OPERATOR C&,1
STANDARD DEVIATIONS AGAINST MEAN
at 30-s intervals for 4 min. Record the maximum
CONCENTRATION FOR INTERLABORATORY
reading obtained in the 4-min period. RECOVERY OF SULFATE FROM DRINKING, GROUND,
11.7 If the sample contains co101 or turbidity, run AND SURFACE WATER’
a sample blank using the procedure 11.2 through 11.6 StandardDeviation,mg/L
without the addition of the barium chloride. Mean Concentrationt%,
mg/L ST so
11.8 If interferences are suspected, dilute the sample 6.9 0.7 0.5
with an equal volume of water, and determine the 20.2 2.2 1.8
sulfate concentration again. If the value so determined 63.3 4.5 1.6
is one half that in the undiluted sample, interferences A Thetest methodis linearto 40 mg/L. Testingat the 63.9 levelwas
may be assumed to be absent. accomplishedthrough dilution as describedin 11.2.

12. Calculation
12.1Convert the photometer readings obtained with
the sample to milligrams per litre sulfate ion (SO4--)
by use of the calibration curve described in Section 10.
13. Precisionand Bias
13.1The precision and bias data presented in this test
method meet the requirements of Practice D 2777.86.
13.2 The overall and single-operator precision of the
test method, within its designated range, varies with
the quantity being tested according to Table 1 for
reagent water and Table 2 for drinking, ground, and
surface waters.
13.2.1 Seven laboratories participated in the round
robin at three levels in triplicate, making a total of 21
observations at each level for reagent water and for
matrix water (drinking, ground, and surface water).
13.3 Recoveries of known amounts of snlfate from
reagent water and drinking, ground, and surface waters
are as shown in Table 3.
13.3.1A table for estimating the bias of the test
method through its applicable concentration range can
be found in Table 4.
13.3.2 These collaborative test data were obtained
on reagent grade water and natural waters. For other
matrices, these data may not apply.
14. Keywords
14.1 drinking water; ground water; sulfate; surface
water; turbidimetric

451
SD-516 2001 SECTION V

TABLE 3 TABLE 4
DETERMINATION OF BIAS” MEAN SULFATE RECOVERY AGAINST
CONCENTRATIONADDEDWITH OVERALLSTANDARD
Statistically
Amount Amount Significant DIVISION SHOWN FOR INTERLABORATORY
Added, Found, at 5% Level EXPERIMENTALRECOVERYOFSULFATEFROM
w/L mg/L *Bias *%Bias (at * 0.05) REAGENT WATER AND DRINKING, GROUND, AND
SURFACE WATER’
Reagent water 20.8 20.4 -0.4 -1.9% NO
63.9A 63.7A -0.2 -0.2% NO Mean Surface Recovery (x), mg/L
7.0 6.6 -0.4 -5.3% NO Sufate
Drinking, ground Added, mg/L Reagent Water CSJ Matrix Water (So)
and surface 7.0 6.6 (0.5) 6.9 (0.7)
water 20.8 20.2 -0.6 -2.7% NO 20.8 20.4 (1.0) 20.2 (2.2)
63.9A 63.3” -0.6 -0.9% NO 63.9 63.7 12.5) 63.3 (4.5)
7.0 6.9 -0.1 -1.8% NO
A The test method is linear ta 40 mg/L. Testing at the 63.9 level was
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.
accomplished through dilution as described in 11.2.

APPENDIX

(Nonmandatory Information)

Xl. RATIONALE FOR DISCONTINUATION Xl.2 Volumetric:

OF METHODS
X1.2.1 This test method was discontinued in 1988.
X1.1 Gravimetric: The test method may be found in the 1988 Annual
X1.1.1 This test method was discontinued in 1988. Book of ASTM Standards, Vol 11 .Ol. The test method
The test method may be found in the 1988 Annual was originally issued in I959 as a non-referee method,
Book of ASTM Standards, Vol 11.01. The test method and made the primary method in the 1980 issue of
was originally issued in 1938. Test Method D 516.

X1.1.2 This test method covers the determination X1.2.2 This test method covers the determination
of sulfate in water and wastewater. Samples containing of sulfate in industrial water. Samples containing from
from 20 to 100 mg/L sulfate may be analyzed. 5 to 1000 mg/L of sulfate may be analyzed.

X1.1.3 Sulfate is precipitated and weighted as
barium sulfate after removal of silica and other insoluble
matter.
X1.1.4 This test method was discontinued because
there were insufficient laboratories interested in partici-
pating in another collaborative study to obtain the
necessary precision and bias as required by Practice
D 2111.
X1.2.3 Sulfate is titrated in an alcoholic solution
under controlled acid conditions with a standard barium
chloride solution using thorin as the indicator.
X1.2.4 This test method was discontinued because
there were insufficient laboratories interested in partici-
pating in another collaborative study to obtain the
necessary precision and bias as required by Practice
D 2117.

452
 STANDARD TEST METHOD FOR
CHLORINE IN NEW AND USED PETROLEUM
PRODUCTS (BOMB METHOD)
SD-808
(Identical
with ASTMD 808-95)
1. SCOpe
1.1 This test method covers the determinationof
chlorinein lubricatingoils andgreases,includingnew
and usedlubricatingoils and greasescontainingaddi-
tives,andin additiveconcentrates.Its rangeof apphca-
bility is 0.1 to 50% chlorine.The procedureassumes
thatcompoundscontaininghalogensotherthanchlorine
will not be present.
1.2 The preferredunits are masspercentand SI.
1.3 This standard does not purport to address all
of the safety concerns, if any, associated with its use.
It is the responsibility of the user of this standard to
establish appropriate safety and health practices and
determine the applicability of regulatory limitations
prior to use.
2. Referenced Documents
2.1 ASTM Standards:
D 1193Specificationfor ReagentWater
D 4057Practicefor ManualSamplingof Petroleumand
PetroleumProducts
3. Summary of Test Method
3.1 The sampleis oxidizedby combustionin a bomb
containingoxygen under pressure(Caution - See
Note 1). The chlorine compoundsthus liberatedare
absorbed in a sodiumcarbonatesolutionandtheamount
of chlorine presentis determinedgravimetricallyby
precipitationas silver chloride.
453
NOTE 1: (Caution - Safety - Strict adherence to all of the
provisions prescribed hereinafter enwes against explosive rupture
of the bomb, or a blow-out, provided the bomb is of proper design
and construction and in good mechanical condition. It is d&able,
however, that the bomb be enclosed in a shield of steel plate at
least 13 mm (‘/? in.) thick, or equivalent protection be provided
against unforseeable contingencies.
4. Significance and Use
4.1 This test methodmay be usedto measurethe
level of chlorine-containingcompoundsin petroleum
products,This knowledgecan be usedto predictper-
formanceor handlingcharacteristicsof the productin
question.
5. Apparatus
5.1 Bomb, having a capacityof not less than 300
mL, so constructedthat it will not leak duringthe test,
and that quantitativerecoveryof the liquids from the
bomb may be readily achieved.The inner surfaceof
the bomb may be madeof stainlesssteelor any other
material that will not be affectedby the combustion
processor products.Materialsusedin thebombassem-
bly, suchas the headgasketand lead-wireinsulation,
shallbe resistantto heatandchemicalaction,andshall
not undergoany reactionthat will affect the chlorine
contentof the liquid in the bomb.
platinum,24mm in outsidediameter
5.2 Sample Cup.
at the bottom, 27 mm in outsidediameterat the top,
12 mm in height outside,and weighing IO to 11 g.
5.3 Firing Wire, platinum,No. 26 B & S gage0.41
(16 thou), 27 SWG or equivalent.
SlKwR 2001 SECTION V
5.4 Ignition Circuir, capable of supplying sufficient
current to ignite the nylon thread or cotton wicking
without melting the wire.
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.
5.5 Nylon Sewing Thread, or Cotton Wicking, white.
5.6 Filter Crucible, f&ted-glass, 30.mL capacity,
medium porosity.
6. Reagents and Materials
6.1 Purity of Reagents - Reagent grade chemicals
shall be used in all tests. Unless otherwise indicated,
it is intended that all reagents shall conform to the
specifications of the Committee on Analytical Reagents
of the American Chemical Society, where such specifi-
cations are available. Other grades may be used, pro-
vided it is first ascertained that the reagent is of
sufficiently high purity to permit its use without less-
ening the accuracy of the determination.
6.2 Purity of Water - Unless otherwise indicated,
references to water shall be understood to mean reagent
water as defined by Type 11 or III of Specification
D 1193.
6.3 Nitric Acid (1 + I) - Mix equal volumes of
concentrated nitric acid (HNO3, sp gr 1.42) and water.
6.4 Oxygen, free of combustible material and halogen
compounds, available at a pressure of 41 kgf/cm* (40
atmos). (Warning - See Note 2.)
NOTE 2: Warning - Oxygenvigorouslyacceleratescombustion.
6.5 Silver Nitrate Solution (SO g AgNO$) - Dis-
solve 50 g of silver nitrate (AgN03) in water and
dilute to 1 L.
6.6 Sodium Carbonate Solution (50 g Na&Os/L) -
Dissolve 50 g of anhydrous Na$Os, 58.5 g of NazCO,
HzO, or 135 g of Na.$03 10 Hz0 in water and
dilute to I L.
6.7 White Oil, refined.
7. Sampling
7.1 Take samples in accordance with the instructions
in Practice D 4057.
7.2 Take care that the sample is thoroughly representa-
tive of the material to be tested and that the portion
454
TABLE 1
QUANTITIES OF SAMPLE AND WHITE OIL
ChlorineContent,
% Weiuht of Samole.o Weight of White Oil, 4
2 and under 0.8 0.0
Above2 to 5, incl 0.4 0.4
Above5 to 10, incl 0.2 0.6
Above10 to 20, incl 0.1 0.7
Above20 to 50, incl 0.05 0.7
of the sample used for the test is thoroughly representa-
tive of the whole sample.
8. Procedure
8.1 Preparation of Bomb and Sample - Cut a piece
of firing wire approximately 100 mm in length. Coil
the middle section (about 20 mm) and attach the free
ends to the terminals. Arrange the coil so that it will
be above and to one side of the sample cup. Insert
into the coil a nylon thread, or wisp of cotton, of such
length that one end will extend into the sample cup.
Place about 5 ml of Na2COl solution in the bomb
and by means of a rubber policeman, wet the interior
surface of the bomb, including the head, as thoroughly
as possible. Introduce into the sample cup the quantities
of sample and white oil (Notes 3 and 4) specified in
Table 1 (Caution - Note 5), weighing the sample to
the nearest 0.2 mg. (When white oil is used, stir the
mixture with a short length of quartz rod and allow the
rod to remain in the sample cup during the combustion.)
8.1.1 After repeated use of the bomb for chlorine
determination, a film may be noticed on the inner
surface. This dullness can be removed by periodic
polishing of the bomb. A satisfactory method for doing
this is to rotate the bomb in a lathe at about 300 ‘pm
and polish the inside with Grit No. 2/O or equivalent
paper coated with a 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
pits and put a high polish on the surface. Before using
the bomb wash it with soap and water to remove oil
or paste left from the polishing operation. Bombs with
porous or pitted surfaces should never be used because
of the tendency to retain chlorine from sample to
sample.
8.12 When the sample is not readily miscible
with white oil, some other nonvolatile, chlorine-free
combustible diluent may be employed in place of white
 ARTICLE 24 -~.~L1QUlD PENETRANT STANDARDS
TABLE 2
GAGEPRESSURE
MinimumGage MaximumGage
P~ersure,~kgflcn? Pressure,”kgflcmZ
Capacityof Bomb,mL hl) Mm)
300 to 350 39 (38) 41 (40)
350 to 400 36 (35) 38 (37)
400 to 450 31 (30) 33 (32)
450 to 500 28 (27) 30 (29)
A The minimumpressuresare specifiedto providesufficientOxygen
for completecombustion,and the maximumpressuresrepresenta
safety requirement
oil. However, the combined weight of sample and
nonvolatile diluent shall not exceed 1 g. Some solid
additives are relatively insoluble, but may be satisfacto-
rily burned when covered with a layer of white oil.
NOTE3 - Thepracticeof runningalternatelyhigh and low samples
in chlorinecontentshallbe avoidedwheneverpassible.1, is difficult
to rinse the last tracesof chlorinefrom the walls of the bomb and
the tendencyfor residualchlorine to czv over from sampleto
samplehas been observedin a number of laboratories.When a
samplehigh in chlorinehas precededone low in chlorine content,
the test on the low-chlorinesampleshall be repeatedand one or
bath of the low valuesthus obtainedcan be consideredsuspectif
they do nat agreewithin the limits af repeatabilityof this method.
NOTE 4: Caution - Do not use more than 1 g total of sample
and white oil or other chlorine-freecombustiblematerial.
8.2 Addition of Oxygen - Place the sample cup in
position and arrange the nylon thread, or wisp of cotton,
so that the end dips into the sample. Assemble the
bomb and tighten the cover securely. Admit oxygen
(Caution - See Note 8) slowly (to avoid blowing
the oil from the cup) until a pressure is reached as
indicated in Table 2.
NOTE 5: Caution - Do KV add oxygen or ignite the sampleif
the bomb has beenjarred, dropped,01 tilted.
8.3 Combustion - Immerse the bomb in a cold
water bath. Connect the terminals to the open electrical
circuit. Close the circuit to ignite the sample. Remove
the bomb from the bath after immersion for at least
10 min. Release the pressure at a slow, uniform rate
such that the operation requires not less than 1 min.
Open the bomb and examine the contents. If traces of
unburned oil or sooty deposits are found, discard the
determination, and thoroughly clean the bomb before
again putting it in use (8.1.1).
8.4 Collection of Chlorine Solution - Rinse the
interior of the bomb, the sample cup, and the inner
surface of the bomb cover with a fine jet of water,
and collect the washings in a 600.mL beaker. Scrub
45s
SD-808
the interior of the bomb and the inner surface of the
bomb cover with a rubber policeman. Wash the base
of the terminals until the washings are neutral to the
indicator methyl red. (The volume of the washings is
normally in excess of 300 mL.) Take special care not
to lose any wash water.
8.5 Determination of Chlorine - Acidify the solution
by adding HNO, (1 + 1) drop by drop until acid to
methyl red. Add an excess of 2 mL of the HN03
solution. Filter through a qualitative paper [if the solu-
tion is cloudy, the presence of lead chloride (PbC12)
is indicated and the solution should be brought to a
boil before filtering] and collect in a second 600~mL
beaker. Heat the solution to about 60°C (140°F) and,
while protecting the solution from strong light, add
gradually, while stirring, 5 mL of AgNOJ solution.
Heat to incipient boiling and retain at this temperature
until the supernatant liquid becomes clear. Test to
ensure complete precipitation by adding a few drops
of the AgN03 solution. If more precipitation takes
place, repeat the above steps which have involved
heating, stirring, and addition of AgN03, as often as
necessary, until the additional drops of AgNO3 produce
no turbidity in the clear, supernatant liquid. Allow the
beaker and contents to stand in a dark place for at
least an hour. Filter the precipitate by suction on a
weighed fritted-glass filter crucible. Wash the precipitate
with water containing 2 mL of HNO? (1 + 1)iL. Dry
the crucible and precipitate at 110°C for 1 h. Cool in
a desiccator, and weigh.
8.6 Blank - Make a blank determination with 0.7
to 0.8 g of white oil by following the normal procedure
but omitting the sample (Notes 6 and 9). Repeat this
blank whenever new batches of reagents or white oil
are used. The blank must not exceed 0.03% chlorine
based upon the weight of the white oil.
NOTE 6 - This proceduremeasureschlorinein the white ail and
in the reagentsused,as well as that introducedfrom contamination.
9. Calculation
9.1 Calculate the chlorine content of the sample as
follows:
Chlorine, mass % = [(P - 19)x 24.741/W
where:
P= grams of AgCl obtained from the sample,
B = grams of AgCl obtained from the blank, and
W= grams of sample used.
SD-XOX 2001 SIX’l’ION V

10. Precision and Bias two single and independent results obtained by different
operators working in different laboratories on identical
10.1 The precision of this test method is not known
test material would, in the long run, in the normal and
to have been obtained in accordance with currently
correct operation of the test method exceed the following
accepted guidelines (for example, in Committee D-2
values only in one case in twenty:
Research Report RR:D2-1007, Manual on Determining
Precision Data for ASTM Methods on Petroleum Prod- Chlorine. % Reproducibility
ucts and Lubricants). 0.1 to 1.9 0.10
2.0 to 5.0 0.30
10.2 The precision of this test method as obtained Above 5.0 5% of amOUnt present
by statistical examination of interlaboratory test results
is as follows: 10.3 Bias:

10.2.1 Repeatability - The difference between 10.3.1 Cooperative data indicate that deviations of
successive test results obtained by the same operator test results from the true chlorine content are of the
with the same apparatus under constant operating condi- same order of magnitude as the reproducibility.
tions on identical test material would, in the long run, 10.3.2 It is not practicable to specify the bias of
in the normal and correct operation of the test method this test method for measuring chlorine because the
exceed the following values only in one case in twenty: responsible subcommittee, after diligent search, was
Chlorine. % Repeatability unable to attract volunteers for an interlaboratory study.
0.1 to 1.9 0.07
2.0 ta 5.0 0.15
Above 5.0 3% of anlo”“, present 11. Keywords
10.2.2 Reproducibility - The difference between 11.1 bomb; chlorine

456
 STANDARD TEST METHOD FOR
SULFUR IN PETROLEUM PRODUCTS
(HIGH-TEMPERATURE METHOD)
SD-1552
(Identical with ASTM D 1552-95)
1. SCOpe
1.1 This test method covers three procedures for the
determination of total sulfur in petroleum products
including lubricating oils containing additives, and in
additive concentrates. This test method is applicable to
samples boiling above 177°C (350°F) and containing
not less than 0.06 mass % sulfur. Two of the three
procedures use iodate detection; one employing an
induction furnace for pyrolysis, the other a resistance
furnace. The third procedure uses IR detection following
pyrolysis in a resistance furnace.
1.2 Petroleum coke containing up to 8 mass % sulfur
can be analyzed.
1.3 This standard may involve hazardous materials,
operations, and equipment. This standard does not
purport to address all of the safety concerns, if any,
associated with its use. It is the responsibility of the
uw of this standard to establish appropriate safety
and health practices and determine the applicability
of regulatory limitations prior to use.
2. Referenced Documents
2.1 ASTM Standards:
D 1193 Specification for Reagent Water
D 1266 Test Method for Sulfur in Petroleum Products
(Lamp Method)
D 4057 Practice for Manual Sampling of Petroleum and
Petroleum Products
457
3. Summary of Test Method
3.1 Iodate Detection System -The sample is burned
in a stream of oxygen at a sufficiently high temperature
to convert about 97% of the sulfur to sulfur dioxide.
A standardization factor is employed to obtain accurate
results. The combustion products are passed into an
absorber containing an acid solution of potassium iodide
and starch indicator. A faint blue co101 is developed
in the absorber solution by the addition of standard
potassium iodate solution. As combustion proceeds,
bleaching the blue color, more iodate is added. The
amount of standard iodate consumed during the combus-
tion is a measure of the sulfur content of the sample.
3.2 IR Detection System - The sample is weighed
into a special ceramic boat which is then placed into
a combustion furnace at 1371°C (2500°F) in an oxygen
atmosphere. Most sulfur present is combusted to SOa
which is then measured with an infrared detector after
moisture and dust are removed by traps. A microproces-
sor calculates the mass percent sulfur from the sample
weight, the integrated detector signal, and a predeter-
mined calibration factor. Both the sample identification
number and mass percent sulfur are then printed out.
The calibration factor is determined using standards
approximating the material to be analyzed.
4. Significance and Use
4.1 This test method provides a means of monitoring
the sulfur level of various petroleum products and
additives. This knowledge can be used to predict per-
formance, handling, or processing properties. In some
cases the presence of sulfur compounds is beneficial
SD-1552 2001 SECTION V

to the product and monitoring the deplction of sulfur

can provide useful information. In other cases the
presence of sulfur compounds is detrimental to the
processing or use of the product.

5. Interferences
5.1 For the iodate systems, chlorine in concentrations
less than 1 mass % does not interfere. The IR system
can tolerate somewhat higher concentrations. Nitrogen
when present in excess of 0.1 mass % may interfere
with the iodate systems; the extent of such interference
may be dependent on the type of nitrogen compound
as well as the combustion conditions. Nitrogen does
not interfere with the IR system. The alkali and alkaline
earth metals, as well as zinc, phosphorus, and lead,
do not interfere with either system.

FIG. 1 COMBUSTION TUBE

6. Apparatus
6.1 Combustion and lodare Derecrion System
6.1.1 Furnaces - Two major types are available,
the primary difference being the manner in which the
necessary high temperatures are obtained. These two NOTE 2 - Also suitable for use with either type of furnace is an
automatic titrator. specifically designed for iodometry. This combines
types are as follows: the functions of absorption and titration to a predetermined end point.

6.1.1.1 Induction Type, which depends upon the

high-frequency electrical induction method of heating.
This assembly shall be capable of attaining a temperature
of at least 1482°C (2700°F) in the sample combustion
zone, under the conditions set forth in Section 10 and
shall be equipped with an additional induction coil
located above the combustion zone, substantially as
shown in Fig. 1.
6.1.1.2 The furnace work coil should have a
minimum output of 500 W: the minimum input rating
of the furnace must be 1000 W. With the correct
amount of iron chips, weighed to ~~0.05g, the maximum
plate current will be between 350 and 450 mA.
6.1.3 Buret, standard 25-mL or automatic types
available from the manufacturers of the specific combus-
tion units, are suitable (Note 2).
6.2 Combustion and IR Derecrion System, comprised
of automatic balance, oxygen flow controls, drying
tubes, combustion furnace, infrared detector and micro-
processor. The furnace shall be capable of maintaining
a nominal operating temperature of 1350°C (2460°F).

NOTE I: Warning - This type of furnace is capable of inflicting 6.3 Miscellaneous Apparatus - Specific combustion
high-frequency burns and high-voltage shocks. In addition to other
precautions, maintain all guards properly. Precaution - Disconnect assemblies require additional equipment such as cruci-
the furnace from the power line whenever electrical repairs or bles, combustion boats, crucible lids, boat pushers,
adjustments are made. separator disks, combustion tubes, sample inserters,
oxygen flow indicator, and oxygen drying trains. The
6.1.1.3 Resistance Type, capable of maintaining additional equipment required is dependent on the type
a temperature of at least 1371°C (2500°F). of furnace used and is available from the manufacturer
of the specific combustion unit. To attain the lower
6.1.2 Absorber, as described in Test Method sulfur concentration given in Section 1, the ceramics
D 1266. used with the induction furnace assembly shall be

458
 ARTIC1.E 24 ~ LIQUID PENETRANT STANDARDS SD-1552

ignited in a muffle furnace at 1371°C (2500°F) for at 7.11 Potassium lodale, Srandard Solution (0.01248
least 4 h before use. M, 1 mL = 0.2 mg S) - Measure exactly 200 mL
of KI03 solution (0.06238 M, 1 mL = I mg S) into
6.4 Sieve, 60.mesh (250.mm).
a I-L volumetric flask and dilute to volume with water.
Thoroughly mix the solution.

1. Reagents and Materials 7.12 Ascarite, 8 to 20 mesh.

7.1 Purity of Reagenfs - Reagent grade chemicals 7.13 Special Materials for Induction-Type Furnaces:
shall be used in all tests. Unless otherwise indicated,
it is intended that all reagents shall conform to the 7.13.1 Tin (20 to 30-mesh).
specifications of the Committee on Analytical Reagents
of the American Chemical Society, where such specifi- 7.13.2 Iron-Chip Accelerator having a sulfur con-
cations are available. Other grades may be used, pro- tent of not more than 0.005 mass %.
vided it is first ascertained that the reagent is of
7.14 Standard Sample-Potassium alum [AlK(SO&
sufficiently high purity to permit its use without less-
12H,O].
ening the accuracy of the determination.
7.2 Purity of Water - Unless otherwise indicated, 7.15 Starch-Iodide Sol&m - Make a paste by
references to water shall be understood to mean reagent adding 9 g of soluble starch to 15 mL of water. Add
water as defined by Type II or III of Specification this mixture, with stirring, to 500 mL of boiling water.
D 1193. Cool the mixture, add 15 g of potassium iodide (KI),
and dilute to 1 L with water.
7.3 Alundum (A1203) or Magnesium Oxide (Com-
Aid). 7.16 Suljiuic Acid (relative density 1.84) - Concen-
trated sulfuric acid (H,SO,).
7.4 Anhydrone (Magnesium Perchlorare).
NOTE 3: Precaution - In addition Lo other precautions, handle NOTE 6: Warning - Poison. Corrosive. Strong oxidizer.
magnesium perchlomtc with can Avoid contacting it with acid and
organic materials. Reactions with fuel may be violent. 7.17 Vanadium Pentoxide, anhydrous, powdered
v205.
7.5 Hydrochloric Acid (3 + 197) - Dilute 30 mL
of concentrated hydrochloric acid (HCI, relative density
1.19) to 2 L with water.
NOTE 4: Warning - Poison. Corrosive. May be fatal if swallowed. 8. Sampling
Liquid and vapor cause were bums.
8.1 Take samples in accordance with the instructions
7.6 Oxygen (Extra Dry) - The oxygen shall be at in Practice D 4057.
least 99.5% pure and show no detectable sulfur by
blank determination.
NOTE 5: Warning - Oxygen vigorously accelerates combustion.
9. Preparation of Apparatus
7.1 Phosphorus Pentoxide (P,O,).
9.1 Induction-Type Furnace - Assemble the appara-
7.8 Potassium Alum (Aluminum Potassium Sulfate). tus according to the instructions furnished by the manu-
facturer. Purify the oxygen by passing it through (1)
7.9 Porassium lodate, Standard Solution (0.06238
HzS04 (relative density 1.84), (2) Ascarite, and (3)
M, 1 mL = 1 mg S) - Dissolve 2.225 g of potassium
magnesium perchlorate [Mg(ClO&] or phosphorus
iodate (KIOs) that has been dried at about 180°C to
pentoxide (P205) (Precaution - see Note 3). Connect
constant weight, in water and dilute to 1 L. Thoroughly
a rotameter between the purifying train and the furnace.
mix the solution.
Insert a small glass-wool plug in the upper end of the
7.10 Potassium lodate, Standard Solution (0.006238 glass tubing connecting the furnace with the absorber
M, 1 mL = 0.1 mg S) - Measure exactly 100 mL to catch oxides of tin. Connect the exit end of the
of KIO! solution (0.06238 M, 1 mL = 1 mg S) into combustion tube to the absorber with glass tubing,
a I-L volumetric flask, and dilute to volume with water. using gum rubber tubing to make connections. Position
Thoroughly mix the solution. the absorber so as to make this delivery line as short as

459
SD-1552 2001 SECTION V

Induction
Rotameter

Absorber

FIG. 3 SCHEMATIC ILLUSTRATION OF

FIG. 2 SCHEMATIC ILLUSTRATION OF RESISTANCE-TYPE FURNACE
INDUCTION-TYPE FURNACE

TABLE 2
SAMPLE WEIGHT FOR RESISTANCE FURNACE
TABLE 1 Normalityof Standard
SAMPLE WEIGHT FOR INDUCTION FURNACE Weight of Sample KIO, Solutionfor
Normality of Standard Sulfur Content. % to Be Taken.in4 Titration
Weight of Sample KIOsSolutionfor 0 ta 2 100 to 200 0.006238
Sulfur Content,% to Be Taken, mg Titration 2 to 5 100 to 200 0.01248
Lit0 10 100 to 200 0.06238
0 to 2 90/' 0.006238
2 to 4 soto 90 0.006238
over 10 (Note 7) (Note 7)
4to 10 50 ta 90 0.01248
Over 10 12.1.1 (Note 7)
A Approximate
drops of the appropriate standard KIOs solution (Table
2) to produce a faint blue color. Adjust the buret to zero.
9.3 Resistance-Type Furnace-IR Detection - Assem-
possible. Figure 2 illustrates schematically the assembled ble and adjust apparatus according to manufacturer’s
apparatus. Adjust the oxygen flow to 1 * 0.05 Umin. instructions. lnitialize microprocessor, check power sup-
Add 65 mL of HCI (3 + 197) and 2 mL of starch- plies, set oxygen pressure and flows and set furnace
iodide solution to the absorber. Add a sufficient amount temperature to 1371°C (2500°F).
of the appropriate standard KIO3 solution (Table I) to
9.3.1 Condition a fresh anhydrone scrubber with
produce a faint blue color. This co101 will serve as
four coal samples.
the end point for the titration. Adjust the buret to zero.
Turn on the furnace filament switch and allow at least 9.3.2 Calibrate the automatic balance according to
1 min warm-up before running samples (Precaution - manufacturer’s instructions.
see Note 3).
9.2 Resistance-Type Furnace-Assemble the appara-
10. Standardization
tus according to the instructions furnished by the manu-
facturer. Purify the oxygen by passing it through (1) 10.1 For Iodate Methods:
H$04 (relative density 1.84), (2) Ascarite, and (3)
Mg(ClO& or PzOs (Precaution - see Note 3). Connect
10.1.1 Determination of Alum Factor:
a rotameter between the purifying train and the furnace. 10.1.1.1 Because these rapid combustion meth-
Figure 3 illustrates schematically the assembled appara- ods involve the reversible reaction 2S02 + O2 = 2SOs,
tus. Turn on the current and adjust the furnace control it is not possible to evolve all the sulfur as SO*. The
to maintain a constant temperature of 1316 f 14°C equilibrium of the reaction is temperature dependent
(2400 f 25°F). Adjust the oxygen flow rate to 2 * and, in an oxygen atmosphere above 1316”C, about
0.1 L/min. Add 65 tnL of HCl (3 f 197) and 2 mL 97% of the sulfur is present as SO*. To assure that
of starch-iodide solution to the absorber. Add a few the furnace is in proper adjustment and that its operation

460
 ARTICLE 24 ~
produces acceptably high temperature, potassium alum
is employed for standardizing the apparatus. Depending
on the type of combustion equipment used, proceed as
described in Sections IO to 13 to determine the alum
factor. Use 15 mg weighed to +O.l mg of potassium
alum for this determination. Use the same materials in
the determination of the alum and standardization factors
as for the unknown samples. For example, V205 has
a definite effect and should be included if used for
unknowns as recommended in the procedure with the
resistance-type furnace (Note IO).
10.1.1.2 Calculate the alum factor as follows:
Alum factor (AF) = (S, x WA)/[lOO(V,, - V,)
x Cl1
where:
.S, = mass percent sulfur in potassium alum used,
WA= milligrams of potassium alum used,
V,= millilitres of standard KIOs solution used in
determining the alum factor,
V,= millilitres of standard KI03 solution used in the
blank determination, and
Cl = sulfur equivalent of the standard KI03 solution
used in determining the alum factor, mg/mL.
10.1.1.3 The alum factor should be in the range
from 1.02 to 1.08. If values smaller than 1.02 are
observed, confirm independently the sulfur content of
the alum and the sulfur equivalent of the KI03 solution
before repeating the alum factor determination. If values
larger than 1.08 are observed, make adjustments in
the equipment in accordance with the manufacturer’s
recommendation and repeat the alum factor determi-
nation.
10.1.2 Determination of Standardization Factor:
10.1.2.1 Because effects such as sample volatility
can also affect the relative recovery as SO> of the
sulfur originally present in the sample, it is necessary
to determine a standardization factor. Proceed
scribed in Sections 10 to 13, using an oil sample of
similar type to the unknown sample and of accurately
known sulfur content.
10.1.2.2 For IR detection, determine and load
the microprocessor with the calibration factor for the
particular type of sample to be analyzed (lubricating
oil, petroleum coke, residual fuel) as recommended by
the manufacturer.
10.1.2.3 Calculate the standardization factor as
follows:
LIQUID PENETRANT STANDARDS SD-1552
Standardization factor (F,J = (& x tV,)/[lOO (lJ, (2)
- VI>) x Cl
where:
S, = mass percent sulfur in standardization sample
used,
W, = milligrams of standardization sample used,
V, = millilitres of standard KIOJ solution used in the
blank determination,
!J,= millilitres of standard K103 solution used in
determining the standardization factor, and
C= sulfur equivalent of the standard KI03 solution
used in determining the standardization factor,
mg/mL.
(1)
10.1.3 Quality Control-Run a suitable analytical
quality control sample several times daily. When the
observed value lies between acceptable limits on a
quality control chart, proceed with sample determina-
tions.
11. Preparation of Coke
11.1 It is assumed that a representative sample has
been received for analysis.
11.2 Grind and sieve the sample received so as to
pass a 60-mesh (250~mm) sieve.
11.3 Dry the sieved material to constant weight at
105 to 110°C.
12. Procedure With Induction-Type Furnace
12.1 Sample Preparation - Add a 3.2 to 4.8~mm
(‘/8 to 3/&) layer of alundum or magnesium oxide
to a sample crucible. Make a depression in the bed
with the end of a stirring rod. Weigh the crucible to
0.1 mg. Weigh into the depression the proper amount
of sample according to Table 1 (12.1.1) (Note 7). Cover
the sample with a separator disk (Note 8. Place on
as de-
the separator disk the predetermined amount of iron
chips necessary to obtain the required temperature
(6.1.1.2). This is usually between 1.2 and 2.0 g, but
should be held constant with kO.05 g. Sprinkle about
0.1 g of tin on the iron. Cover the crucible with a lid
and place on the furnace pedestal.
12.1.1 Under no conditions shall an organic sample
larger than 100 mg be burned in an induction-type
furnace.
NOTE 7 - More concentrated KIO, solutions, such BS the 0.06238
N solution, may be found more convenient for samples containing
461
Sl).1552
NOTE 8 - The use of Ihc separator disk is optional.
12.2 Combustion and Titration - Turn on the plate
current switch. After about 1 min for warmup, raise
the pedestal and lock into position. The plate current
will fluctuate for a few seconds and should gradually
rise to a maximum value. Add the appropriate standard
K103 solution (Table 1) to the absorber to maintain
the blue color. Should the absorber solution become
completely colorless, discard the determination. Make
KIO, additions as the rate of evolution of SO:! dimin-
ishes such that, when combustion is completed, the
intensity of the blue color is the same as the initial
intensity. Combustion is complete when this color re-
mains for at least 1 min and the plate current has
dropped considerably. Record the volume of KI03
solution required to titrate the SOz evolved.
12.3 Blank Determination-Make a blank determina-
tion whenever a new supply of crucibles, materials, or
reagents is used. Follow the preceding procedure, but
omit the sample.
13. Procedure With Resistance-Type Furnace
13.1 Sample Preparation-Weigh into a combustion
boat the proper amount of sample according to Table
2. Add 100 * 5 mg of vanadium pentoxide and com-
pletely cover the mixture with Alundum.
13.2 Combustion and Titration - Place the boat in
the cool portion of the combustion tube, near the
entrance. To proceed with the combustion, push the
boat containing the sample progressively into the hotter
zone of the combustion tube using the equipment
provided by the manufacturers. The boat should be
advanced as rapidly as possible consistent with the rate
of evolution of SOz. Add the appropriate standard KI03
solution (Table 2) to the absorber to maintain the blue
c&x. Should the absorber solution become completely
colorless, discard the determination. Make KI03 addi-
tions as the rate of evolution of SO2 diminishes such
that, when combustion is completed, the intensity of
the blue color is the same as the initial intensity.
Combustion is complete when this color remains for
at least 1 min. Record the volume of KI03 solution
required to titrate the SO* evolved.
13.3 Blank Determination-Make a blank determina-
tion whenever a new supply of combustion boats,
materials, or reagents is used. Follow the above proce-
dure, but omit the sample.
2001 SECTION V
14. Procedure With Resistance Furnace-
IR Detection
14.1 Allow the system to warm up and the furnace
to reach operating temperature.
14.2 After homogeneity of the sample is assured,
select the sample size as follows: for liquid samples,
take up to 0.13 g for analysis and for solid samples,
take up to 0.4 g for analysis. In each case, mass percent
sulfur times weight of sample. must be less than or
equal to four in the case of the SC32 instrument, and
two in the case of the SC132 instrument. For other
instruments, consult the manufacturer’s instructions.
14.3 Determine and store the system blank value.
14.4 Weigh the samples into combustion boats and
record the net weights. It is possible to weigh and
store several weights in the microprocessor before
beginning a series of burns.
14.4.1 Fill the combustion boat to one-third capac-
ity with evenly spread MgO powder.
14.4.2 Form a slight trench in the MgO powder
with a scoop.
14.4.3 Place the combustion boat on the balance
and weigh an appropriate amount of the sample into
the trench in the MgO powder. Enter the weight.
14.4.4 Remove the combustion boat from the
balance and add MgO powder until the combustion
boat is filled to two-thirds capacity.
NOTE 9 - If unacceptable repeatability is encountered for particular
oil samples, combwion promoter such as V205 or the LECO product
Cm-Aid can be subsdtuted for the MgO.
NOTE IO - Caution - V201 can causedeteriorationof the furnace
ceramics so use it with arc.
14.5 Initiate oxygen flow and load boat into furnace.
14.6 When the analysis is complete, read the result
from the microprocessor.
14.7 Remove the expended combustion boat from
the furnace.
14.8 Make repeated runs until two results differ by
less than the repeatability of the method.
15. Calculation
15.1 Calculation for Iodate Detection - Calculate
the sulfur content of the sample as follows:
462
 ARTICLE 24 ~ LIQUID PENETRANT STANDARDS SD-1552

Sulfur, mass % = [lo0 (V - V,,) x F,Tx L-j/W (3) operators working in different laboratories on identical
test material would, in the long run, in the normal and
where: correct operation of the test method, exceed the follow-
V= standard KIO3 solution, mL, used in the ing values in only one case in twenty:
analysis, Sulf!Jr,Mass,% Reproducibility
V, = standard KIOs solution, mL, used in the blank Rhl”ge lodnte IRE
determination, 0.0 to 0.5 0.08 0.13
F, = standardization factor (see lO.l.‘Z), 0.5 to 1.0 0.11 0.21
C= sulfnr equivalent of the standard KIO? solution 1.0 to 2.0 0.17 0.27
used in the analysis, mg/mL, and 2.0 to 3.0 0.26 0.38
3.0 to 4.0 0.40 0.44
W= milligrams of sample used in the analysis. 4.0 to 5.0 0.54 0.49
15.2 Calculation for IR Detection: 11.2 For Petroleum Cokes by Iodate and IR Meth-
15.2.1 Report all results using the microprocessor. ods - The precision of the test method as determined
by statistical examination of interlaboratory results is
15.2.2 Report the average of two results.
as f0110ws:
17.2.1 Repeatability - The difference between
16. Report two test results obtained by the same operator with
the same apparatus under constant operating conditions
16.1 In the range from 0.05 to 5.00 mass % sulfur, on identical test material would, in the long run, in
report to the nearest 0.01 mass %. In the range from the normal and correct operation of the test method,
5 to 30 mass % sulfur, report to the nezuest 0.1 mass %. exceed the following values in only one case in twenty:

I = 0.05x
17. Precision and Bias
17.1 For Petroleum Products by Iodate and IR where X is the average of the two test results.
Methods - The precision of this test method as deter-
17.2.2 Reproducibility - The difference between
mined by statistical examination of interlaboratory re-
two single and independent results obtained by different
sults is as follows:
operators working in different laboratories on identical
17.1.1 Repeatability - The difference between test material could, in the long run, in the normal and
two test results obtained by the same operator with correct operation of the test method, exceed the follow-
the same apparatus under constant operating conditions ing values in only one case in twenty:
on identical test material would, in the long run, in
the normal and correct operation of the test method, R = 0.22X
exceed the following values in only one case in twenty:
where X is the average of the two test results.
Sulfur. Mass, % Repeatability
Range lodade IRE 17.3 Bias - The bias of the procedure in this test
0.0 to 0.5 0.05 0.04 method is being determined.
0.5 to 1.0 0.07 0.07
I .a to 2.0 0.10 0.09
2.0 to 3.0 0.16 0.12
3.0 to 4.0 0.22 0.13 18. Keywords
4.0 to 5.0 0.24 0.16
18.1 furnace; high temperature; induction furnace;
17.1.2 Reproducibility - The difference between iodate titration; IR detection; petroleum; resistance;
two single and independent results obtained by different sulfnr; titration

463
 STANDARD TEST METHOD FOR
LIQUID PENETRANT EXAMINATION
SE-165
(Identical with ASTM Specification E 165-95)
1. SCOp2
1.1 This test method covers procedures for penetrant
examination of materials. They are nondestructive test-
ing methods for detecting discontinuities that are open
to the surface such as cracks, seams, laps, cold shuts,
laminations, through leaks, or lack of fusion and are
applicable to in-process, final, and maintenance exami-
nation. They can be effectively used in the examination
of nonporous, metallic materials, both ferrous and non-
ferrous, and of nonmetallic materials such as glazed
OTfolly densified ceramics, certain nonporous plastics,
and glass.
1.2 This test method also provides a reference:
1.2.1 By which a liquid penetrant examination
process recommended or required by individual organi-
zations can be reviewed to ascertain its applicability
and completeness.
1.2.2 For use in the preparation of process specifi-
cations dealing with the liquid penetrant examination
of materials and parts. Agreement by the user and
the supplier regarding specific techniques is strongly
recommended.
1.2.3 For use in the organization of the facilities
and personnel concerned with the liquid penetrant exam-
ination.
1.3 This test method does not indicate or suggest
criteria for evaluation of the indications obtained. It
should be pointed out, however, that after indications
have been produced, they must be interpreted or classi-
fied and then evaluated. For this purpose there must
be a separate code or specification or a specific
agreement to define the type, size, location, and direction
of indications considered acceptable, and those consid-
ered unacceptable.
1.4 The values stated in inch-pound units are to be
regarded as the standard. SI units are provided for
information only.
1.5 This standard does nof purport fo address all
of the safety concerns, if any, associated wirh ifs use.
Ir is the responsibility of the US~Tof this standard fo
esrablish appropria@ safety and health practices and
de&mine the applicability of regularory limitations
prior lo use. For specific hazard statements, see Notes
5, 12, and 20.
2. Referenced Documents
2.1 ASTM Srandards:
D 129 Test Method for Sulfur in Petroleum Products
(General Bomb Method)
D 516 Test Method for Sulfate Ion in Water
D 808 Test Method for Chlorine in New and Used Petro-
leum Products (Bomb Method)
D 1193 Specification for Reagent Water
D 1552 Test Method for Sulfur in Petroleum Products
(High-Temperature Method)
D 4327 Test Method for Anions in Water in Chemically
Suppressed Ion Chromatography
E 433 Reference Photographs for Liquid Penetrant In-
spection
E 543 Practice for Evaluating Agencies that Perform
Nondestructive Testing
E 1208 Test Method for Fluorescent Liquid Pen&ant
Examination Using the Lipophilic Post-Emulsification
Process
E 1209 Test Method for Fluorescent Liquid Penetrant
Examination Using the Water-Washable Process
E 1210 Test Method for Fluorescent Liquid Penetrant
Examination Using the Hydrophilic Post-Emulsifica-
tion Process
 ARTICLE 24 ~ LIOUID PENEI’RANT STANDAKIIS SE-165

E 1219 Test Method for Fluorescent Liquid Pen&ant TABLE 1

Examination Using the Solvent-Removable Process CLASSIFICATION OF PENETRANT EXAMINATION
E 1220 Test Method for Visible Penetrant Examination TYPES AND METHODS
Using the Solvent-Removable Process Type I - Fluorescent Penetvant Examination
E 1316 Terminology for Nondestructive Examinations Method A - Water-washable (see Test Method E 1209,
E 1418 Test Method for Visible Pen&rant Examination Method B - Post-emulsifiable, lipophilic (see Test Method E
Using the Water-Washable Process 1208)
Method C ~ Solvent removable (see Test Method E 1219)
2.2 ASNT Document: Method D - Post-emulsifiable, hydrophilic (see Teat Method
Recommended Practice SNT-TC-IA for Nondestructive
Testing Personnel Qualification and Certification Type II - Visible Pen&ant Examination
Method A - Water-washable (see Test Method E 1418)
2.3 Military Standard: Method C - Solvent removable (see Test Method E
MIL-STD-410 Nondeshwtive Testing Personnel Quali- 1220)
fication and Certification
2.4 APHA Standard:
429 Method for the Examination of Water and Waste-
water
Each of the various methods has been designed for
specific uses such as critical service items, volume of
3. Terminology parts, portability or localised areas of examination. The
method selected will depend accordingly on the service
3.1 The definitions relating to liquid penetrant exami-
requirements.
nation, which appear in Terminology E 1316, shall
apply to the terms used in this standard.
6. Classification of Penetrations and Methods
4. Summary of Test Method 6.1 Liquid penetrant examination methods and types
are classified as shown in Table 1.
4.1 A liquid pen&rant which may be a visible or a
fluorescent material is applied evenly over the surface 6.2 Fluorescent penetrant examination utilizes pene-
being examined and allowed to enter open discontinu- trants that fluoresce brilliantly when excited by black
ities. After a suitable dwell time, the excess surface light (see 8.9.1.2). The sensitivity of fluorescent pene-
penetrant is removed. A developer is applied to draw trants depends on their ability to be retained in the
the entrapped pen&ant out of the discontinuity and various size discontinuities during processing, then to
stain the developer. The test surface is then examined bleed out into the developer coating and produce indica-
to determine the presence or absence of indications. tions that will fluoresce. Fluorescent indications are
many times brighter than their surroundings when
NOTE I: - The developer may be omilted by agreement between
purchaser and supplier.
viewed under black light illumination.

NOTE 2: Caution - Fluorescent pen&ant examination shall nol

follow a visible penetrant examination unless the procedurehas been
qualified in accordance with 10.2, because visible dyes may CRUST
deterioration 01 quenchingof fluorescentdyes.
4.2 Processing parameters, such as surface preclean-
ing, penetration time and excess penetrant removal
methods, are determined by the specific materials used,
the nature of the part under examination (that is, size,
shape, surface condition, alloy), and type of discontinu-
ities expected.
5. Significance and Use
5.1 Liquid penetrant examination methods indicate
the presence, location and, to a limited extent, the
nature and magnitude of the detected discontinuities.
6.3 Visible penerrant examination uses a penetrant
that can be seen in visible light. The pen&ant is
usually red, so that the indications produce a definite
contrast with the white background of the developer.
The visible penetrant process does not require the use
of black light. However, visible penetrant indications
must be viewed under adequate white light (see X.9.2.1).
I. Types of Materials
7.1 Liquidpenetrant examination materials (see Notes
3, 4, and 5) consist of fluorescent and visible penetrants,
emulsifiers (oil-base and water-base; fast and slow
acting), solvent removers and developers. A family of
liquid penetrant examination materials consists of the
applicable pen&ant and emulsifier or remover, as rec-

465
SE-165
ommcnded by the manufacturer. Intermixing of materi-
als from various manufacturers is not recommended.
NOTE 5: Warning - These materials may be flammable
hazardous and foxi~ vapors. Observe all manufacturer’s
and precautionary statements.
7.2 Penetrants:
7.2.1 Post-EmulsiJiable Penetranfs are designed to
be insoluble in water and cannot be removed with
water rinsing alone. They are designed to be selectively
removed from the surface using a separate emulsifier.
The emulsifier, properly applied and given a proper
emulsification time, combines with the excess surface
penetrant to form a water-washable mixture, which can
be rinsed from the surface, leaving the surface free of
fluorescent background. Proper emulsification time must
be experimentally established and maintained to ensure
that over-emulsification does not occur, resulting in
loss of indications.
7.2.2 Water-Washable Peneirants are designed to
be directly water-washable from the surface of the test
part, after a suitable penetrant dwell time. Because the
emulsifier is “built-in” to the water-washable penetrant,
it is extremely important to exercise proper process
control in removal of excess surface pen&ant to ensure
against overwashing. Water-washable penetrants can be
washed out of discontinuities if the rinsing step is too
long or too vigorous. Some penetrants are less resistant
to overwashing than others.
7.2.3 Solvent-Removable Penetrants are designed
so that excess surface penetrant can be removed by
wiping until most of the pen&ant has been removed.
The remaining traces should be removed with the
solvent remover (see 8.6.4.1). To minimize removal of
penetrant from discontinuities, care should be taken to
avoid the use of excess solvent. Flushing the surface
with solvent to remove the excess penetrant is pro-
hibited.
7.3 Emulsifiers:
7.3.1 Lipophilic Emulsijiers are oil-miscible liquids
used to emulsify the excess oily pen&rant on the surface
of the pan, rendering it water-washable. The rate of
diffusion establishes the emulsification time. They are
either slow- or fast-acting, depending on their viscosity
2001 SECTION V
and chemical composition, and also the surface
roughness of the area being examined (see 8.6.2).
13.2 Hydrophilic Emulsijiers are water-miscible
liquids used to emulsify the excess oily fluorescent
penetrant on the surface of the part, rendering it water-
washable (see 8.6.3). These water-base emulsifiers (de-
tergent-type removers) aTe supplied as concentrates to
be diluted with water and used as a dip or spray.
or emit The concentration, use and maintenance shall be in
instructions
accordance with manufacturer’s recommendations.
7.3.2.1 Hydrophilic emulsifiers function by dis-
placing the excess penetrant film from the surface of
the part through detergent action. The force of the
water spray or air/mechanical agitation in an open dip
tank provides the scrubbing action while the detergent
displaces the film of penetrant from the part surface.
The emulsification time will vary, depending on its
concentration, which can be monitored by the use of
a suitable refractometer.
7.4 Solvent Removers function by dissolving the
penetrant, making it possible to wipe the surface clean
and free of excess penetrant as described in 8.6.4.
7.5 Developers - Development of penetrant indica-
tions is the process of bringing the pen&ant out of open
discontinuities through blotting action of the applied
developer, thus increasing the visibility of the indica-
tions.
7.5.1 Dry Powder Developers are used as supplied
(that is, free-flowing, non-caking powder) in accordance
with 8.8.2. Care should be taken not to contaminate
the developer with fluorescent penetrant, as the penetrant
specks can appear as indications.
7.52 Aqueous Developers are normally supplied
as dry powder particles to be either suspended or
dissolved (soluble) in water. The concentration, use and
maintenance shall be in accordance with manufacturer’s
recommendations (see 8.8.3).
NOTE 6: Caution - Aqueousdevelopers may causestrippingof
indications if not properly applied and controlled. The procedure
should be qualified in accordance with 10.2.
7.5.3 Nonaqueous Wet Developers are supplied as
suspensions of developer particles in a nonaqueous
solvent carrier ready for use as supplied. Nonaqueous,
wet developers form a coating on the surface of the
part when dried, which serves as the developing medium
(see 8.8.4).
NOTE 7: Caution-This type of developer is intended for applicntion
by spray only.
466
 ARTICLI? 24 ~ LIQUID
7.5.4 Liquid Film Urvelopers are solutions or
colloidal suspensions of resins/polymer in a suitable
carrier. These developers will form a transparent or
translucent coating on the surface of the part. Certain
types of film developer may be stripped from the part
and retained for record purposes (see X.8.5).
8. Procedure
8.1 The following general processing guidelines apply
(see Figs. 2, 3, and 4) to both fluorescent and visible
penetrant examination methods (see Fig. 1).
8.2 Temperature Limits - The temperature of the
pen&ant materials and the surface of the part to be
processed should be between 50 and 100°F (10 and
38°C). Where it is not practical to comply with these
temperature limitations, qualify the procedure as de-
scribed in 10.2 at the temperature of intended use and
as agreed to by the contracting parties.
8.3 Surface Conditioning Prior to Penetrant Examina-
tion - Satisfactory results usually may be obtained
on surfaces in the as-welded, as-rolled, as-cast, or as-
forged conditions (or for ceramics in the densified
conditions). Sensitive penetrants are generally less easily
rinsed away and are therefore less suitable for rough
surfaces. When only loose surface residuals are present,
these may be removed by wiping with clean lint-
free cloths. However, precleaning of metals to remove
processing residuals such as oil, graphite, scale, insulat-
ing materials, coatings, and so forth, should be done
using cleaning solvents, vapor degreasing or chemical
removing processes. Surface conditioning by grinding,
machining, polishing or etching shall follow shot, sand,
grit or vapor blasting to remove the peened skin and
when pen&rant entrapment in surface irregularities
might mask the indications of unacceptable discontinu-
ities or otherwise interfere with the effectiveness of
the examination. For metals, unless otherwise specified,
etching shall be performed when evidence exists that
previous cleaning, surface treatments or service usage
have produced a surface condition that degrades the
effectiveness of penetrant examination. (See Annex
Al .I, I .8 for precautions.)
NOTE s - When agreed between purchaserand supplier,grit
blastingwithout subsequentetchingmay be an acceptable cleaning
method.
NOTE 9: Caution - Saud or shot blasting may possibly close
discontinuities and extreme care should be used with grinding and
machining operations to avoid masking discontinuities.
NOTE 10 ~ For stNClUrat or ekCmOniC CeretiCS, SIU’ke preQEdkm
by grinding, sand blasting and etching for penetrant examinatiou is
not recommended because of the potentialfor damage.
461
PENETRANT STANDARDS SE-165
8.4 Removal of Surjkace Contaminants:
8.4.1 Prccleurring - The snccess of any penetrant
examination procedure is greatly dependent upon the
surrounding surface and discontinuity being free of any
contaminant (solid or liquid) that might interfere with
the pen&rant process. All parts or areas of parts to be
examined must be clean and dry before the penetrant
is applied. If only a section of a part, such as a weld,
including the heat affected zone is to be examined, all
contaminants shall be removed from the area being
examined as defined by the contracting parties. “Clean”
is intended to mean that the surface must be free of
rnst, scale, welding flux, weld spatter, grease, paint,
oily films, dirt, and so forth, that might interfere with
the penetrant process. All of these contaminants can
prevent the penetrant from entering discontinuities (see
Annex or Cleaning of Parts and Materials).
NOTE II: Caution - Residues from cleaning processes such 8s
stroug alkalies,pickling solutionsand chromates.in p.urticular,may
adversely react with the pen&ant and reduce its sensitivity and
perf”rma”ce.
8.4.2 Drying afler Cleaning - It is essential that
the surface of parts be thoroughly dry after cleaning,
since any liquid residue will hinder the entrance of
the pen&rant. Drying may be accomplished by warming
the parts in drying ovens, with infrared lamps, forced
hot air, or exposure to ambient temperature.
8.5 Penerrant Application - After the part has been
cleaned, dried, and is within the specified temperature
range, the pen&rant is applied to the surface to be
examined so that the entire part or area under examina-
tion is completely covered with penetrant.
8.5.1 Modes of Application - There are various
modes of effective application of pen&rant such as
dipping, brushing, flooding, or spraying. Small parts
are quite often placed in suitable baskets and dipped
into a tank of penetrant. On larger parts, and those
with complex geometries, penetrant can be applied
effectively by brushing or spraying. Both conventional
and electrostatic spray guns are effective means of
applying liquid pen&rants to the part surfaces. Electro-
static spray application can eliminate excess liquid
build-up of penetrant on the part, mini&e overspray,
and minimize the amount of penetrant entering hollow-
cored passages which might serve as penetrant reser-
voirs, causing severe bleedout problems during examina-
tion. Aerosol sprays are conveniently portable and
suitable for local application.
SR-165 2001 SECTION V

FIG. 1 FLUORESCENT AND VISIBLE PENETRANT INSPECTION GENERAL PROCESSING PROCEDURES

FLOWSHEET

NOTE 12: Caution - Not all penetrant materials are suitable for should be taken to prevent pools of penetrant from
electmtatic spray applications, so tests should be conducted prior
m use. forming on the part), while allowing for proper pen&rant
dwell time (see Table 2). The length of time the
NOTE 13: Warning - With spray applications. it is important that
there be proper venfilalion. This is generally accomplished through penetrant must remain on the part to allow proper
the use of a properly designed spray booth and exhaust system. penetration should be as recommended by the pen&ant
manufacturer. Table 2, however, provides a guide for
8.5.2 Penetranf Dwell Time - After application, selection of penetrant dwell times for a variety of
allow excess pen&ant to drain from the part (care materials, forms, and types of discontinuity. Unless

468
 ARTICLE 24 ~ LIQUID PENETRANT STANDARDS

FIG. 2 GENERAL PROCEDURE FLOWSHEET FOR PENETRANT EXAMINATION USING THE WATER-
WASHABLE PROCESS (TEST METHOD E 1209 FOR FLUORESCENT AND TEST METHOD E 1220 FOR VISIBLE
LIGHT)

otherwise specified, the dwell time shall not exceed
the maximum recommended by the manufacturer.
NOTE 14 ~ For smne specificapplicationsin structuralceramics
(for example, detecting parting lines in slip-cast material), the required
penetrant dwell time should be determined experimentally and may
he longer than that shown in Table 1 and its notes.
8.6 Penetrant Removal
8.6.1 Water Washable:
8.6.1.1 Removal of Excess Penetrants - After
the required penetration time, the excess pen&ant on
the surface being examined must be removed with
water, usually a washing operation. It can be washed
off manually, by the use of automatic or semi-automatic
water-spray equipment or by immersion. For immersion
rinsing, parts are completely immersed in the water
bath with air or mechanical agitation. Accumulation of
water in pockets or recesses of the surface must be
avoided. If the final rinse step is not effective, as
evidenced by excessive residual surface penetrant after
rinsing, dry (see 8.7) and reclean the part, then reapply
the penetrant for the prescribed dwell time.
(a) The temperature of the water should be relatively
constant and should be maintained within the range of
50 to 100°F (10 to 38°C).
(bj Spray-rinse water pressure should not be greater
than 40 psi (280 kPa).

469
SIC-165 2001 SECTION V

FIG. 3 TYPE 2 - POST EMULSIFIABLE PROCEDURES A-2 (FLUORESCENT) AND B-2 (VISIBLE)

(c) Rinse time should not exceed 120 s unless other- the surface with a clean, absorbent material dampened
wise specified by part of material specification. with water until the excess surface penetrant is removed,
as determined by examination under black light for
NOTE 15: Caution - Avoid overwashing. Excessive washing can
causepenetrantto be washed ouLof discontinuities.With fluorescent fluorescent methods and white light for visible methods.
penetrantmethodsperform the rinsing operationunder black light
so that it can be determinedwhen the surfacepenetranthas been 8.6.2 Lipophilic Emulsijication:
adequately removed.
8.6.2.1 Application of Emulsijier -
After the
8.6.1.2 Removal by Wiping -In special applica- required penetration time, the excess pen&rant on the
tions, pen&ant removal may be performed by wiping part must be emulsified by immersing or flooding

470
 ARTICLE 24 - LlQUll, PENETRANT STANDARDS

FIG. 4 SOLVENT-REMOVABLE PENETRANT EXAMINATION GENERAL PROCEDURE FLOWSHEET

(TEST METHOD E 1219 FOR FLUORESCENT AND TEST METHOD E 1220 FOR VISIBLE LIGHT)

the parts with the required emulsifier (the emulsifier
combines with the excess surface penetrant and makes
the mixture removable with water rinsing). After appli-
cation of the emulsifier, the parts are drained in a
manner that prevents the emulsifier from pooling on
the part(s).
8.6.2.2 Emulsi&afion Dwell Time begins as soon
as the emulsifier has been applied. The length of time that
the emulsifier is allowed to remain on a part and in contact
with the penetrant is dependent on the type of emulsifier
employed and the surface condition (smooth or rough).
Nominal emulsification time should be as recommended
by the manufacturer. The actual emulsification time must
be determined experimentally for each specific applica-
tion. The surface finish (roughness) of the part is a signifi-
cant factor in the selection of and in the emulsification time
of an emulsifier. Contact time should be kept to the least
possible time consistent with an acceptable background
and should not exceed the maximum time specified for the
part or material.
8.6.2.3 Post Rinsing - Effective post rinsing
of the emulsified pen&rant from the surface can be

471
SF,-165 2001 SECTION V

TABLE 2
RECOMMENDED MINIMUM DWELL TIMES
Dwell Times” (minutes)
Typeof
Material Form Discontinuity Penetrant8 DeveloperC
Alumioum, 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 forms1 10 10
forgings, plate
Carbide-tipped tools lack of fusion, porosity, cracks 5 10
Plastic all forms cracks 5 10
GlElSS all forms cracks 5 10
Ceramic all forms cracks, porosity 5 10

A For temperature range from 50 to loooF (10 to 38°C) for fluorescent penetrants and 50 to 1WF (lo to 52°C) for visible penetrant.
‘Maximum penetrant dwell time in accordance with 8.52.
cDevelopment 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

accomplished using either manual, semi-automated, or 8.6.3 Hydrophilic Emulsijication:

automated water immersion or spray equipment or
combinations thereof.
8.6.2.4 immersion - For immersion post rinsing,
parts are completely immersed in the water bath with
air or mechanical agitation. The time and temperature
should be kept constant.
(a) The maximum dip-rinse time should not exceed
120 s unless otherwise specified by part or material
specification.
(bj The temperature of the water should be relatively
constant and should be maintained within the range of
50 to 100°F (10 to 38°C). Caution: A touch-up rinse
may be necessary after immersion.
8.6.2.5 Spray Post Rinsing - Effective post
rinsing following emulsification can also be accom-
plished by either manual or automatic water spray
rinsing of the parts as follows:
(a) Control rinse water temperature within the range
of 50 to 100°F (10 to 38°C).
(b) Spray rinse water pressure should be in accord-
ance with manufacturers’ recommendations.
(c) The maximum spray rinse time should not exceed
120 s unless othemise specified by part or materials
specification.
8.6.2.6 Rinse EfSectiveness - If the emulsifica-
tion and final rinse step is not effective, as evidenced
by excessive residual surface penetrant after emulsifica-
tion and rinsing, dry (see 8.7) and reclean the part and
reapply the penetrant for the prescribed dwell time.
8.6.3.1 Prerinsing - Directly after the required
penetration time, it is recommended that the parts be
prerinsed with water prior to emulsification (8.6.3.3).
This step allows for the removal of excess surface
penetrant from the parts prior to emulsification so as
to minimize the degree of pen&rant contamination in
the hydrophilic emulsifier bath, thereby extending its
life. In addition, prerinsing of penetrated parts minimizes
possible oily penetrant pollution in the final rinse step
of this process. This is accomplished by collecting the
prerinsings in a holding tank, separating the penetrant
from water.
8.6.3.2 Prerinsing Controls - Effective prerins-
ing is accomplished by either manual or automated
water spray rinsing of the parts as follows:
(a) Water should be free of contaminants that could
clog spray nozzles or leave a residue on parts.
(bJ Control water temperature within the range of
50 to 100°F (10 to 38°C).
(c) Spray rinse at a water pressure of 25 to 40 psi
(175 to 275 kPa).
(d) Prerinse time should be the least possible time
(nominally 60 s maximum) to provide a consistent
residue of penetrant on parts. Wash time is to be as
specified by the part or material specification.
(e) Remove water trapped in cavities using filtered
shop air at a nominal pressure 25 psi (175 kPa) or a
suction device to remove water from pooled areas.
of Emulsifier - After the
8.6.3.3 Application
required penetration time and following the prerinse,

472
 ARTICIB 24 ~ LlQtJlD
the residual surface penetrant on part(s) must be emulsi-
fied by immersing the part(s) in a hydrophilic emulsifier
bath (8.6.3.4) or by spraying the part(s) with the
emulsifier (8.6.3.5) thereby rendering the remaining
residual surface penetrant water-washable in the final
rinse station (8.6.3.6).
8.6.3.4 Immersion -For immersion application,
parts are completely immersed in the emulsifier bath.
The hydrophilic emulsifier should be gently agitated
throughout the contact cycle.
(aj Bath concentration should be as recommended
by the manufacturer. Most hydrophilic emulsifiers are
used within the range of 20 to 33% in water. Nominal
use concentration for immersion applications is 20%.
(b) Bath temperatures should be maintained between
50 and 100°F (10 to 38°C).
(cl Immersion contact time should he kept to the
minimum time consistent with an acceptable background
and should not exceed 120 s or the maximum time
stipulated by the part or material specification.
(d) Emulsifier drain time begins immediately after
parts have been withdrawn from the emulsifier tank
and continues until the parts are washed in the final
rinse station (8.6.3.6). This drain time should be kept
to a minimum to avoid over emulsification and should
not exceed 90 s.
8.6.3.5 Spray Application - For spray applica-
tion following the prerinse step, parts are emulsified
by the spray application of an emulsifier. All part
surfaces should be evenly and uniformly sprayed to
effectively emulsify the residual pen&rant on part sur-
faces to render it water-washable.
(al The concentration of the emulsifier for spray
apphcatmn should be in accordance with the manufac-
turer’s recommendations, but should not exceed 5%.
(b) Temperature to be maintained at 50 to 100°F
(IO to 38°C).
(cl The spray pressure should be 25 psi (175 kPa)
max for air and 40 psi (280 kPa) max for water.
(d) Contact time should be kept to the minimum
consistent with an acceptable background and should
not exceed 120 s or the maximum time stipulated by
the part or material specification.
8.6.3.6 Post-Rinsing of Hydrophilic Emulsified
Parts - Effective post-rinsing of emulsified penetrant
from the surface can be accomplished using either
manual, semi-automated, or automated water immersion
or spray equipment or combinations thereof.
413
PENETRANT STANDARDS SE-165
8.6.3.1 Immersion Post-Rinsing - Paris are to
be completely immersed in the water bath with air or
mechanical agitation.
(a) The temperature of the water should be relatively
constant and should be maintained within the range of
50 to 100°F (10 to 38°C).
(b) The maximum dip rinse time should not exceed
120 s unless otherwise specified by part or material
specification, Caution: A touch-up rinse may be neces-
sary after immersion.
8.6.3.8 Spray Post-Rinsing-Following emulsi-
fication parts can be post-rinsed by water spray rinsing
as follows:
(aI Control rinse water temperature within the range
of 50 to 100°F (IO to 38°C).
(b) Spray rinse water pressure should be in accord-
ance with manufacturer’s instructions.
(c) The maximum spray rinse time should not exceed
120 s unless otherwise specified by part or materials
specification.
8.6.3.9 If the emulsification and final rinse steps
are not effective, as evidenced by excessive residual
surface pen&ant after emulsification and rinsing, dry
(see 8.7) and reclean the part and reapply the penetrant
for the prescribed dwell time.
8.6.4 Solvent-Removable Penetrants:
8.6.4.1 Removal of Excess Penetrant - After
the required penetration time, the excess penetrant is
removed insofar as possible, by using wipers of a dry,
clean, lint-free material and repeating the operation
until most traces of penetrant have been removed. Then
using a lint-free material lightly moistened with solvent
remover the remaining traces are gently wiped to avoid
removing penetrant from discontinuities. Avoid the use
of excess solvent. If the wiping step is not effective,
as evidenced by difficulty in removing the excess
pen&rant, dry the part (see 8.7), and reapply the pene-
trant for the prescribed dwell time. Flushing the surface
with solvent following the application of the penetrant
and prior to developing is prohibited.
8.7 Drying - Drying the surface of the part(s) is
necessary prior to applying dry or nonaqueous devel-
opers or following the application of the aqueous devel-
oper. Drying time will vary with the size, nature, and
number of parts under examination.
8.7.1 Drying Modes - Parts can be dried by
using a hot-air recirculating oven, a hot or cold air
blast, or by exposure to ambient temperature, particu-
larly when the excess surface penetrant was removed
SK-l(i5
with a solvent. Drying is best done in a thermostatically
controlled recirculating hot-air dryer. Local heating or
cooling is permitted provided the temperature of the
part remains in the range of 50 to 100°F (10 to 38°C)
for fluorescent methods and in the range of 50 to
125°F (IO to 52°C) for visible methods unless otherwise
agreed by the contracting parties.
NOTE 16: Caution - Drying oven temperature should
160°F (71°C).
8.7.2 Drying Time Limits - Do not allow parts
to remain in the drying oven any longer than is necessary
to dry the surface. Times over 30 min in the dryer
may impair the sensitivity of the examination.
8.8 Developer Application:
8.8.1 Modes of Application - There are various
modes of effective application of the various types of
developers such as dusting, immersing, flooding or
spraying. The size, configuration, surface condition,
number of parts to be processed, and so forth, will
influence the choice of developer application.
8.8.2 Dry Powder Developer - Dry powder devel-
opers should be applied immediately after drying in
such a manner as to ensure complete part coverage.
Parts can be immersed in a container of dry developer
or in a fluid bed of dry developer. They can also be
dusted with the powder developer through a hand
powder bulb or a conventional or electrostatic powder
gun. It is common and effective to apply dry powder
in an enclosed dust chamber, which creates an effective
and controlled dust cloud. Other means suited to the
size and geometry of the specimen may be used,
provided the powder is dusted evenly over the entire
surface being examined. Excess powder may be removed
by shaking or tapping the part, or by blowing with
low-pressure (5 to 10 psi) (34 to 70 kPa) dry, clean,
compressed air.
NOTE 17: Caution - The air ~~esrn intensity should
experimentally for each application.
8.8.3 Aqueous Developers - Aqueous developers
should be applied to the part immediately after the
excess penetrant has been removed and prior to drying.
Aqueous developers should be prepared and maintained
in accordance with the manufacturer’s instructions and
applied in such a manner as to ensure complete, even,
part coverage. Caution should be exercised when using
an aqueous developer with water-washable penetrants
to avoid possible stripping of indications. Aqueous
developers may be applied by spraying (see Note 17),
flowing, or immersing the part. It is common to immerse
2001 SECTION V
the parts in a prepared developer bath. Immerse parts
only long enough to coat all of the part surfaces with
the developer (see Note 18). Then remove parts from
the developer bath and allow to drain. Drain all excess
developer from recesses and trapped sections to elimi-
nate pooling of developer, which can obscure discontinu-
ities. Dry the parts in accordance with 8.7. The dried
developer coating appears as a translucent or white
not exceed
coating on the part.
NOTE 18: Caution - Atomised spraying is not recommended since
a spotty film may result.
NOTE 19: Caution - If parts are left in the bath too long,
indications may leach out.
8.8.4 Nonaqueous Wet Developers - After the
excess penetrant has been removed and the surface has
been dried, apply developer by spraying in such a
manner as to ensure complete part coverage with a
thin, even film of developer. These types of developer
carrier evaporate very rapidly at normal room tempera-
ture and do not, therefore, require the use of a dryer (see
Note 20). Dipping or flooding parts with nonaqueous
developers is prohibited, since they may flush or dissolve
the penetrant from within the discontinuities because
of the solvent action of these types of developers.
NOTE 20: Warning - The vapors from the evaporadng, volatile
solvent developer carrier may be hazardous. Proper ventilation should
be provided in ali cases, but especially when the surface to be
examined is inside a closed volume, such as a process drum or a
small storage tank.
8.8.5 Liquid Film Developers -Apply by spraying
as recommended by the manufacturer. Spray parts in
such a manner as to ensure complete part coverage of
the area being examined with a thin, even film of
developer.
8.8.6 Developing Time - The length of time the
developer is to remain on the part prior to examination
be established should be not less than IO min. Developing time
begins immediately after the application of dry powder
developer and as soon as the wet (aqueous and nonaque-
ous) developer coating is dry (that is, the solvent carrier
has evaporated to dryness). The maximum permitted
developing times are 2 h for aqueous developers and
1 h for nonaqueous developers.
8.9 Examination - Perform examination of parts
after the applicable development time as specified in
8.8.6 to allow for hleedout of penetrant from discontinu-
ities into the developer coating. It is good practice to
observe the bleedout while applying the developer as
an aid in interpreting and evaluating indications.
414
 ARTICLE 24 ~ LlQUID
8.9.1 Fluorescent Light Examination:
8.9.1.1 Visible Ambient Light Level - Examine
fluorescent pen&rant indications under black light in a
darkened area. Visible ambient light should not exceed
2 ft candles (20 Lx). The measurement should be made
with a suitable photographic-type visible light meter
on the surface being examined.
8.9.1.2 Black Light Level Control - Black
light intensity, minimum of 1000 pW/cn?, should be
measured on the surface being examined, with a suitable
black light meter. The black light wavelength shall be
in the range of 320 to 380 nm. The intensity should
be checked weekly to ensure the required output. Re-
flectors and filters should be checked daily for cleanli-
ness and integrity. Cracked or broken ultraviolet (UV)
filters should be replaced immediately. Defective bulbs,
which radiate UV energy, must be replaced before
further use. Since a drop in line voltage can cause
decreased black light output with consequent inconsist-
ent performance, a constant-voltage transformer should
be used when there is evidence of voltage fluctuation.
Caution: Certain high-intensity black light may emit unacceptable
anmunts of visible light, which will cause fluorescent indications ta
disappear. Care shauld be taken ta use only bulbs certified by the
supplier to be suitable for such examination purposes.
NOTE 21 ~ The recommended minimum light intensity in X.9.1.2
is intcnded for general usage. For critical examinations, higher
intensity levels may he required.
8.9.1.3 Black Light Warm-Up - Allow the
black light to warm up for a minimum of 10 min prior
to its use or measurement of the intensity of the
ultraviolet light emitted.
8.9.1.4 Visual Adaptation - The examiner
should be in the darkened area for at least 1 min
before examining parts. Longer times may be necessary
under some circumstances.
NOTE 22: Caution -Photochromic lenses shall not he worn during
examination.
8.92 Visible Light Examination:
8.9.2.1 Visible Light Level - Visible penetrant
indications can be examined in either natural or artificial
light. Adequate illumination is required to ensure no
loss in the sensitivity of the examination. A minimum
light intensity at the examination site of 100 fc (1000
Lx) is recommended.
PENETRANT STANDARDS SE-165
8.9.3 Housekeeping - Keep the examination area
free of interfering debris, including fluorescent objects.
Practice good housekeeping at all times.
8.9.4 Evaluation - Unless otherwise agreed, it
is normal practice to interpret and evaluate the disconti-
nuity based on the size of the indication (see Referenced
Photographs E 433).
8.10 Post Cleaning - Post cleaning is necessary in
those cases where residual pen&ant or developer could
interfere with subsequent processing or with service
requirements, It is particularly important where residual
penetrant examination materials might combine with
other factors in service to produce corrosion. A suitable
technique, such as a simple water rinse, waterspray,
machine wash, vapor degreasing, solvent soak, or ultra-
sonic cleaning may be employed (see Annex on Post
Cleaning). It is recommended that if developer removal
is necessary, it should be carried out as promptly as
possible after examination so that it does not “fix”
on the part.
NOTE 23: Caution - Developers should he removed prior to vapor
degreasing. Vapor degreasing can bake the developer on parts.
9. Special Requirements
9.1 Impurities:
9.1.1 When using penetrant materials on austenitic
stainless steels, titanium, nickel-base or other high-
temperature alloys, the need to restrict impurities such
as sulfur, halogens and alkali metals must be considered.
These impurities may cause embrittlement or corrosion,
particularly at elevated temperatures. Any such evalua-
tion should also include consideration of the form in
which the impurities are present. Some penetrant materi-
als contain significant amounts of these impurities in
the form of volatile organic solvents. These normally
evaporate quickly and usually do not cause problems.
Other materials may contain impurities which are not
volatile and may react with the part, particularly in
the presence of moisture or elevated temperatures.
9.1.2 Because volatile solvents leave the surface
quickly without reaction under normal examination
procedures, pen&rant materials are normally subjected
to an evaporation procedure to remove the solvents
before the materials are analyzed for impurities. The
residue from this procedure is then analyzed in accord-
ance with Test Method D 129, Test Method D 1552,
or Test Method D 129 decomposition followed by Test
Method D 516, Method B (Turbidimetric Method) for
sulfur. The residue may also be analyzed by Test
SE-165 2001 SECTION
Method D 808 or Annex A2 on Methods for Measuring
Total Chlorine Content in Combustible Liquid Penetrant
Materials (for halogens other than fluorine) and Annex
A3 on Method for Measuring Total Fluorine Content
in Combustible Liquid Penetration Materials (for Ruo-
rine). An alternative procedure, Annex A4 on Determi-
nation of Anions by Ion Chromatography, provides
a single instrumental technique for rapid sequential
measurement of cormnon anions such as chloride, fluo-
ride, and sulfate. Alkali metals in the residue are
determined by flame photometry or atomic absorption
spectrophotometry.
NOTE 24: - Some current standards indicate that impurity levels
of sulfur and halogens exceeding 1% of any one suspect element
may be considered excessive. However, this high a level may be
unacceptable for some applications. so the actual maximum acceptable
impurity level must be decided between supplier and user on B case
by case basis.
9.2 Evaluated-Temperature Examination - Where
pen&ant examination is performed on parts that must be
maintained at elevated temperature during examination,
special materials and processing techniques may be
required. Such examination requires qualification in
accordance with 10.2. Manufacturer’s recommendations
should be observed.
10. Qualification and Requalification
10.1 Personal Qual$cation - When required by
user/supplier agreement, all examination personnel shaI1
ANNEXES
(MandatoryInformation)
Al. Cleaning of Parts and Materials
Al.1 Choice of Cleaning Method
Al.l.l The choice of a suitable cleaning method
is based on such factors as: (1) type of contaminant
to be removed since no one method removes all contami-
nants equally well; (2) effect of the cleaning method
on the parts; (3) practicality of the cleaning method
for the part (for example, a large part cannot be put
into a small degreaser or ultrasonic cleaner); and (4)
specific cleaning requirements of the purchaser. The
following cleaning methods are recommended:
Al.l.l.l Detergent Cleaning - Detergent clean-
ers are nonflammable water-soluble compounds con-
taining specially selected surfactants for wetting, pene-
trating, emulsifying, and saponifying various types of
V
be qualified/certified in accordance with a written proce-
dure conforming to the applicable edition of rccorn-
mended Practice SNT-TC-IA or MIL-STD-410.
10.2 Procedure Qualification - Qualification of
procedures using times or conditions differing from
those specified or for new materials may be performed
by any of several methods and should be agreed by
the contracting parties. A test piece containing one or
more discontinuities of the smallest relevant size is
used. The test piece may contain real or simulated
discontinuities, providing it displays the characteristics
of the discontinuities encountered in product exami-
nation.
10.3Nondestructive Testing Agency Qual#ication -
If a nondestructive testing agency as described in
Practice E 543 is used to perform the examination, the
agency shall meet the requirements of Practice E 543.
10.4Requalijcation may be required when a change
or substitution is made in the type of penetrant materials
or in the procedure (see 10.2).
11. Keywords
11.1 fluorescent liquid penetrant testing; hydrophilic
emulsification: lipophilic emulsification: liquid penetrant
testing; nondestructive testing; solvent removable; visi-
ble liquid penetrant testing; water-washable methods
soils, such as grease and oily films, cutting and machin-
ing fluids, and unpigmented drawing compounds, etc.
Detergent cleaners may be alkaline, neutral, or acidic
in nature, but must be noncorrosive to the item being
inspected. The cleaning properties of detergent solutions
facilitate complete removal of soils and contamination
from the surface and void areas, thus preparing them
to absorb the penetrant. Cleaning time should average
10 to 15 min at 170 to 200°F (77 to 93°C) with
moderate agitation, using concentrations (generally 6
to 8 oz./gal or 45 to 60 kg/& recommended by the
manufacturer of the cleaning compound.
A1.1.1.2Solvent Cleaning-There are a variety
of solvent cleaners that can be effectively utilized to
dissolve such soils as grease and oily films, waxes and
sealants, paints, and in general, organic matter. These
 AIIT1CI.F. 24 ~ LIQUID
solvents should be residue-free, especially when used
as a hand-wipe solvent or as a dip-tank degreasing
solvent. Solvent cleaners are not recommended for the
removal of rust and scale, welding flux and spatter,
and in general, inorganic soils. Caution: Some cleaning
solvents are flammable and can be toxic. Observe all
manufacturers’ instructions and precautionary notes.
A1.1.1.3 Vapor Degreasing - Vapor degreasing
is a preferred method of removing oil or grease-
type soils from the surface of parts and from open
discontinuities. It will not remove inorganic-type soils
(dirt, corrosion, salts, etc.), and may not remove resinous
soils (plastic coatings, varnish, paint, etc.). Because of
the short contact time, degreasing may not completely
clean out deep discontinnities and a subsequent solvent
soak is recommended.
A1.1.1.4 Alkaline Cleaning:
(ai Alkaline cleaners are nonflammable water solu-
tions containing specially selected detergents for wet-
ting, penetrating, emulsifying, and saponifying various
types of soils. Hot alkaline solutions are also used for
rust removal and descaling to remove oxide scale
which can mask surface discontinuities. Alkaline cleaner
compounds must be used in accordance with the manu-
facturers’ recommendations. Caution: Parts cleaned by
the alkaline cleaning process must be rinsed completely
free of cleaner and thoroughly dried by heat prior to
the penetrant inspection process [part temperature at
the time of penetrant application shall not exceed 125°F
(WC)].
(bj Steam cleaning is a modification of the hot-
tank alkaline cleaning method, which can be used for
preparation of large, unwieldy parts. It will remove
inorganic soils and many organic soils from the surface
of parts, but may not reach to the bottom of deep
discontinuities, and a subsequent solvent soak is recom-
mended.
A1.1.1.5 Ultrasonic Cleaning - This method
adds ultrasonic agitation to solvent or detergent cleaning
to improve cleaning efficiency and decrease cleaning
time. It should be used with water and detergent if
the soil to be removed is inorganic (rust, dirt, salts,
corrosion products, etc.), and with organic solvent if
the soil to be removed is organic (grease and oily
films, etc.). After ultrasonic cleaning, parts should be
heated to remove the cleaning fluid, then cooled to at
least 125°F (.52”C), before application of pen&ant.
A1.1.1.6 Paint Removal - Paint films can be
effectively removed by bond release solvent paint re-
mover or disintegrating-type hot-tank alkaline paint
471
PENETRANT STANDARDS SE-165
strippers. In most cases, the paint film must be com-
pletely removed to expose the surface of the metal.
Solvent-type paint removers can be of the high-viscosity
thickened type for spray or brush application or can
be of low viscosity two-layer type for dip-tank applica-
tion. Both types of solvent paint removers are generally
used at ambient temperatures, as received. Hot-tank
alkaline strippers are water-soluble powder compounds
generally used at 8 to 16 w/gal (60 to 120 kg/m3) of
water at 180 to 200°F (82 to 93°C). After paint removal,
the parts must be thoroughly rinsed to remove all
contamination from the void openings and then thor-
oughly dried.
A1.1.1.7 Mechanical Cleaning and Surjke Con-
ditioning - Metal-removing processes such as filing,
buffing, scraping, mechanical milling, drilling, reaming,
grinding, liquid honing, sanding, lathe cutting, tumble
or vibratory deburring, and abrasive blasting, including
abrasives such as glass beads, sand, aluminum oxide,
ligno-cellulose pellets, metallic shot, etc., are often used
to remove such soils as carbon, rust and scale, and
foundry adhering sands, as well as to dehurr or produce
a desired cosmetic effect on the part. These processes
may decrease the effectiveness of the penetrant examina-
tion by smearing or peening over metal surfma and
filling discontinuities open to the sut$xe, especially
for soft metals such as aluminum, titanium, magnesium,
and beryllium alloy.
A1.1.1.8 Acid Etching -Inhibited acid solutions
(pickling solutions) are routinely used for descaling
part surfaces. Descaling is necessary to remove oxide
scale, which can mask surface discontinuities and pre-
vent penetrant from entering. Acid solutionsletchants
are also used routinely to remove smeared metal that
peens over surface discontinuities. Such etchants should
be used in accordance with the manufacturers’ recom-
mendations. Caution:
NOTE Al - Etched pans and materials must be rinsed completely
free of etchants, the surface neutmlized and thoroughly dried by
heat prior to application of penetrants. Acids and chromates can
adversely affect the fluorescence of fluorescent materials.
NOTE A2 ~ Whenever there is a possibility of hydrogen embrittle-
mcnt as a result of acid solution/etching, the pa? should be baked
at a suitable temperature for an axppropriate time to remove the
hydrogen before funher processing. After baking, the paa shall
be cooled to a temperature below 125°F (52°C) before applying
penetmnts.
A1.1.1.9 Air Firing of Ceramics - Heating of
a ceramic part in a clean, oxidizing atmosphere is an
effective way of removing moisture or light organic
soil or both. The maximum temperature that will not
SE-165 2001
cuse degradation of the properties of the ceramic
should be used.
Al.2 Post Cleaning
A1.2.1 Removal of Developer - Dry powdel
developer can be effectively removed with an air blow-
off (free of oil) or it can be removed with water rinsing.
Wet developer coatings can be removed effectively by
water rinsing or water rinsing with detergent either by
hand or with a mechanical assist (scrub brushing,
washing machine, etc.). The soluble developer coatings
simply dissolve off of the part with a water rinse.
A1.2.2 Residual penetrant may be removed through
solvent action. Vapor degreasing (IO min minimum),
solvent soaking (15 min minimum), and ultrasonic
solvent cleaning (3 min minimum) techniques are rec-
ommended. In some cases, it is desirable to vapor
degrease, then follow with a solvent soak. The actual
time required in the vapor degreaser and solvent soak
will depend on the nature of the part and should be
determined experimentally.
A2. Methods for Measuring Total Chlorine
Content in Combustible Liquid Penetrant
Materials
A2.1 Scopeand Application
A2.1.1These methods cover the determination of
chlorine in combustible liquid penetrant materials, liquid
or solid. Its range of applicability is 0.001 to 5% using
either of the alternative titrimetric procedures. The
procedures assume that bromine or iodine will not be
present. If these elements are present, they will he
detected and reported as chlorine. The full amount of
these elements will not be reported. Chromate interferes
with the procedures, causing low or nonexistent end
points. The method is applicable only to materials that
are totally combustible.
A2.2 Summary of Methods
A2.2.1The sample is oxidized by combustion in
a bomb containing oxygen under pressure (Caution,
see A2.2.1 .I). The chlorine compounds thus liberated
aTe absorbed in a sodium carbonate solution and the
amount of chloride present is determined titrimetrically
either against silver nitrate with the end point detected
potiomettically (Method A) or coulometrically with the
end point detected by current Row increase (Method B).
A2.2.1.1 Safety- Strict adherence to all of
the provisions prescribed hereinafter ensures against
explosive rupture of the bomb, or a blow-out, provided
SECTION v
the bomb is of proper design and construction and in
good mechanical condition. It is desirable, however,
that the bomb be enclosed in a shield of steel plate
at least ‘/z in. (12.7 mm) thick, or equivalent protection
be provided against unforeseeable contingencies.
A2.3 Apparatus
A2.3.1 Bomb, having a capacity of not less than
300 mL, so constructed that it will not leak during
the test, and that quantitative recovery of the liquids
from the bomb may be readily achieved. The inner
surface of the bomb may be made of stainless steel
or any other material that will not be affected by the
combustion process or products. Materials used in the
bomb assembly, such as the head gasket and leadwire
insulation, shall be resistant to heat and chemical action,
and shall not undergo any reaction that will affect the
chlorine content of the liquid in the bomb.
A2.3.2 Sample Cup, platinum, 24 mm in outside
diameter at the bottom, 27 mm in outside diameter at
the top, 12 mm in height outside and weighing 10 to
11 g, opaque fused silica, wide-form with an outside
diameter of 29 mm at the top, a height of 19 mm,
and a 5-mL capacity (Note l), or nickel (Kawin capsule
form), top diameter of 28 mm, 15 mm in height, and
5.mL capacity.
NOTE A2.1 - Fused silica crucibles are much more economical
and longer-lasting than platinum. After each use, they should be
scrubbed out with fine, wet emery cloth. heated to dull red heat
over a burner, soaked in bat water for 1 b, then dried and stored
in a desiccator before reuse.
A2.3.3 Firing Wire, platinum, approximately No.
26 B & S gage.
A2.3.4 Ignirion Circuit (Note A2.2), capable of
supplying sufficient current to ignite the nylon thread
or cotton wicking without melting the wire.
NOTE A2.2: Caution - The switch in the ignition circuit shall be
of a type that remains open, except when held in closed position
by the operator.
A2.3.5 Nylon Sewing Thread, or Cotton Wicking,
white.
A2.4 Purity of Reagents
A2.4.1 Reagent grade chemicals shall be used in
all tests. Unless otherwise indicated, it is intended that
all reagents shall conform to the specifications of the
Committee on Analytical Reagents of the American
Chemical Society, where such specifications are avail-
able. Other grades may be used provided it is first
ascertained that the reagent is of sufficiently high purity
478
 ARTICLE 24 ~ LIQUID PENETRANT STANDARDS S&-165

to permit its use without lessening the accuracy of the TABLE AZ.1
determination. GAGE PRESSURES
Gage Pressure, atm (MPal
A2.4.2 Unless otherwise indicated, references to
water shall be understood to mean referee grade reagent Cauacitv of Bomb, mL min” max
water conforming to Specification D 1193.
300 to 350 38 (3.85) 40 (4.05)
A2.5 Decomposition 350 ta 400 35 (3.55) 37 (3.75)
400 to 450 30 (3.04) 32 (3.24)
A2.5.1 Reagents and Materials: 450 to 500 27 (2.74) 29 (2.94)

A2.5.1.1 Oxygen, free of combustible material li The minimum pressures are specified to provide sufficient oxygen
for complete combustion and the maximum pressures present a safety
and halogen compounds, available at a pressure of 40 reouirement.
atm (4.05 MPa).

A2.5.1.2 Sodium Carbonate Solution (SO g

Na$03/LJ - Dissolve 50 g of anhydrous Na&Os or
58.5 g of Na&Os H,O) or 135 g of NasCOs lOH*O
employed in place of white oil. However, the combhed weight of
in water and dilute to 1 L. sample and nonvolatile diluent shall not exceed 1 g. Some solid
additives are relatively insoluble, but may be satisfactorily burned
A2.5.1.3 White Oil, refined. when covered with a layer of white oil.

A2.5.2 Procedure: NOTE A2.5 - The practice of running alternately samples high
and low in chlorine content should be avoided whenever possible.
A2.5.2.1 Preparation of Bomb and Sample - It is difficult to rinse the last traces of chlorine from the walls of
Cut a piece of firing wire approximately 100 mm in the bomb and the tendency for residual chlorine to carry over from
sample to sample has been observed in a number of laboratories.
length. Coil the middle section (about 20 mm) and When a sample high in chlorine has preceded one low in chlorine
attach the free ends to the terminals. Arrange the coil content, the test on the low-chlorine sample should be repeated and
so that it will be above and to one side of the sample one or both of the low values thus obtained should be considered
suspect if they do not agree within the limits of repeatability of this
cup. Place 5 mL of Na2C0s solution in the bomb method.
(Note A2.3), place the cover on the bomb and vigorously
shake for 15 s to distribute the solution over the inside
of the bomb. Open the bomb, place the sample-filled A2.5.2.2 Addition of oxygen -Place the sample
sample cup in the terminal holder, and insert a short cup in position and arrange the nylon thread, or wisp
length of thread between the firing wire and sample. of cotton so that the end dips into the sample. Assemble
Use of a sample weight containing over 20 mg of the bomb and tighten the cover securely. Admit oxygen
chlorine may cause corrosion of the bomb. The sample (Caution, Note A2.6) slowly (to avoid blowing the
weight should not exceed 0.4 g if the expected chlorine sample from the cup) until a pressure is reached as
content is 2.5% or above. If the sample is solid, not indicated in Table A2.1.
more than 0.2 g should be used. Use 0.8 g of white
oil with solid samples. If white oil will be used (Note Note A2.6: Caution - Do not add oxygen or ignite the sample if
A2.4) add it to the sample cup by means of a dropper tbe bomb has been jarred, dropped, or tilted.

at this time (Caution, see Notes A2.5 and A2.6).

NOTE A2.3 - After repeated use of the bomb for chlorine determina- A2.5.2.3 Combustion - Immerse the bomb in
tion, a film may be noticed on the inner surface. ‘This dullness
should be removed by periodic polishing of the bomb. A satisfactory
a cold-water bath. Connect the terminals to the open
method for doing this is to rotate the bomb in a lathe at about 300 electrical circuit. Close the circuit to ignite the sample.
rpm and polish the inside surface with Grit No. 2/O or equivalent Remove the bomb from the bath after immersion for
paper coated with a light machine oil to prevent cutting, and then
with a paste of grit-free chromic oxide and water. This procedure
at least ten minutes. Release the pressure at a slow,
will remove all but very deep pits md put a high polish on the uniform rate such that the operation requires not less
surface. Before using the bomb, it should be washed wide soap and than I min. Open the bomb and examine the contents.
water to remove oil or paste left from the polishing operation. Bombs
with porous or pitted surfaces should never be used because of the If traces of unburned oil or sooty deposits are found,
tendency to retain chlorine from sample to sample. Caution: Do discard the determination, and thoroughly clean the
not use more than 1 g total of sample and white oil or other chlorine- bomb before again putting it in use (Note A2.3).
free combustible material.

NOTE A2.4 - If the sample is not readily miscible with white oil, A2.6 Analysis, Method A, Potentiometric Titration
some other nonvolatile, chlorine-free combustible diluent may be Procedure

479
SE-165
A2.6.1 A/~pmm~:
A2.6.1.1 Silver Billet Electrode.
A2.6.1.2 Glass Electrode, pH measurement type.
A2.6.1.3 Buret, 7.5~mL capacity, 0.05-mL gradu-
ations.
A2.6.1.4 Millivolt Meter, or expanded scale pH
meter capable of measuring 0 to 220 mV.
Note A2.7 - An automatic titrator is highly recommended
of items A2.6.1.3 through A2.6.1.4. Repeatability and sensitivity
the method are much enhanced by the automatic equipment
much tedious effort is avoided.
A2.6.2 Reagents and Materials:
A2.6.2.1 Acetone, chlorine-free.
A2.6.2.2 Methanol, chlorine-free.
A2.6.2.3 Silver Nitrate Solution (0.0282 N) -
Dissolve 4.7910 f 0.0005 g of silver nitrate (AgN03)
in water and dilute. to 1 L.
A2.6.2.4 Sodium Chloride Solution (0.0282
Nj - Dry a few grams of sodium chloride (NaCl) for
2 h at 130 to 15o”C, weigh out 1.6480 * 0.0005 g
of the dried NaCl, dissolve in water, and dilute to 1 L.
A2.6.2.5 Sulfuric Acid (I + 2/ - Mix 1 volume
of concentrated sulfuric acid (HzS04, sp. gr 1.84) with
2 volumes of water.
A2.6.3 Collecrion of Chlorine Solution - Remove
the sample cup with clean forceps and place in a 400.
mL beaker. Wash down the walls of the bomb shell
with a line stream of methanol from a wash bottle,
and pour the washings into the beaker. Rinse any
residue into the beaker. Next, rinse the bomb cover
and terminals into the beaker. Finally, rinse both inside
and outside of the sample crucible into the beaker,
Washings should equal but not exceed 100 mL. Add
methanol to make 100 mL.
A2.6.4 Determination of Chlorine - Add 5 mL
of HzS04 (1:2) to acidify the solution (solution should
be acid to litmus and clear of white Na&Os precipitate).
Add 100 mL of acetone. Place the electrodes in the
solution, start the stirrer (if mechanical stirrer is to be
used), and begin titration. If titration is manual, set
the pH meter cm the expanded millivolt scale and note
the reading. Add exactly 0.1 mL of AgN03 solution
from the buret. Allow a few seconds stirring; then
record the new millivolt reading. Subtract the second
reading from the first. Continue the titration, noting
2001 SECTION V
each amount of AgN03 solution and the ammmt of
difference between the present reading and the last
reading. Continue adding 0.1.mL increments, making
readings and determining differences between readings
until a maximum difference between readings is ob-
tained. The total amount of AgN03 solution required
to produce this maximum differential is the end point.
Automatic titrators continuously stir the sample, add
titrant, measure the potential difference, calculate the
differential, and plot the differential cm a chart. The
in place maximum differential is taken at the end point.
of
while NOTE A2.8 - For maximum sensitivity, 0.00282 N AgNO, solution
may be used with the automatic titrator. This dilute reagent should
not be used with I.wge samples or where chlorine content may be
over 0.1% since these tests will cause end points of 10 mL or
higher. The large amount of water used in such titrations reduces
the differential between 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 AgNOl solution will be required to avoid exceeding
the IO-* water dilution limit,
A2.6.5 Blank - Make blank determinations with
the amount of white oil used but omitting the sample.
(Liquid samples normally require only 0.15 to 0.25 g
of white oil while solids require 0.7 to 0.8 g,) Follow
normal procedure, making two or three test runs to be
sure the results are within the limits of repeatability
for the test. Repeat this blank procedure whenever new
batches of reagents or white oil are used. The purpose
of the blank run is to measure the chlorine in the white
oil, the reagents, and that introduced by contamination.
A2.6.6 Standardizafion - Silver nitrate solutions
are not permanently stable, so the true activity should
be checked when the solution is first made up and
then periodically during the life of the solution. This
is done by titration of a known NaCl solution as
follows: Prepare a mixture of the amounts of the
chemicals (Na2C03 solution, H,SO, solution, acetone,
and methanol) specified for the test. Pipet in 5.0 mL
of 0.0282-N NaCl solution and titrate to the end point.
Prepare and titrate a similar mixture of all the chemicals
except the N&l solution, thus obtaining a reagent blank
reading. Calculate the normality of the AgNOs solution
as follows:
where:
N .QNO~ = normality of the AgNQ solution,
N Nail = normality of the NaCl solution,
V, = millilitres of AgN03 solution used for the
titration including the NaCl solution, and
480
 ARTICLE 24 ~~ LIQUID
V, = millilitres of AgN03 solution used for the
titration of the reagents only.
A2.6.7 Culcularion - Calculate the chlorine con-
tent of the sample as follows:
(l’s - V,) x N x 3.545
Chlorine, weight % =
W tion is: Add approximately 1 L or hot distilled or
where:
v, = millilitres of AgN03 solution used by the
sample,
v, = millilitres of AgNOs solution used by the blank,
N= normality of the AgN03 solution, and
w=
grams of sample used.
A2.6.8 Precision and Accuracy.
A2.6.8.1 The following criteria should be used
for judging the acceptability of results:
A2.6.8.1.1 Repeatability - Results by the same
analyst should not be considered suspect unless they
differ by more than 0.006% or 10.5% of the value
determined, whichever is higher.
A2.6.8.1.2 Reproducibility - Results by differ-
ent laboratories should not be considered suspect unless
they differ by more than 0.013% or 21.3% of the value
detected, whichever is higher.
A2.6.8.1.3 Accuracy - The average recovery
of the method is 86% to 89% of the actual amount
present.
A2.7 Analysis, Method R, Coulometric Titration
A2.7.1 Apparatus:
A2.7.1.1 Coulometric Chloride Titrator.
A2.7.1.2 Beakers, two, 100-n& or glazed cruci-
bles (preferably with 1’/2 in.-outside diameter bottom).
A2.7.1.3 Refrigerator.
A2.7.2 Reagents:
A2.7.2.1 Acetic Acid, Glacial.
A2.7.2.2 Dry Gelatin Mixture.
A2.1.2.3 Nitric Acid
A2.7.2.4 Sodium Chloride Solution - 100 meq
C/l. Dry a quantity of NaCl for 2 h at 130 to 150°C.
Weigh out 5.8440 f 0.0005 g of dried NaCl in a closed
container, dissolve in water, and dilute to 1 L.
481
PENETRANT STANDARDS SE-165
A2.7.3 Reagent Preparation:
NOTE A2.9 - The normal reagent preparation process has been
slightly changed, due 1” the interference from the 50 mL of water
required to wash the bomb. This modified process eliminates the
interference and does not alter the quality of the titration.
A2.7.3.1 Gelatin Solution - A typical prepara-
deionized water to the 6.2 g of dry gelatin mixture
contained in one vial supplied by the equipment manu-
facturer. Gently heat with continuous mixing until the
gelatin is completely dissolved.
A2.7.3.2 Divide into aliquots each sufficient for
one day’s analyses. (Thirty millilitres is enough for
approximately eleven titrations.) Keep the remainder
in a refrigerator, but do not freeze. The solution will
keep for about 6 months in the refrigerator. When
ready to use, immerse the day’s aliquot in hot water
to liquefy the gelatin.
A2.7.3.3 Glacial Acetic Acid-Nitric Acid Solu-
tion - A typical ratio is 12.5 to 1 (12.5 parts CH$OOH
to 1 part HNO,).
A2.7.3.4 Mix enough gelatin solution and of
acetic acid-nitric acid mixture for one titration. (A
typical mixture is 2.5 mL of gelatin solution and 5.4
mL of acetic-nitric acid mixture.)
NOTE A2.10 - The solution may he premixed in a larger quantity
for convenience, hut may not be useahle after 24 b.
A2.7.3.5 Run at least three blank values and
take an average according to the operating manual of
the titrator. Determine separate blanks for both 5 drops
of mineral oil and 20 drops of mineral oil.
A2.7.4 Titration:
A2.7.4.1 Weigh to the nearest 0.1 g and record
the weight of the 100.mL beaker.
A2.7.4.2 Remove the sample crucible from the
cover assembly support ring using a clean forceps, and,
using a wash bottle, rinse both the inside and the
outside with water into the 100.mL beaker.
A2.7.4.3 Empty the bomb shell into the IOO-
mL beaker. Wash down the sides of the bomb shell
with water, using a wash bottle.
A2.7.4.4 Remove the cover assembly from the
cover assembly support, and, using the wash bottle,
rinse the under side, the platinum wire, and the terminals
SF.-165 2001 SECTlON V

into the same IOO-mL beaker. The total amount of
washings should be 50 f 1 g.
A2.7.4.5 Add specified amounts of gelatin mix-
ture and acetic acid-nitric acid mixture, or gelatin mix-
acetic acid-nitric acid mixture, if this was premixed,
into the lOO-mL beaker that contains the 50 g of
washings including the decomposed sample.
A2.7.4.6 Titrate using a coulometric titrimeter,
according to operating manual procedure.
A3. Method for Measuring Total Fluorine
Content in Combustible Liquid Pen&rant
Materials
A3.1 Scope and Application
A3.1.1 This method covers the determination of
fluorine in combustible liquid penetrant materials, liquid
or solid, that do not contain appreciable amounts of
interfering elements, or have any insoluble residue after
combustion. Its range of applicability is 1 to 200
000 ppm.

A3.1.2 The measure of the fluorine content employs

A2.7.5 Calculations - Calculate the chloride ion
the fluoride selective ion electrode.
concentration in the sample as follows:
A3.2 Summary of Method
(P - B) x M A3.2.1 The sample is oxidized by combustion in
Chlorine, weight % = w
a bomb containing oxygen under pressure (Caution,
see A3.2.1.1). The fluorine compounds thus liberated
are absorbed in a sodium citrate solution and the amount
where: of fluorine present is determined potentiometrically
P= counter reading obtained with the sample, through the use of a fluoride selective ion electrode.
B= average counter reading obtained with average
of the three blank readings, A3.2.1.1 Safety - Strict adherence to all of
M= standardization constant. This is dependent on the provisions prescribed hereinafter ensures against
the instrument range setting in use and the read- explosive rupmre of the bomb, or a blow-out, provided
ing obtained with a known amount of the 100 the bomb is of proper design and construction and in
meq of Cl per litre of solution, and good mechanical condition. It is desirable, however,
w= weight of sample used, g. that the bomb be enclosed in a shield of steel plate
at least ‘/* in. (12.7 mm) thick, or equivalent protection
A2.7.6 Precision and Accuracy: be provided against unforeseeable contingencies.

A2.7.6.1 Duplicate results by the same operator A3.3 Interferences

can be expected to exhibit the following relative standard
deviations: A3.3.1 Silicon, calcium, alnminum, magnesium,
and other metals forming precipitates with fluoride ion
Approximate W Chlorine RSD, o/c will interfere if they are present in sufficient concentra-
1.0 and above 0.10 tion to exceed the solubility of their respective fluorides.
0.1 2.5 Insoluble residue after combustion will entrain fluorine
0.003 5.9 even if otherwise soluble.

A3.4 Apparatus
A2.7.6.2 The method can be expected to report
values that vary from the true value by the following A3.4.1 Bomb, having a capacity of not less than
amounts: 300 mL, so constructed that it will not leak during
the test, and that quantitative recovery of the liquids
0.1% chlorine and above -22% from the bomb may be readily achieved. The inner
0.001 to 0.01% cbkrine *9%. surface of the bomb may be made of stainless steel
or any other material that will not be affected by the
combustion process or products. Materials used in the
A2.7.6.3 If bromine is present, 36.5% of the bomb assembly, such as the head gasket and leadwire
true amount will be reported. If iodine is present, 20.7% insulation, shall be resistant to heat and chemical action,
of the true amount will be reported. Fluorine will not and shall not undergo any reaction that will affect the
be detected. fluorine content of the liquid in the bomb.

482
 ARTICLE
A3.4.2 Saw@ Cup, nickel, 20 mm in outside
diameterat the bottom,28 mm in outsidediameterat
the top, and 16 mm in height:or platinum,24 mm in
outside diameterat the bottom, 27 mm in outside
diameterat the top, 12 mm in height, and weighing
10 to 11 g.
A3.4.3 Firing Wire, platinum,approximatelyNo.
26 B & S gage.
A3.4.4 Ignition Circuit (Note A3.1), capableof
supplyingsufficientcurrentto ignite.the nylon thread
or cottonwicking without melting the wire.
NOTE A3.1 Caution - The switch in the ignition circuit
of a type that remains open, except when held in closed
by the operator.
A3.4.5 Nylon Sewing Thread, or Cotton Wicking,
white.
A3.4.6 Funnel, polypropylene(Note A3.2).
A3.4.1 Volumerric Flask, polypropylene,IOO-mL
(Note A3.2).
A3.4.8 Beaker, polypropylene,150-n& (Note
A3.2).
A3.4.9Pipei, 100.pL,Eppendorf-type
(NoteA3.2).
A3.4.10MagneticStirrer andTF’F-coatedmagnetic
stirring bar.
A3.4.11 Fluoride Specific Ion Electrode and suit-
able referenceelectrode.
A3.4.12Millivolt Meter capableof measuringto
0.1 mv.
NOTE ~43.2 - Ok,ssware should neves be used to handle a fluoride
solution as it will remove fluoride ions from solution or an subsequent
use cay fluoride ion from a concentrated solution to one more dilute.
A3.5 Reagents
A3.5.1 Purity ofReagents- Reagentgradechemi-
calsshallbeusedin all tests.Unlessotherwiseindicated,
it is intendedthat all reagentsshall conform to the
specificationsof the Committeeon Analytical Reagents
of the AmericanChemicalSociety,wheresuchspecifi-
cationsare available.Othergradesmay be used,pro-
vided it is first ascertainedthat the reagentis of
sufficientlyhigh purity to permit its use without less-
ening the accuracyof the determination.
A3.5.2Purity of Water- Unlessotherwiseindi-
cated,all referencesto water shall be understoodto
meanType I reagentwaterconformingto Specification
D 1193.
24 - LIQUID PBNETRANT STANDARDS SE-165
A3.5.3 Fluoride Solution, Stock (2000 ppm) -
Dissolve 4.4200 * 0.0005g of predried(at 130 to
1SlYC for 1 h, then cooled in a desiccator)sodium
fluoride in distilled waterand dilute to 1 L.
A3.5.4 Oxyeen,free of combustiblematerialand
halogencompounds,availableat a pressureof 40 atm
(4.05MPa).
A3.5.5 Sodium Citrate Solution - Dissolve27 g
of sodiumcitratedihydratein wateranddilute to 1 L.
A3.5.6 SodiumHydroxideSolution(5 NJ - Dis-
solve 200 g of sodium hydroxide(NaOH) pellets in
shall be wateranddiluteto 1L, storein a polyethylenecontainer.
position
A3.5.7Wash Solution (Modified TISAB, Total Ionic
Srrengrh Adjustment Buffer) - To 300 mL of distilled
water,add32 mL of glacialaceticacid,6.6 g of sodium
citratedihydrate,and 32.15g of sodiumchloride.Stir
to dissolveand then adjustthe pH to 5.3 using 5 N
NaOH solution.Cool and dilute to 1 L.
A3.5.8 White Oil, refined.
A3.6 Decomposition Procedure
A3.6.1 Preparation of Bomb and Sample - Cut
a pieceof firing wire approximately100mm in length.
Coil the middle section(about20 mm) and attachthe
free endsto the terminals.Arrangethe coil so that it
will be aboveandto onesideof the samplecup.Place
10 mL of sodiumcitrate solutionin the bomb, place
the cover on the bomb, and vigorouslyshakefor 15
s to distributethe solutionover the insideof the bomb.
Openthe bomb,placethe sample-filledsamplecup in
the terminalholder,andinserta shortlengthof thread
betweenthe firing wire and the sample.The sample
weight usedshouldnot exceed1 g. If the sampleis
a solid, add a few dropsof white oil at this time to
ensureignition of the sample.
NOTE A3.3 - Use of sample weights containing over 20 mg of
chlorine 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 the following table:
Chlorine SZUNpk White Oil
Content, % weight, g weight, g
2 to 5 0.4 0.4
5 to IO 0.2 0.6
IO to 20 0.1 0.7
20 LO 50 0.05 0.7
Caution: Do not use more than 1 g total of sample
andwhiteoil or otherfluorine-freecombustiblematerial.
A3.6.2 Addition of Oxygen - Place the sample
cup in positionand arrangethe nylon thread,or wisp
of cottonsothattheenddipsinto thesample.Assemble
thebomb andtightenthecoversecurely.Admit oxygen
483
SE-165 2001 SWI‘ION V

TABLE A3.1 A3.7.4 Add 100 p,L of stock fluoride solution and
GAGEPRESSURES obtain the reading after the same length of time neces-
Gage Pressure, atm sary for A3.7.3.
(MPa)
A3.8 Calculation
Capacityof Bomb,mL minA max
300 to 350 38 ‘lo A3.8.1 Calculate the fluorine content of the sample
350to400 35 37 as follows:
400 to 450 30 32
450 to 500 27 29
2 x 10-4 2 x 10-4
A The minimum P~~SSU~~S are specified to provide sufficient oxygen
IOAE,IS - I - lOAE,IS - 1
for complete combustion and the maximum pressures present a safety Fluorine, ppm = I x 106
requirement. W

(Caution, Note A3.4) slowly (to avoid blowing the
sample from the cup) until a pressure is reached as
indicated in Table A3.1.
NOTE A3.4: Caulion - DO not add oxygen or ignite the sample
if the bomb has been jarred, dropped. or tilted.
A3.6.3 Combustion - Immerse the bomb in a
cold-water bath. Connect the terminals to the open
electrical circuit. Close the circuit to ignite the sample.
Remove the bomb from the bath after immersion for
at least 10 min. Release the pressure at a slow, uniform
rate such that the operation requires not less than 1
min. Open the bomb and examine the contents. If
traces of unburned oil or sooty deposits are found,
discard the determination, and thoroughly clean the
bomb before again putting it in use.
A3.6.4 Collection of Fluorine Solution - Remove
the sample cup with clean forceps and rinse with wash
solution into a 100.mL volumetric flask. Rinse the
walls of the bomb shell with a fine stream of wash
solution from a wash bottle, and add the washings to
the flask. Next, rinse the bomb cover and terminals
into the volumetric flask. Finally, add wash solution
to bring the contents of the flask to the line.
A3.7 Procedure
A3.7.1 Ascertain the slope (millivolts per ten-fold
change in concentration) of the electrode as described
by the manufacturer.
A3.7.2 Obtain a blank solution by performing the
procedure without a sample.
A3.7.3 Immerse the fluoride and reference elec-
trodes in solutions and obtain the equilibrium reading
to 0.1 mV. (The condition of the electrode determines
the length of time necessary to reach equilibrium. This
may be as little as 5 min or as much as 20 min.)
where:
AE, = millivolt change in sample solution on addition
of 100 pL of stock fluoride solution,
AE, = millivolt change in blank solution on addition
of 100 pL of the stock fluoride solution,
S= slope of fluoride electrode as determined in
A3.7.1, and
w= grams of sample.
A3.9 Precision and Bias
A3.9.1 Repeatability-The results of two determi-
nations by the same analyst should not be considered
suspect unless they differ by more than 1 .I ppm
(0.00011%) or 8.0% of the amount detected, whichever
is greater.
A3.9.2 Reproducibility-The results of two deter-
minations by different laboratories should not be consid-
ered suspect unless they differ by 6.7 ppm or 129.0%
of the amount detected, whichever is greater.
A3.9.3 Bias -The average recovery of the method
is 62 to 64% of the amount actually present although
83 to 85% recoveries can be expected with proper
technique.
A4. Determination of Anions by Ion
Chromatography With Conductivity
Measurement
A4.1 Scope and Application
A4.1.1 This method is condensed from ASTM
procedures and APHA Method 429 and optimized for
the analysis of detrimental substances in organic based
materials. It provides a single instrumental technique
for rapid, sequential measurement of common anions
such as bromide, chloride, fluoride, nitrate, nitrite, phos-
phate, and sulfate.
 ART1CI.E 24 -- LlQUlD
A42 Summary of Method
A4.2.1 The material must be put in the form of
an aqueous solution before analysis can be attempted.
The sample is oxidized by combustion in a bomb
containing oxygen under pressure. The products liber-
ated are absorbed in the eluant present in the bomb
at the time of ignition. This solution is washed from
the bomb, filtered, and diluted to a known volume.
A4.2.1.1 A filtered aliquot of sample is injected
into a stream of carbonate-bicarbonate eluant and passed
through a series of ion exchangers. The anions of
interest are separated on the basis of their relative
affinities for a low capacity, strongly basic anion ex-
changer (guard and separator column). The separated
anions are directed onto a strongly acidic cation ex-
changer (suppressor column) where they are converted
to their highly conductive acid form and the carbonate-
bicarbonate eluant is converted to weakly conductive
carbonic acid. The separated anions in their acid form
are measured by conductivity. They are identified on
the basis of retention time as compared to standards.
Quantitation is by measurement of peak area or peak
height. Blanks are prepared and analyzed in a similar
fashion.
A4.2.2 Interferences - Any substance that has a
retention time coinciding with that of any anion to be
determined will interfere. For example, relatively high
concentrations of low-molecular-weight organic acids
interfere with the determination of chloride and fluoride.
A high concentration of any one ion also interferes
with the resolution of others. Sample dilution overcomes
many interferences. To resolve uncertainties of identifi-
cation or quantitation use the method of known addi-
tions. Spurious peaks may result from contaminants in
reagent water, glassware, or sample processing appara-
tus. Because small sample volumes are used, scrupu-
lously avoid contamination.
A4.2.3 Minimum Detectable Concentration - The
minimum detectable concentration of an anion is a
function of sample size and conductivity scale used.
Generally, minimum detectable concentrations are in
the range of 0.05 mg/L for F- and 0.1 mg/L for BT,
Cl’, N03-, NO*-, PO,,., and S04*- with a lOO+L
sample loop and a lo-pmho full-scale setting on the
conductivity detector. Similar values may be achieved
by using a higher scale setting and an electronic integ-
rator.
A4.3 Apparatus
A4.3.1 Bomb, having a capacity of not less than
300 mL, so constructed that it will not leak during
485
PENETRANI’ STANDARDS SE-165
the test, and that quantitative recovery of the liquids
from the bomb may be readily achieved. The inner
surface of the bomb may be made of stainless steel
or any other material that will not be affected by the
combustion process or products. Materials used in the
bomb assembly, such as the head gasket and leadwire
insulation, shall be resistant to heat and chemical action,
and shall not undergo any reaction that will affect the
chlorine content of the liquid in the bomb.
A4.3.2 Sample Cup, platinum, 24 mm in outside
diameter at the bottom, 27 mm in outside diameter at
the top, 12 mm in height outside, and weighing 10 to
11 g; opaque fused silica, wide-form with an outside
diameter of 29 mm at the top, a height of 19 mm,
and a 5-mL capacity (Note A4.1), or nickel (Kawin
capsule form), top diameter of 28 mm, 15 mm in
height, and 5-mL capacity.
NOTE A4.1 - Fused silica crucibles are much more economical
and longer lasting than platinum. After each use, they should be
scrubbed out with 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.
A4.3.3 Fit@ Wire, platinum, approximately No.
26 B and S gage.
A4.3.4 Ignition Circuit (Note A4.2), capable of
supplying sufficient current to ignite the nylon thread
or cotton wicking without melting the wire.
NOTE A4.2: Caution - The switch in the ignition circuit shall be
of a type that remains open, except when held in closed position
by the operator.
A4.3.5 Nylon Sewing Thread, or Cotton Wick&
white.
A4.3.6 Ion Chromatograph, including an injection
valve, a sample loop, guard, separator, and suppressor
columns, a temperature-compensated small-volume con-
ductivity cell (6 pL or less), and a strip chart recorder
capable of full-scale response of 2 s or less. An
electronic peak integrator is optional. The ion chromato-
graph shall be capable of delivering 2 to 5 mL eluant/
min at a pressure of 1400 to 6900 kPa.
A4.3.7 Anion Separator Column, with styrene divi-
nyl-benzene-based low-capacity pellicular anion-ex-
change resin capable of resolving Br-, Cl-, F, NO;,
NO;, PO.+-, and SO4’-; 4 x 250 mm.
A4.3.8 Guard Column, identical to separator col-
umn except 4 x 50 mm, to protect separator column
from fouling by particulates or organics.
SE.165 2001 SECTION V

A4.3.9 Suppressor Column, high-capacity cation- light; contains IO mg/L each of Cl-, F, NO?-, NOz-,
exchange resin capable of converting eluant and sepa- and POdi-, I mg BI/L, and 100 mg S04’7L. Prepare
rated anions to their acid forms. fresh daily.
A4.3.10 Syringe, minimum capacity of 2 mL and A4.4.8 Combined Working Standard Solution, Low
equipped with a male pressure fitting. Range - Dilute 100 mL combined working standard
A4.4 Reagents solution, high range, to 1000 mL and store in a plastic
bottle protected from light; contains I.0 mg/L each
A4.4.1 Purity of Reagents - Reagent grade chemi- Cl-, F, N03-, NO*-, and PO,,-, 0.1 mg BiiL, and
cals shall be used in all tests. Unless otherwise indicated, 10 mg S04*-/L. Prepare fresh daily.
it is intended that all reagents shall conform to the
specifications of the Committee on Analytical Reagents A4.4.9 Alternative Combined Working Standard
of the American Chemical Society, where such specifi- Solutions - Prepare appropriate combinations ac-
cations are available. Other grades may be used, pro- cording to anion concentration to be determined. If
vided it is first ascertained that the reagent has snffi- NO*- and POd3- are not included, the combined working
ciently high purity to permit its use without lessening standard is stable for one month.
the accuracy of the determination.
A4.5 Decomposition Procedure
A4.4.2 Deionized or Distilled Water, free from
interferences at the minimum detection limit of each
A4,5.1 Preparation of Bomb and Sample - Cut
constituent and filtered through a 0.2~pm membrane a piece of firing wire approximately 100 mm in length.
filter to avoid plugging columns. Coil the middle section (about 20 mm) and attach the
A4.4.3 Eluant Solution, sodium bicarbonate-sodium free ends to the terminals. Arrange the coil so that it
carbonate, 0.003M NaHCO?- 0.0024M NazCOs: dis- will be above and to one side of the sample cup. Place
solve 1.008 g NaHC03 and 1.0176 g Na&Os in water 5 mL of Na2C0sMaHC03 solution in the bomb, place
and dilute to 4 L. the cover on the bomb, and vigorously shake for I5
s to distribute the solution over the inside of the bomb.
A4.4.4 Regenerant Solution 1, H2S0.,. I N, use
Open the bomb, place the sample-filled sample cup in
this regenerant when suppressor is not a continuously the terminal holder, and insert a short length of thread
regenerated one. between the firing wire and the sample. The sample
A4.4.5 Regenerant Solution 2. HzSO.+. 0.025 N, weight used should not exceed 1 g. If the sample is
dilute 2.8 mL cone H2S04 to 4 L or 100 mL regenerant a solid, add a few drops of white oil at this time to
solution I to 4 L. Use this regenerant with continuous ensure ignition of the sample.
regeneration tiber suppressor system.
NOTE A4.3 - Use of sample weights containing over 20 mg of
A4.4.6 Standard Anion Solutions, 100 mg/L, pre- chlorine may cause corrosion of the bomb. To avoid this if is
pare a series of standard anion solutions by weighing recommended that far samples containing over 2% chlorine, the
sample weight be based an the following:
the indicated amount of salt, dried to a constant weight chlorine Sample White Oil
at 105”C, to 1000 mL. Store in plastic bottles in a content. % weight, g weight, g
refrigerator; these solutions are stable for at least one 2 to 5 0.4 0.4
month. St010 0.2 0.6
Al”O”“t, 10 to 20 0.1 0.7
Anion salt 20 to 50 0.05 0.7
Sk
CAUTION: Do not use more than I g total of sample and white oil
Cl- N&l I.6485 or other fluorine-free combustible material.
F NUF 2.2100
Bi NaBr 1.2876 A4.5.2 Addition of Oxygen - Place the sample
NO, NaNOl 1.3707 cup in position and arrange the nylon thread, or wisp
NO*- Nah’O, 1.4998 of cotton so that the end dips into the sample. Assemble
Pod’- KHsPOd 1.4330 the bomb and tighten the cover securely. Admit oxygen
SOd2- WO, 1.8141 (Caution, Note A4.4) slowly (to avoid blowing the
A4.4.1 Combined Working Standard Solution, High sample from the cup) until a pressure is reached as
Range - Combine IO mL of the Cl-, Fe, No-, NOz-, indicated in Table A4.1.
and PO,,- standard anion solutions, I mL of the Br-,
and 100 mL of the SO,*- standard solutions, dilute to NOTE A4.4: Caution - Do not add oxygen or ignite the sample
1000 mL, and store in a plastic bottle protected from if the bomb has been jarred, dropped, 01 tilted.

486
 ART1CI.E 24 ~
TABLEA4.1
GAGEPRESSURES
Gage Prersures,
Caaacitv of Bomb. mL minm
*The minimum pressures are specified to provide sufficient
for complete combustion and the maximum pressures present
reauirement.
A453 Combustion - Immerse the bomb in a
cold-water bath. Connect the terminals to the open
electrical circuit. Close the circuit to ignite the sample.
Remove the bomb from the bath after immersion for
at least 10 min. Release the pressure at a slow, uniform
rate such that the operation requires not less than 1
min. Open the bomb and examine the contents. If
traces of unburned oil or sooty deposits are found,
discard the determination, and thoroughly clean the
bomb before again putting it in use.
A4.5.4 Collection of Solurion - Remove the sam-
ple cup with clean forceps and rinse with deionized
water and filter the washings into a 100~mL volumetric
Bask. Rinse the walls of the bomb shell with a fine
stream of deionized water from a wash bottle, and add
the washings through the filter paper to the flask. Next,
rinse the bomb cover and terminals and add the washings
through the filter into the volumetric flask. Finally, add
deionized water to bring the contents of the flask to
the line. Use aliquots of this solution for the ion
chromatography (IC) analysis.
A4.6 Procedure
A4.6.1 System Equilibration - Turn on ion chro-
matograph and adjust eluant flow rate to approximate
the separation achieved in Fig. A4.1 (‘2 to 3 mL/min).
Adjust detector to desired setting (usually 10 pmho)
and let system come to equilibrium (15 to 20 min).
A stable base line indicates equilibrium conditions.
Adjust detector offset to zero-out eluant conductivity;
with the fiber suppressor adjust the regeneration flow
rate to maintain stability, usually 2.5 to 3 mL/min.
A4.6.1.1 Set up the ion chromatograph in accord-
ance with the manufacturer’s instructions.
A4.6.2 Calibration - Inject standards containing
a single anion or a mixture and determine approximate
retention times. Observed times vary with conditions
IJQUID PENETRANT STANDARDS SE-165
”
atm
max
oxygen
a safety
FIG. A4.1 TYPICAL ANION PROFILE
but if standard eluant and anion separator column are
used, retention always in the order F, Cl’, NOz-,
POd3-, Br-, NOJ-, and S04’-. Inject at least three
different concentrations for each anion to be measured
and construct a calibration curve by plotting peak height
or area against concentration on linear graph paper.
Recalibrate whenever the detector setting is changed.
With a system requiring suppressor regeneration, NO*-
interaction with the suppressor may lead to erroneous
NO*- results; make this determination only when the
suppressor is at the same stage of exhaustion as during
standardization or recalibrate frequently. In this type.
of system the water dip (see Note A4.4) may shift
slightly during suppressor exhaustion and with a fast
run column this may lead to slight interference for F-
or Cl-. To eliminate this interference, analyze standards
that bracket the expected result or eliminate the water
dip by diluting the sample with eluant or by adding
concentrated &ant to the sample to give the same
HC03-/C03*- concentration as in the eluant. If sample
adjustments are made, adjust standards and blanks
identically.
NOTE A4.4 - Water dip occurs because water couducdvity in
sample is less than eluant conductivity (eluanl is diluted by wakr).
A4.6.2.1 If linearity is established for a given
detector setting, it is acceptable to calibrate with a
single standard. Record the peak height or area and
retention time to permit calculation of the calibration
factor, F.
A4.6.3 Sample Analysis-Remove sample particu-
late& if necessary, by filtering through a prewashed
0.2.pm-porediam membrane filter. Using a prewashed
487
SE-165 200 I SECTlON V

syringe of 1 to 10 mL capacity equipped with a male TABLE A4.2

luer fitting inject sample or standard. Inject enough PRECISION AND ACCURACY OBSERVED FOR ANIONS
sample to flush sample loop several times: for 0.1 AT VARIOUS CONCENTRATION LEVELS IN REAGENT
mL sample loop inject at least 1 mL. Switch ion WATER
chromatograph from load to inject mode and record Single-
peak heights and retention times on strip chart recorder. Amount Amount Overall operator Significant
After the last peak (SO,*-) has appeared and the Added, Found, Precision, Precision, Bias95%
Anion mg/L mg/L mg/L llKJ/L Level
conductivity signal has returned to base line, another
sample can be injected. F- 0.48 II.49 0.05 0.03 NO
F- 4.84 4.64 0.52 0.46 NO
A4.6.4 Regeneration - For systems without fiber Cl 0.76 0.86 0.38 0.11 NO
suppressor regenerate with 1 N HzS04 in accordance cl- 17 17.2 0.82 0.43 NO
with the manufacturer’s instructions when the conductiv- Cl 455 471 46 13 NO
NO> 0.45 0.09 0.09 o.ll4 Yes,neg
ity base line exceeds 300 pmho when the suppressor NO2 21.8 19.4 1.9 1.3 Yes,neg
column is on line. Br- 0.25 0.25 0.04 o.ll* NO
Bi 13.7 12.9 1.0 0.6 NO
A4.7 Calculation Po13- II.18 0.10 0.06 0.03 Yes, neg

A4.7.1 Calculate concentration of each anion, in PO,‘. 0.49 0.34 0.15 0.17 Yes,neg
NO>- 0.50 0.33 0.16 0.03 NO
mg/L, by referring to the appropriate calibration cutw. NO; 15.1 14.8 1.15 0.9 NO
Alternatively, when the response is shown to be linear, S0,2- 0.51 0.52 0.07 0.03 NO
use the following equation: S042- 43.7 43.5 2.5 2.2 NO

C=HxFxD
where:
C = mg anion&
H = peak height or area,
A4.8 Precision and Bias
F = response factor - concentration of standard/
height (or area) of standard, and A4.8.1 Samples of reagent water to which were
D = dilution factor for those samples requiring di- added the common anions were analyzed in 15 labora-
lution. tories with the results shown in Table A4.2.

488
STANDARD TEST METHOD FOR FLUORESCENT 01
PENETRANT EXAMINATION USING
THE WATER-WASHABLE PROCESS

SE-1209

(Identical with ASTM Specification E 1209.87)

DELETED

489
01 STANDARD TEST METHOD FOR FLUORESCENT
PENETRANT EXAMINATION
USING THE SOLVENT-REMOVABLE PROCESS
SE-1219

(Identical with ASTM Specification E 1219-87)

DELETED
 STANDARD TEST METHOD FOR VISIBLE 01

PENETRANT EXAMINATION
USING THE SOLVENT-REMOVABLE PROCESS
SE-1220

(Identical with ASTM Specification E 1220.87)

DELETED

491