Norma Astm e 165

An American National Standard
Designation: E 165 – 02
Standard Test Method for

Liquid Penetrant Examination1
This standard is issued under the fixed designation E 165; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.
1. Scope D 129 Test Method for Sulfur in Petroleum Products (Gen-

1.1 This test method2 covers procedures for penetrant ex- eral Bomb Method)3
amination of materials. They are nondestructive testing meth- D 516 Test Method for Sulfate Ion in Water4
ods for detecting discontinuities that are open to the surface D 808 Test Method for Chlorine in New and Used Petro-
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such as cracks, seams, laps, cold shuts, laminations, through leum Products (Bomb Method)3
leaks, or lack of fusion and are applicable to in-process, final, D 1193 Specification for Reagent Water4
and maintenance examination. They can be effectively used in D 1552 Test Method for Sulfur in Petroleum Products
the examination of nonporous, metallic materials, both ferrous (High-Temperature Method)3
and nonferrous, and of nonmetallic materials such as glazed or D 4327 Test Method for Anions in Water by Chemically
fully densified ceramics, certain nonporous plastics, and glass. Suppressed Ion Chromatography4
1.2 This test method also provides a reference: E 433 Reference Photographs for Liquid Penetrant Inspec-
1.2.1 By which a liquid penetrant examination process tion5
recommended or required by individual organizations can be E 543 Practice for Evaluating Agencies that Perform Non-
reviewed to ascertain its applicability and completeness. destructive Testing5
1.2.2 For use in the preparation of process specifications E 1208 Test Method for Fluorescent Liquid Penetrant Ex-
dealing with the liquid penetrant examination of materials and amination Using the Lipophilic Post-Emulsification Pro-
parts. Agreement by the user and the supplier regarding cess5
specific techniques is strongly recommended. E 1209 Test Method for Fluorescent Liquid Penetrant Ex-
1.2.3 For use in the organization of the facilities and amination Using the Water-Washable Process5
personnel concerned with the liquid penetrant examination. E 1210 Test Method for Fluorescent Liquid Penetrant Ex-
1.3 This test method does not indicate or suggest criteria for amination Using the Hydrophilic Post-Emulsification Pro-
evaluation of the indications obtained. It should be pointed out, cess5
however, that after indications have been produced, they must E 1219 Test Method for Fluorescent Liquid Penetrant Ex-
be interpreted or classified and then evaluated. For this purpose amination Using the Solvent-Removable Process5
there must be a separate code or specification or a specific E 1220 Test Method for Visible Penetrant Examination
agreement to define the type, size, location, and direction of Using the Solvent-Removable Process5
indications considered acceptable, and those considered unac- E 1316 Terminology for Nondestructive Examinations5
ceptable. E 1418 Test Method for Visible Penetrant Examination
1.4 The values stated in inch-pound units are to be regarded Using the Water-Washable Process5
as the standard. SI units are provided for information only. 2.2 ASNT Document: 6
1.5 This standard does not purport to address all of the Recommended Practice SNT-TC-1A for Nondestructive
safety concerns, if any, associated with its use. It is the Testing Personnel Qualification and Certification
responsibility of the user of this standard to establish appro- ANSI/ASNT CP-189 Standard for Qualification and Certi-
priate safety and health practices and determine the applica- fication of Nondestructive Testing Personnel
bility of regulatory limitations prior to use. 2.3 Military Standard:
MIL-STD-410 Nondestructive Testing Personnel Qualifica-
2. Referenced Documents tion and Certification7
2.1 ASTM Standards: 2.4 APHA Standard:
1 3
This test method is under the jurisdiction of ASTM Committee E07 on Annual Book of ASTM Standards, Vol 05.01.
4
Nondestructive Testing and is the direct responsibility of Subcommittee E07.03 on Annual Book of ASTM Standards, Vol 11.01.
5
Liquid Penetrant and Magnetic Particle Methods. Annual Book of ASTM Standards, Vol 03.03.
6
Current edition approved February 10, 2002. Published April 2002. Originally Available from the American Society for Nondestructive Testing, 1711 Arlin-
published as E 165 – 60 T. Last previous edition E 165 – 95. gate Lane, Columbus, OH 43228-0518.
2 7
For ASME Boiler and Pressure Vessel Code applications see related Recom- Available from Standardization Documents Order Desk, Bldg. 4 Section D, 700
mended Test Method SE-165 in the Code. Robbins Ave., Philadelphia, PA 19111-5094, Attn: NPODS.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
Copyright ASTM International 1 Document provided by IHS Licensee=ASMAR/325000001, 11/04/2004 12:16:26 MST
Reproduced by IHS under license with ASTM Questions or comments about this message: please call the Document Policy Group
at 303-397-2295.
E 165
429 Method for the Examination of Water and Wastewater8 require the use of black light. However, visible penetrant
2.5 AIA Standard: indications must be viewed under adequate white light (see
NAS-410 Certification and Qualification of Nondestructive 8.9.2.1).
Test Personnel6
TABLE 1 Classification of Penetrant Examination Types and
3. Terminology Methods
3.1 The definitions relating to liquid penetrant examination, Type I—Fluorescent Penetrant Examination
which appear in Terminology E 1316, shall apply to the terms Method A—Water-washable (see Test Method E 1209)
Method B—Post-emulsifiable, lipophilic (see Test Method E 1208)
used in this standard.
Method C—Solvent removable (see Test Method E 1219)
Method D—Post-emulsifiable, hydrophilic (see Test Method E 1210)
4. Summary of Test Method
Type II—Visible Penetrant Examination
4.1 A liquid penetrant which may be a visible or a fluores- Method A—Water-washable (see Test Method E 1418)
cent material is applied evenly over the surface being examined Method C—Solvent removable (see Test Method E 1220)
and allowed to enter open discontinuities. After a suitable
dwell time, the excess surface penetrant is removed. A devel-
oper is applied to draw the entrapped penetrant out of the 7. Types of Materials
discontinuity and stain the developer. The test surface is then 7.1 Liquid penetrant examination materials (see Notes 3
examined to determine the presence or absence of indications. and 4) consist of fluorescent and visible penetrants, emulsifiers
NOTE 1—The developer may be omitted by agreement between pur- (oil-base and water-base), solvent removers and developers. A
chaser and supplier. family of liquid penetrant examination materials consists of the
NOTE 2—Caution: Fluorescent penetrant examination shall not follow applicable penetrant and emulsifier or remover, as recom-
a visible penetrant examination unless the procedure has been qualified in mended by the manufacturer. Intermixing of penetrants and
accordance with 10.2, because visible dyes may cause deterioration or emulsifiers from various manufacturers is not recommended.
quenching of fluorescent dyes.
NOTE 3—Refer to 9.1 for special requirements for sulfur, halogen and
4.2 Processing parameters, such as surface precleaning, alkali metal content.
penetration time and excess penetrant removal methods, are NOTE 4—Caution: While approved penetrant materials will not ad-
determined by the specific materials used, the nature of the part versely affect common metallic materials, some plastics or rubbers may be
under examination, (that is, size, shape, surface condition, swollen or stained by certain penetrants.
alloy) and type of discontinuities expected. 7.2 Penetrants:
7.2.1 Post-Emulsifiable Penetrants are designed to be in-
5. Significance and Use soluble in water and cannot be removed with water rinsing
5.1 Liquid penetrant examination methods indicate the pres- alone. They are designed to be selectively removed from the
ence, location and, to a limited extent, the nature and magni- surface using a separate emulsifier. The emulsifier, properly
tude of the detected discontinuities. Each of the various applied and given a proper emulsification time, combines with
methods has been designed for specific uses such as critical the excess surface penetrant to form a water-washable mixture,
service items, volume of parts, portability or localized areas of which can be rinsed from the surface, leaving the surface free
examination. The method selected will depend accordingly on of fluorescent background. Proper emulsification time must be
the service requirements.
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experimentally established and maintained to ensure that
over-emulsification does not occur, resulting in loss of indica-
6. Classification of Penetrations and Methods tions.
6.1 Liquid penetrant examination methods and types are 7.2.2 Water-Washable Penetrants are designed to be di-
classified as shown in Table 1. rectly water-washable from the surface of the test part, after a
6.2 Fluorescent penetrant examination utilizes penetrants suitable penetrant dwell time. Because the emulsifier is “built-
that fluoresce brilliantly when excited by black light (see in” to the water-washable penetrant, it is extremely important
8.9.1.2). The sensitivity of fluorescent penetrants depends on to exercise proper process control in removal of excess surface
their ability to be retained in the various size discontinuities penetrant to ensure against overwashing. Water-washable pen-
during processing, then to bleed out into the developer coating etrants can be washed out of discontinuities if the rinsing step
and produce indications that will fluoresce. Fluorescent indi- is too long or too vigorous. Some penetrants are less resistant
cations are many times brighter than their surroundings when to overwashing than others.
viewed under black light illumination. 7.2.3 Solvent-Removable Penetrants are designed so that
6.3 Visible penetrant examination uses a penetrant that can excess surface penetrant can be removed by wiping until most
be seen in visible light. The penetrant is usually red, so that the of the penetrant has been removed. The remaining traces
indications produce a definite contrast with the white back- should be removed with the solvent remover (see 8.6.4.1). To
ground of the developer. The visible penetrant process does not 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 prohib-
8
Available from American Public Health Association, Publication Office, 1015 ited.
Fifteenth Street, NW, Washington, DC 20005. 7.3 Emulsifiers:
at 303-397-2295.
E 165
7.3.1 Lipophilic Emulsifiers are oil-miscible liquids used to fluorescent and visible penetrant examination methods (see
emulsify the excess oily penetrant on the surface of the part, Figs. 1-3).
rendering it water-washable. The rate of diffusion establishes 8.2 Temperature Limits—The temperature of the penetrant
the emulsification time. They are either slow- or fast-acting, materials and the surface of the part to be processed should be
depending on their viscosity and chemical composition, and between 40° and 125°F (4° and 52°C). Where it is not practical
also the surface roughness of the area being examined (see to comply with these temperature limitations, qualify the
8.6.2). procedure as described in 10.2 at the temperature of intended
7.3.2 Hydrophilic Emulsifiers are water-miscible liquids use and as agreed to by the contracting parties.
used to emulsify the excess oily fluorescent penetrant on the 8.3 Surface Conditioning Prior to Penetrant Examination—
surface of the part, rendering it water-washable (see 8.6.3). Satisfactory results usually may be obtained on surfaces in the
These water-base emulsifiers (detergent-type removers) are as-welded, as-rolled, as-cast, or as-forged conditions (or for
supplied as concentrates to be diluted with water and used as a ceramics in the densified conditions). Sensitive penetrants are
dip or spray. The concentration, use and maintenance shall be generally less easily rinsed away and are therefore less suitable
in accordance with manufacturer’s recommendations. for rough surfaces. When only loose surface residuals are
7.3.2.1 Hydrophilic emulsifiers function by displacing the present, these may be removed by wiping with clean lint-free
excess penetrant film from the surface of the part through cloths. However, precleaning of metals to remove processing
detergent action. The force of the water spray or air/mechanical residuals such as oil, graphite, scale, insulating materials,
agitation in an open dip tank provides the scrubbing action coatings, and so forth, should be done using cleaning solvents,
while the detergent displaces the film of penetrant from the part vapor degreasing or chemical removing processes. Surface
surface. The emulsification time will vary, depending on its conditioning by grinding, machining, polishing or etching shall
concentration, which can be monitored by the use of a suitable follow shot, sand, grit or vapor blasting to remove the peened
refractometer. skin and when penetrant entrapment in surface irregularities
7.4 Solvent Removers function by dissolving the penetrant, might mask the indications of unacceptable discontinuities or
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making it possible to wipe the surface clean and free of excess otherwise interfere with the effectiveness of the examination.
penetrant as described in 8.6.1.2 and 8.6.4. For metals, unless otherwise specified, etching shall be per-
7.5 Developers—Development of penetrant indications is formed when evidence exists that previous cleaning, surface
the process of bringing the penetrant out of open discontinui- treatments or service usage have produced a surface condition
ties through blotting action of the applied developer, thus that degrades the effectiveness of penetrant examination. (See
increasing the visibility of the indications. A1.1.1.8 for precautions.)
7.5.1 Dry Powder Developers are used as supplied (that is, NOTE 7—When agreed between purchaser and supplier, grit blasting
free-flowing, non-caking powder) in accordance with 8.8.2. without subsequent etching may be an acceptable cleaning method.
Care should be taken not to contaminate the developer with NOTE 8—Caution: Sand or shot blasting may possibly close disconti-
fluorescent penetrant, as the penetrant specks can appear as nuities and extreme care should be used with grinding and machining
indications. operations to avoid masking discontinuities.
7.5.2 Aqueous Developers are normally supplied as dry NOTE 9—For structural or electronic ceramics, surface preparation by
powder particles to be either suspended or dissolved (soluble) grinding, sand blasting and etching for penetrant examination is not
recommended because of the potential for damage.
in water. The concentration, use and maintenance shall be in
accordance with manufacturer’s recommendations (see 8.8.3). 8.4 Removal of Surface Contaminants:
NOTE 5—Caution: Aqueous developers may cause stripping of indica-
8.4.1 Precleaning—The success of any penetrant examina-
tions if not properly applied and controlled. The procedure should be tion procedure is greatly dependent upon the surrounding
qualified in accordance with 10.2. surface and discontinuity being free of any contaminant (solid
or liquid) that might interfere with the penetrant process. All
7.5.3 Nonaqueous Wet Developers are supplied as suspen- parts or areas of parts to be examined must be clean and dry
sions of developer particles in a nonaqueous solvent carrier before the penetrant is applied. If only a section of a part, such
ready for use as supplied. Nonaqueous, wet developers form a as a weld, including the heat affected zone is to be examined,
coating on the surface of the part when dried, which serves as all contaminants shall be removed from the area being exam-
the developing medium (see 8.8.4). ined as defined by the contracting parties. “Clean” is intended
NOTE 6—Caution: This type of developer is intended for application to mean that the surface must be free of rust, scale, welding
by spray only. flux, weld spatter, grease, paint, oily films, dirt, and so forth,
7.5.4 Liquid Film Developers are solutions or colloidal that might interfere with the penetrant process. All of these
suspensions of resins/polymer in a suitable carrier. These contaminants can prevent the penetrant from entering discon-
developers will form a transparent or translucent coating on the tinuities (see Annex on Cleaning of Parts and Materials).
surface of the part. Certain types of film developer may be NOTE 10—Caution: Residues from cleaning processes such as strong
stripped from the part and retained for record purposes (see alkalies, pickling solutions and chromates, in particular, may adversely
8.8.5). react with the penetrant and reduce its sensitivity and performance.
8.4.2 Drying after Cleaning—It is essential that the surface
8. Procedure of parts be thoroughly dry after cleaning, since any liquid
8.1 The following processing guidelines apply to both residue will hinder the entrance of the penetrant. Drying may
at 303-397-2295.
E 165
Incoming Parts
PRECLEAN Vapor De- Solvent

Alkaline Steam Acid Etch
grease Wash
(See 8.4.1)
Mechanical Paint Stripper Ultrasonic Detergent
DRY
(See 8.4.2) Dry
PENETRANT Apply Water-

APPLICATION Washable
(See 8.5) Penetrant
FINAL RINSE
Water Wash
(See 8.6.1)
Spray Dip
DRY DEVELOP
(See 8.7) (See 8.8)
Developer
Dry
(Aqueous)
DEVELOP DRY Developer,

(See 8.8) (See 8.7) Dry,
Nonaqueous
or Dry
Liquid Film
EXAMINE
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Fluorescent (See 8.9.1) Examine
Visible (See 8.9.2)
Mechanical
Water Rinse Detergent
Wash
POST CLEAN
(See 8.10 and An-
nex A1
on Post Cleaning.)
Dry
Vapor De- Ultrasonic

Solvent Soak
grease Clean
Outgoing Parts
FIG. 1 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)
be accomplished by warming the parts in drying ovens, with applied effectively by brushing or spraying. Both conventional
infrared lamps, forced hot air, or exposure to ambient tempera- and electrostatic spray guns are effective means of applying
ture. liquid penetrants to the part surfaces. Electrostatic spray
8.5 Penetrant Application—After the part has been cleaned, application can eliminate excess liquid build-up of penetrant on
dried, and is within the specified temperature range, the the part, minimize overspray, and minimize the amount of
penetrant is applied to the surface to be examined so that the penetrant entering hollow-cored passages which might serve as
entire part or area under examination is completely covered penetrant reservoirs, causing severe bleedout problems during
with penetrant. examination. Aerosol sprays are conveniently portable and
8.5.1 Modes of Application—There are various modes of suitable for local application.
effective application of penetrant such as dipping, brushing,
flooding, or spraying. Small parts are quite often placed in NOTE 11—Caution: Not all penetrant materials are suitable for elec-
suitable baskets and dipped into a tank of penetrant. On larger trostatic spray applications, so tests should be conducted prior to use.
parts, and those with complex geometries, penetrant can be NOTE 12—Warning: With spray applications, it is important that there
at 303-397-2295.
E 165
FIG. 2 General Procedure Flowsheet for Post-emulsifiable Method

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at 303-397-2295.
E 165
Incoming Parts
PRECLEAN Vapor De-

Alkaline Steam Solvent Wash Acid Etch
(See 8.4.1) grease
Mechanical Paint Stripper Ultrasonic Detergent

DRY
(See 8.4.2)
Dry
PENETRANT Apply
APPLICATION Solvent-
(See 8.5) Removable
Fluorescent
Penetrant
REMOVE EXCESS
PENETRANT Solvent
(See 8.6.4) Wipe-Off
DRY
(See 8.7) Dry
DEVELOP Nonaqueous
(See 8.8) Wet or Liquid Aqueous
Film Devel- Developer
oper
DRY
(see 8.7) Dry
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EXAMINE
Fluorescent (See 8.9.1) Examine
Visible (See 8.9.2)
Mechanical
Water Rinse Detergent Wash
POST CLEAN
(See 8.10 and An-

nex A1
on Post Cleaning)
Dry
Vapor De- Ultrasonic

Solvent Soak
grease Clean
Outgoing Parts
FIG. 3 Solvent-Removable Penetrant Examination General Procedure Flowsheet
(Test Method E 1219 for Fluorescent and Test Method E 1220 for Visible Light)
be proper ventilation. This is generally accomplished through the use of a NOTE 13—For some specific applications in structural ceramics (for
properly designed spray booth and exhaust system. example, detecting parting lines in slip-cast material), the required
penetrant dwell time should be determined experimentally and may be
8.5.2 Penetrant Dwell Time—After application, allow ex- longer than that shown in Table 1 and its notes.
cess penetrant to drain from the part (care should be taken to
prevent pools of penetrant from forming on the part), while 8.6 Penetrant Removal
allowing for proper penetrant dwell time (see Table 2). The 8.6.1 Water Washable:
length of time the penetrant must remain on the part to allow 8.6.1.1 Removal of Excess Penetrant—After the required
proper penetration should be as recommended by the penetrant penetration time, the excess penetrant on the surface being
manufacturer. Table 2, however, provides a guide for selection examined must be removed with water, usually a washing
of penetrant dwell times for a variety of materials, forms, and operation. It can be washed off manually, by the use of
types of discontinuity. Unless otherwise specified, the dwell automatic or semi-automatic water-spray equipment or by
time shall not exceed the maximum recommended by the immersion. For immersion rinsing, parts are completely im-
manufacturer. mersed in the water bath with air or mechanical agitation.
at 303-397-2295.
E 165
TABLE 2 Recommended Minimum Dwell Times
Type of Dwell TimesA (minutes)
Material Form
Discontinuity PenetrantB DeveloperC
Aluminum, magnesium, steel, castings and welds cold shuts, porosity, lack of fusion, 5 10
brass cracks (all forms)
and bronze, titanium and
high-temperature alloys
wrought materials—extrusions, laps, cracks (all forms) 10 10
forgings, plate
Carbide-tipped tools lack of fusion, porosity, cracks 5 10
Plastic all forms cracks 5 10
Glass all forms cracks 5 10
Ceramic all forms cracks, porosity 5 10
A
For temperature range from 50° to 125°F (10° to 52°C). For temperatures between 40° and 50°F (4.4° and 10°C), recommend a minimum dwell time of 20 minutes.
B
Maximum penetrant dwell time in accordance with 8.5.2.
C
Development time begins as soon as wet developer coating has dried on surface of parts (recommended minimum). Maximum development time in accordance with
8.8.6.
Accumulation of water in pockets or recesses of the surface 8.6.2.3 Post Rinsing—Effective post rinsing of the emulsi-
must be avoided. If the final rinse step is not effective, as fied penetrant from the surface can be accomplished using
evidenced by excessive residual surface penetrant after rinsing, either manual, semi-automated, or automated water immersion
dry (see 8.7) and reclean the part, then reapply the penetrant for or spray equipment or combinations thereof.
the prescribed dwell time. 8.6.2.4 Immersion—For immersion post rinsing, parts are
(a) The temperature of the water should be relatively completely immersed in the water bath with air or mechanical
constant and should be maintained within the range of 50° to agitation. The time and temperature should be kept constant.
100°F (10° to 38°C). (a) The maximum dip-rinse time should not exceed 120 s
(b) Spray-rinse water pressure should not be greater than unless otherwise specified by part or material specification.
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40 psi (280 kPa). (b) The temperature of the water should be relatively
(c) Rinse time should not exceed 120 s unless otherwise constant and should be maintained within the range of 50° to
specified by part of material specification. 100°F (10° to 38°C). Caution: A touch-up rinse may be
NOTE 14—Caution: Avoid overwashing. Excessive washing can cause
necessary after immersion.
penetrant to be washed out of discontinuities. With fluorescent penetrant 8.6.2.5 Spray Post Rinsing—Effective post rinsing follow-
methods perform the rinsing operation under black light so that it can be ing emulsification can also be accomplished by either manual
determined when the surface penetrant has been adequately removed. or automatic water spray rinsing of the parts as follows:
8.6.1.2 Removal by Wiping—In special applications, pen- (a) Control rinse water temperature within the range of 50°
etrant removal may be performed by wiping the surface with a to 100°F (10° to 38°C).
clean, absorbent material dampened with water until the excess (b) Spray rinse water pressure should not exceed 40 psi
surface penetrant is removed, as determined by examination (275 kPa).
under black light for fluorescent methods and white light for (c) The maximum spray rinse time should not exceed 120
visible methods. s unless otherwise specified by part or materials specification.
8.6.2 Lipophilic Emulsification: 8.6.2.6 Rinse Effectiveness—If the emulsification and final
8.6.2.1 Application of Emulsifier—After the required pen- rinse step is not effective, as evidenced by excessive residual
etration time, the excess penetrant on the part must be surface penetrant after emulsification and rinsing, dry (see 8.7)
emulsified by immersing or flooding the parts with the required and reclean the part and reapply the penetrant for the pre-
emulsifier (the emulsifier combines with the excess surface scribed dwell time.
penetrant and makes the mixture removable with water rins- 8.6.3 Hydrophilic Emulsification:
ing). After application of the emulsifier, the parts are drained in 8.6.3.1 Prerinsing—Directly after the required penetration
a manner that prevents the emulsifier from pooling on the time, it is recommended that the parts be prerinsed with water
part(s). prior to emulsification (8.6.3.3). This step allows for the
8.6.2.2 Emulsification Dwell Time begins as soon as the removal of excess surface penetrant from the parts prior to
emulsifier has been applied. The length of time that the emulsification so as to minimize the degree of penetrant
emulsifier is allowed to remain on a part and in contact with the contamination in the hydrophilic emulsifier bath, thereby
penetrant is dependent on the type of emulsifier employed and extending its life. In addition, prerinsing of penetrated parts
the surface condition (smooth or rough). Nominal emulsifica- minimizes possible oily penetrant pollution in the final rinse
tion time should be as recommended by the manufacturer. The step of this process. This is accomplished by collecting the
actual emulsification time must be determined experimentally prerinsings in a holding tank, separating the penetrant from
for each specific application. The surface finish (roughness) of water.
the part is a significant factor in the selection of and in the 8.6.3.2 Prerinsing Controls—Effective prerinsing is accom-
emulsification time of an emulsifier. Contact time should be plished by either manual or automated water spray rinsing of
kept to the least possible time consistent with an acceptable the parts as follows:
background and should not exceed the maximum time speci- (a) Water should be free of contaminants that could clog
fied for the part or material. spray nozzles or leave a residue on parts.
at 303-397-2295.
E 165
(b) Control water temperature within the range of 50 to unless otherwise specified by part or material specification.
100°F (10 to 38°C). Caution: A touch-up rinse may be necessary after immersion.
(c) Spray rinse at a water pressure of 25 to 40 psi (175 to 8.6.3.8 Spray Post-Rinsing—Following emulsification parts
275 kPa). can be post-rinsed by water spray rinsing as follows:
(d) Prerinse time should be the least possible time (nomi- (a) Control rinse water temperature within the range of 50
nally 60 s maximum) to provide a consistent residue of to 100°F (10 to 38°C).
penetrant on parts. Wash time is to be as specified by the part (b) Spray rinse water pressure should not exceed 40 psi
or material specification. (275 kPa).
(e) Remove water trapped in cavities using filtered shop air (c) The maximum spray rinse time should not exceed 120
at a nominal pressure of 25 psi (175 kPa) or a suction device s unless otherwise specified by part or materials specification.
to remove water from pooled areas. 8.6.3.9 If the emulsification and final rinse steps are not
8.6.3.3 Application of Emulsifier—After the required pen- effective, as evidenced by excessive residual surface penetrant
--``,,```,````,`,``,`,``,``,`-`-`,,`,,`,`,,`---
etration time and following the prerinse, the residual surface after emulsification and rinsing, dry (see 8.7) and reclean the
penetrant on part(s) must be emulsified by immersing the part and reapply the penetrant for the prescribed dwell time.
part(s) in a hydrophilic emulsifier bath (8.6.3.4) or by spraying 8.6.4 Solvent-Removable Penetrants:
the part(s) with the emulsifier (8.6.3.5) thereby rendering the 8.6.4.1 Removal of Excess Penetrant—After the required
remaining residual surface penetrant water-washable in the penetration time, the excess penetrant is removed insofar as
final rinse station (8.6.3.6). possible, by using wipers of a dry, clean, lint-free material and
8.6.3.4 Immersion—For immersion application, parts are repeating the operation until most traces of penetrant have been
completely immersed in the emulsifier bath. The hydrophilic removed. Then using a lint-free material lightly moistened with
emulsifier should be gently agitated throughout the contact solvent remover the remaining traces are gently wiped to avoid
cycle. removing penetrant from discontinuities. Avoid the use of
(a) Bath concentration should be as recommended by the excess solvent. If the wiping step is not effective, as evidenced
manufacturer. Nominal use concentration for immersion appli- by difficulty in removing the excess penetrant, dry the part (see
cations is 20 %. 8.7), and reapply the penetrant for the prescribed dwell time.
(b) Bath temperatures should be maintained between 50 Flushing the surface with solvent following the application of
and 100°F (10 to 38°C). the penetrant and prior to developing is prohibited.
(c) Immersion contact time should be the minimum re- 8.7 Drying—Drying the surface of the part(s) is necessary
quired for adequate surface removal and should not exceed two prior to applying dry or nonaqueous developers or following
min. unless otherwise approved by the cognizant engineering the application of the aqueous developer. Drying time will vary
organization. with the size, nature, and number of parts under examination.
8.6.3.5 Spray Application—For spray application following 8.7.1 Drying Parameters—Components shall be air dried at
the prerinse step, parts are emulsified by the spray application room temperature or in a drying oven. Oven temperatures shall
of an emulsifier. All part surfaces should be evenly and not exceed 160°F (71°C). Drying time shall only be that
uniformly sprayed to effectively emulsify the residual pen- necessary to adequately dry the part. Components shall be
etrant on part surfaces to render it water-washable. removed from the oven immediately after drying. Components
(a) The concentration of the emulsifier for spray applica- shall not be placed in the oven with pooled water or pooled
tion should be in accordance with the manufacturer’s recom- aqueous solutions/suspensions.
mendations, but should not exceed 5 %. 8.7.2 Drying Time Limits—Do not allow parts to remain in
(b) Temperature to be maintained at 50 to 100°F (10 to the drying oven any longer than is necessary to dry the surface.
38°C). Times over 30 min in the dryer may impair the sensitivity of
(c) The spray pressure should be 25 psi (175 kPa) max for the examination.
air and 40 psi (280 kPa) max for water. 8.8 Developer Application:
(d) Contact time should be kept to the minimum consistent 8.8.1 Modes of Application—There are various modes of
with an acceptable background and should not exceed 120 s or effective application of the various types of developers such as
the maximum time stipulated by the part or material specifi- dusting, immersing, flooding or spraying. The size, configura-
cation. tion, surface condition, number of parts to be processed, and so
8.6.3.6 Post-Rinsing of Hydrophilic Emulsified Parts— forth, will influence the choice of developer application.
Effective post-rinsing of emulsified penetrant from the surface 8.8.2 Dry Powder Developer—Dry powder developers
can be accomplished using either manual, semi-automated, or should be applied immediately after drying in such a manner as
automated water immersion or spray equipment or combina- to ensure complete part coverage. Parts can be immersed in a
tions thereof. container of dry developer or in a fluid bed of dry developer.
8.6.3.7 Immersion Post-Rinsing—Parts are to be completely They can also be dusted with the powder developer through a
immersed in the water bath with air or mechanical agitation. hand powder bulb or a conventional or electrostatic powder
(a) The temperature of the water should be relatively gun. It is common and effective to apply dry powder in an
constant and should be maintained within the range of 50 to enclosed dust chamber, which creates an effective and con-
100°F (10 to 38°C). trolled dust cloud. Other means suited to the size and geometry
(b) The maximum dip rinse time should not exceed 120 s of the specimen may be used, provided the powder is dusted
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evenly over the entire surface being examined. Excess powder coating. It is good practice to observe the bleedout while
may be removed by shaking or tapping the part, or by blowing applying the developer as an aid in interpreting and evaluating
with low-pressure 5 psi (34 kPa) dry, clean, compressed air. indications.
8.9.1 Fluorescent Light Examination:
NOTE 15—Caution: The air stream intensity should be established
experimentally for each application. 8.9.1.1 Visible Ambient Light Level—Examine fluorescent
penetrant indications under black light in a darkened area.
8.8.3 Aqueous Developers—Aqueous soluble developers
Visible ambient light should not exceed 2 ft candles (20 Lx).
should not be used with Type 2 penetrants or Type 1, Method
The measurement should be made with a suitable
A penetrants. Aqueous suspendable developers can be used
photographic-type visible light meter on the surface being
with both Type 1 and Type 2 penetrants. Aqueous developers
examined.
should be applied to the part immediately after the excess
8.9.1.2 Black Light Level Control—Black lights shall pro-
penetrant has been removed and prior to drying. Aqueous
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vide a minimum of 1000 µW/cm2, at the examination surface.
developers should be prepared and maintained in accordance
The black light wavelength shall be in the range of 320 to 380
with the manufacturer’s instructions and applied in such a
nm. The intensity should be checked weekly to ensure the
manner as to ensure complete, even, part coverage. Aqueous
required output. Reflectors and filters should be checked daily
developers may be applied by spraying (see Note 16), flowing,
for cleanliness and integrity. Cracked or broken ultraviolet
or immersing the part. It is common to immerse the parts in a
(UV) filters should be replaced immediately. Defective bulbs,
prepared developer bath. Immerse parts only long enough to
which radiate UV energy, must be replaced before further use.
coat all of the part surfaces with the developer (see Note 17).
Since a drop in line voltage can cause decreased black light
Then remove parts from the developer bath and allow to drain.
output with consequent inconsistent performance, a constant-
Drain all excess developer from recesses and trapped sections
voltage transformer should be used when there is evidence of
to eliminate pooling of developer, which can obscure discon-
voltage fluctuation.
tinuities. Dry the parts in accordance with 8.7. The dried
Caution: Certain high-intensity black light may emit unac-
developer coating appears as a translucent or white coating on
ceptable amounts of visible light, which will cause fluorescent
the part.
indications to disappear. Care should be taken to use only bulbs
NOTE 16—Caution: Atomized spraying is not recommended since a certified by the supplier to be suitable for such examination
spotty film may result. purposes.
NOTE 17—Caution: If parts are left in the bath too long, indications
may leach out. NOTE 19—The recommended minimum light intensity in 8.9.1.2 is
8.8.4 Nonaqueous Wet Developers—After the excess pen- intended for general usage. For critical examinations, higher intensity
levels may be required.
etrant has been removed and the surface has been dried, apply
developer by spraying in such a manner as to ensure complete 8.9.1.3 Black Light Warm-Up—Allow the black light to
part coverage with a thin, even film of developer. These types warm up for a minimum of 10 min prior to its use or
of developer carrier evaporate very rapidly at normal room measurement of the intensity of the ultraviolet light emitted.
temperature and do not, therefore, require the use of a dryer. 8.9.1.4 Visual Adaptation—The examiner should be in the
Dipping or flooding parts with nonaqueous developers is darkened area for at least 1 min before examining parts. Longer
prohibited, since they may flush or dissolve the penetrant from times may be necessary under some circumstances.
within the discontinuities because of the solvent action of these NOTE 20—Caution: Photochromic lenses shall not be worn during
types of developers. examination.
NOTE 18—Warning: The vapors from the evaporating, volatile solvent 8.9.2 Visible Light Examination:
developer carrier may be hazardous. Proper ventilation should be provided 8.9.2.1 Visible Light Level—Visible penetrant indications
in all cases, but especially when the surface to be examined is inside a can be examined in either natural or artificial light. Adequate
closed volume, such as a process drum or a small storage tank. illumination is required to ensure no loss in the sensitivity of
8.8.5 Liquid Film Developers—Apply by spraying as rec- the examination. A minimum light intensity at the examination
ommended by the manufacturer. Spray parts in such a manner site of 100 fc (1000 Lx) is recommended.
as to ensure complete part coverage of the area being examined 8.9.3 Housekeeping—Keep the examination area free of
with a thin, even film of developer. interfering debris, including fluorescent objects. Practice good
8.8.6 Developing Time—The length of time the developer is housekeeping at all times.
to remain on the part prior to examination should be not less 8.9.4 Evaluation—Unless otherwise agreed, it is normal
than 10 min. Developing time begins immediately after the practice to interpret and evaluate the discontinuity based on the
application of dry powder developer and as soon as the wet size of the indication (see Reference Photographs E 433).
(aqueous and nonaqueous) developer coating is dry (that is, the 8.10 Post Cleaning—Post cleaning is necessary in those
solvent carrier has evaporated to dryness). The maximum cases where residual penetrant or developer could interfere
permitted developing times shall be 4 h for dry powder with subsequent processing or with service requirements. It is
developer, 2 h for aqueous developer and 1 h for nonaqueous particularly important where residual penetrant examination
developer. materials might combine with other factors in service to
8.9 Examination—Perform examination of parts after the produce corrosion. A suitable technique, such as a simple water
applicable development time as specified in 8.8.6 to allow for rinse, waterspray, machine wash, vapor degreasing, solvent
bleedout of penetrant from discontinuities into the developer soak, or ultrasonic cleaning may be employed (see Annex on
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E 165
Post Cleaning). It is recommended that if developer removal is NOTE 22—Some current standards indicate that impurity levels of
necessary, it should be carried out as promptly as possible after sulfur and halogens exceeding 1 % of any one suspect element may be
examination so that it does not “fix” on the part. considered excessive. However, this high a level may be unacceptable for
some applications, so the actual maximum acceptable impurity level must
NOTE 21—Caution: Developers should be removed prior to vapor be decided between supplier and user on a case by case basis.
degreasing. Vapor degreasing can bake the developer on parts.
9.2 Evaluated-Temperature Examination—Where penetrant
9. Special Requirements examination is performed on parts that must be maintained at
elevated temperature during examination, special materials and
9.1 Impurities:
processing techniques may be required. Such examination
9.1.1 When using penetrant materials on austenitic stainless
requires qualification in accordance with 10.2. Manufacturer’s
steels, titanium, nickel-base or other high-temperature alloys,
recommendations should be observed.
the need to restrict impurities such as sulfur, halogens and
alkali metals must be considered. These impurities may cause
10. Qualification and Requalification
embrittlement or corrosion, particularly at elevated tempera-
tures. Any such evaluation should also include consideration of 10.1 Personnel Qualification—When required by user/
the form in which the impurities are present. Some penetrant supplier agreement, all examination personnel shall be
materials contain significant amounts of these impurities in the qualified/certified in accordance with a written procedure
form of volatile organic solvents. These normally evaporate conforming to the applicable edition of recommended Practice
quickly and usually do not cause problems. Other materials SNT-TC-1A, ANSI/ASNT CP-189, NAS-410, or MIL-STD-
may contain impurities which are not volatile and may react 410.
with the part, particularly in the presence of moisture or 10.2 Procedure Qualification—Qualification of procedures
elevated temperatures. using times or conditions differing from those specified or for
9.1.2 Because volatile solvents leave the surface quickly new materials may be performed by any of several methods
without reaction under normal examination procedures, pen- and should be agreed by the contracting parties. A test piece
etrant materials are normally subjected to an evaporation containing one or more discontinuities of the smallest relevant
procedure to remove the solvents before the materials are size is used. The test piece may contain real or simulated
analyzed for impurities. The residue from this procedure is discontinuities, providing it displays the characteristics of the
then analyzed in accordance with Test Method D 129, Test discontinuities encountered in product examination.
Method D 1552, or Test Method D 129 decomposition fol- 10.3 Nondestructive Testing Agency Qualification—If a
lowed by Test Method D 516, Method B (Turbidimetric nondestructive testing agency as described in Practice E 543 is
Method) for sulfur. The residue may also be analyzed by Test used to perform the examination, the agency shall meet the
Method D 808 or Annex A2 on Methods for Measuring Total requirements of Practice E 543.
Chlorine Content in Combustible Liquid Penetrant Materials 10.4 Requalification may be required when a change or
(for halogens other than fluorine) and Annex A3 on Method for substitution is made in the type of penetrant materials or in the
Measuring Total Fluorine Content in Combustible Liquid procedure (see 10.2).
Penetration Materials (for fluorine). An alternative procedure,
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Annex A4 on Determination of Anions by Ion Chromatogra- 11. Keywords
phy, provides a single instrumental technique for rapid sequen- 11.1 fluorescent liquid penetrant testing; hydrophilic emul-
tial measurement of common anions such as chloride, fluoride, sification; lipophilic emulsification; liquid penetrant testing;
and sulfate. Alkali metals in the residue are determined by nondestructive testing; solvent removable; visible liquid pen-
flame photometry or atomic absorption spectrophotometry. etrant testing; water-washable methods
ANNEXES
(Mandatory Information)
A1. CLEANING OF PARTS AND MATERIALS
A1.1 Choice of Cleaning Method A1.1.1.1 Detergent Cleaning—Detergent cleaners are non-
A1.1.1 The choice of a suitable cleaning method is based on flammable water-soluble compounds containing specially se-
such factors as: (1) type of contaminant to be removed since no lected surfactants for wetting, penetrating, emulsifying, and
one method removes all contaminants equally well; (2) effect saponifying various types of soils, such as grease and oily
of the cleaning method on the parts; (3) practicality of the films, cutting and machining fluids, and unpigmented drawing
cleaning method for the part (for example, a large part cannot compounds, etc. Detergent cleaners may be alkaline, neutral, or
be put into a small degreaser or ultrasonic cleaner); and (4) acidic in nature, but must be noncorrosive to the item being
specific cleaning requirements of the purchaser. The following inspected. The cleaning properties of detergent solutions facili-
cleaning methods are recommended: tate complete removal of soils and contamination from the
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surface and void areas, thus preparing them to absorb the ambient temperatures, as received. Hot-tank alkaline strippers
penetrant. Cleaning time should average 10 to 15 min at 170° are water-soluble powder compounds generally used at 8 to 16
to 200°F (77° to 93°C) with moderate agitation, using concen- oz/gal (60 to 120 kg/m3) of water at 180 to 200°F (82 to 93°C).
trations (generally 6 to 8 oz/gal or 45 to 60 kg/m3) recom- After paint removal, the parts must be thoroughly rinsed to
mended by the manufacturer of the cleaning compound. remove all contamination from the void openings and then
A1.1.1.2 Solvent Cleaning—There are a variety of solvent thoroughly dried.
cleaners that can be effectively utilized to dissolve such soils as A1.1.1.7 Mechanical Cleaning and Surface Conditioning—
grease and oily films, waxes and sealants, paints, and in Metal-removing processes such as filing, buffing, scraping,
general, organic matter. These solvents should be residue-free, mechanical milling, drilling, reaming, grinding, liquid honing,
especially when used as a hand-wipe solvent or as a dip-tank sanding, lathe cutting, tumble or vibratory deburring, and
degreasing solvent. Solvent cleaners are not recommended for abrasive blasting, including abrasives such as glass beads,
the removal of rust and scale, welding flux and spatter, and in sand, aluminum oxide, ligno-cellulose pellets, metallic shot,
general, inorganic soils. Caution: Some cleaning solvents are etc., are often used to remove such soils as carbon, rust and
flammable and can be toxic. Observe all manufacturers’ scale, and foundry adhering sands, as well as to deburr or
instructions and precautionary notes. produce a desired cosmetic effect on the part. These processes
A1.1.1.3 Vapor Degreasing—Vapor degreasing is a pre- may decrease the effectiveness of the penetrant examination by
ferred method of removing oil or grease-type soils from the smearing or peening over metal surfaces and filling disconti-
surface of parts and from open discontinuities. It will not nuities open to the surface, especially for soft metals such as
remove inorganic-type soils (dirt, corrosion, salts, etc.), and aluminum, titanium, magnesium, and beryllium alloy.
may not remove resinous soils (plastic coatings, varnish, paint, A1.1.1.8 Acid Etching—Inhibited acid solutions (pickling
etc.). Because of the short contact time, degreasing may not solutions) are routinely used for descaling part surfaces.
completely clean out deep discontinuities and a subsequent Descaling is necessary to remove oxide scale, which can mask
solvent soak is recommended. surface discontinuities and prevent penetrant from entering.
A1.1.1.4 Alkaline Cleaning: Acid solutions/etchants are also used routinely to remove
(a) Alkaline cleaners are nonflammable water solutions smeared metal that peens over surface discontinuities. Such
containing specially selected detergents for wetting, penetrat- etchants should be used in accordance with the manufacturers’
ing, emulsifying, and saponifying various types of soils. Hot recommendations. Caution:
alkaline solutions are also used for rust removal and descaling NOTE A1.1—Etched parts and materials must be rinsed completely free
to remove oxide scale which can mask surface discontinuities. of etchants, the surface neutralized and thoroughly dried by heat prior to
Alkaline cleaner compounds must be used in accordance with application of penetrants. Acids and chromates can adversely affect the
the manufacturers’ recommendations. Caution: Parts cleaned fluorescence of fluorescent materials.
by the alkaline cleaning process must be rinsed completely free NOTE A1.2—Whenever there is a possibility of hydrogen embrittlement
of cleaner and thoroughly dried by heat prior to the penetrant as a result of acid solution/etching, the part should be baked at a suitable
examination process (part temperature at the time of penetrant temperature for an appropriate time to remove the hydrogen before further
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processing. After baking, the part shall be cooled to a temperature below
application shall not exceed 125°F (52°C).
125°F (52°C) before applying penetrants.
(b) Steam cleaning is a modification of the hot-tank
alkaline cleaning method, which can be used for preparation of A1.1.1.9 Air Firing of Ceramics—Heating of a ceramic part
large, unwieldy parts. It will remove inorganic soils and many in a clean, oxidizing atmosphere is an effective way of
organic soils from the surface of parts, but may not reach to the removing moisture or light organic soil or both. The maximum
bottom of deep discontinuities, and a subsequent solvent soak temperature that will not cause degradation of the properties of
is recommended. the ceramic should be used.
A1.1.1.5 Ultrasonic Cleaning—This method adds ultra-
sonic agitation to solvent or detergent cleaning to improve A1.2 Post Cleaning
cleaning efficiency and decrease cleaning time. It should be A1.2.1 Removal of Developer—Dry powder developer can
used with water and detergent if the soil to be removed is be effectively removed with an air blow-off (free of oil) or it
inorganic (rust, dirt, salts, corrosion products, etc.), and with can be removed with water rinsing. Wet developer coatings can
organic solvent if the soil to be removed is organic (grease and be removed effectively by water rinsing or water rinsing with
oily films, etc.). After ultrasonic cleaning, parts should be detergent either by hand or with a mechanical assist (scrub
heated to remove the cleaning fluid, then cooled to at least brushing, washing machine, etc.). The soluble developer coat-
125°F (52°C), before application of penetrant. ings simply dissolve off of the part with a water rinse.
A1.1.1.6 Paint Removal—Paint films can be effectively A1.2.2 Residual penetrant may be removed through solvent
removed by bond release solvent paint remover or action. Vapor degreasing (10 min minimum), solvent soaking
disintegrating-type hot-tank alkaline paint strippers. In most (15 min minimum), and ultrasonic solvent cleaning (3 min
cases, the paint film must be completely removed to expose the minimum) techniques are recommended. In some cases, it is
surface of the metal. Solvent-type paint removers can be of the desirable to vapor degrease, then follow with a solvent soak.
high-viscosity thickened type for spray or brush application or The actual time required in the vapor degreaser and solvent
can be of low viscosity two-layer type for dip-tank application. soak will depend on the nature of the part and should be
Both types of solvent paint removers are generally used at determined experimentally.
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A2. METHODS FOR MEASURING TOTAL CHLORINE CONTENT IN COMBUSTIBLE LIQUID

PENETRANT MATERIALS
A2.1 Scope and Application without melting the wire.

A2.1.1 These methods cover the determination of chlorine NOTE A2.2—Caution: The switch in the ignition circuit shall be of a
in combustible liquid penetrant materials, liquid or solid. Its type that remains open, except when held in closed position by the
range of applicability is 0.001 to 5 % using either of the operator.
alternative titrimetric procedures. The procedures assume that A2.3.5 Nylon Sewing Thread, or Cotton Wicking, white.
bromine or iodine will not be present. If these elements are
present, they will be detected and reported as chlorine. The full A2.4 Purity of Reagents
amount of these elements will not be reported. Chromate A2.4.1 Reagent grade chemicals shall be used in all tests.
interferes with the procedures, causing low or nonexistent end Unless otherwise indicated, it is intended that all reagents shall
points. The method is applicable only to materials that are conform to the specifications of the Committee on Analytical
totally combustible. Reagents of the American Chemical Society, where such
A2.2 Summary of Methods specifications are available.9 Other grades may be used pro-
A2.2.1 The sample is oxidized by combustion in a bomb vided it is first ascertained that the reagent is of sufficiently
containing oxygen under pressure (Caution, see A2.2.1.1). The high purity to permit its use without lessening the accuracy of
chlorine compounds thus liberated are absorbed in a sodium the determination.
carbonate solution and the amount of chloride present is A2.4.2 Unless otherwise indicated, references to water shall
determined titrimetrically either against silver nitrate with the be understood to mean referee grade reagent water conforming
end point detected potentiometrically (Method A) or coulo- to Specification D 1193.
metrically with the end point detected by current flow increase
A2.5 Decomposition
(Method B).
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A2.2.1.1 Safety—Strict adherence to all of the provisions A2.5.1 Reagents and Materials:
prescribed hereinafter ensures against explosive rupture of the A2.5.1.1 Oxygen, free of combustible material and halogen
bomb, or a blow-out, provided the bomb is of proper design compounds, available at a pressure of 40 atm (4.05 MPa).
and construction and in good mechanical condition. It is A2.5.1.2 Sodium Carbonate Solution (50 g Na2CO3/L)—
desirable, however, that the bomb be enclosed in a shield of Dissolve 50 g of anhydrous Na2CO3 or 58.5 g of Na2CO3· 2O)
steel plate at least 1⁄2 in. (12.7 mm) thick, or equivalent or 135 g of Na2CO3·10H2O in water and dilute to 1 L.
protection be provided against unforeseeable contingencies. A2.5.1.3 White Oil, refined.
A2.5.2 Procedure:
A2.3 Apparatus A2.5.2.1 Preparation of Bomb and Sample—Cut a piece of
A2.3.1 Bomb, having a capacity of not less than 300 mL, so firing wire approximately 100 mm in length. Coil the middle
constructed that it will not leak during the test, and that section (about 20 mm) and attach the free ends to the terminals.
quantitative recovery of the liquids from the bomb may be Arrange the coil so that it will be above and to one side of the
readily achieved. The inner surface of the bomb may be made sample cup. Place 5 mL of Na2CO3 solution in the bomb (Note
of stainless steel or any other material that will not be affected A2.3), place the cover on the bomb and vigorously shake for 15
by the combustion process or products. Materials used in the s to distribute the solution over the inside of the bomb. Open
bomb assembly, such as the head gasket and leadwire insula- the bomb, place the sample-filled sample cup in the terminal
tion, shall be resistant to heat and chemical action, and shall not holder, and insert a short length of thread between the firing
undergo any reaction that will affect the chlorine content of the wire and the sample. Use of a sample weight containing over
liquid in the bomb. 20 mg of chlorine may cause corrosion of the bomb. The
A2.3.2 Sample Cup, platinum, 24 mm in outside diameter at sample weight should not exceed 0.4 g if the expected chlorine
the bottom, 27 mm in outside diameter at the top, 12 mm in content is 2.5 % or above. If the sample is solid, not more than
height outside and weighing 10 to 11 g, opaque fused silica, 0.2 g should be used. Use 0.8 g of white oil with solid samples.
wide-form with an outside diameter of 29 mm at the top, a If white oil will be used (Note A2.4), add it to the sample cup
height of 19 mm, and a 5-mL capacity (Note 1), or nickel by means of a dropper at this time (Caution, see Note A2.5 and
(Kawin capsule form), top diameter of 28 mm, 15 mm in Note A2.6).
height, and 5-mL capacity.
NOTE A2.3—After repeated use of the bomb for chlorine determination,
NOTE A2.1—Fused silica crucibles are much more economical and a film may be noticed on the inner surface. This dullness should be
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. 9
Reagent Chemicals, American Chemical Society Specifications, American
A2.3.3 Firing Wire, platinum, approximately No. 26 B & S Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
gage. Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
A2.3.4 Ignition Circuit (Note A2.2), capable of supplying and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
sufficient current to ignite the nylon thread or cotton wicking MD.
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E 165
removed by periodic polishing of the bomb. A satisfactory method for NOTE A2.7—An automatic titrator is highly recommended in place of
doing this is to rotate the bomb in a lathe at about 300 rpm and polish the items A2.6.1.3 and A2.6.1.4. Repeatability and sensitivity of the method
inside surface with Grit No. 2/0 or equivalent paper coated with a light are much enhanced by the automatic equipment while much tedious effort
machine oil to prevent cutting, and then with a paste of grit-free chromic is avoided.
oxide and water. This procedure will remove all but very deep pits and put
a high polish on the surface. Before using the bomb, it should be washed A2.6.2 Reagents and Materials:
with soap and water to remove oil or paste left from the polishing A2.6.2.1 Acetone, chlorine-free.
operation. Bombs with porous or pitted surfaces should never be used A2.6.2.2 Methanol, chlorine-free.
because of the tendency to retain chlorine from sample to sample. A2.6.2.3 Silver Nitrate Solution (0.0282 N)—Dissolve
Caution: Do not use more than 1 g total of sample and white oil or other 4.7910 6 0.0005 g of silver nitrate (AgNO3) in water and
chlorine-free combustible material. dilute to 1 L.
NOTE A2.4—If the sample is not readily miscible with white oil, some
other nonvolatile, chlorine-free combustible diluent may be employed in
A2.6.2.4 Sodium Chloride Solution (0.0282 N)—Dry a few
place of white oil. However, the combined weight of sample and grams of sodium chloride (NaCl) for 2 h at 130 to 150°C,
nonvolatile diluent shall not exceed 1 g. Some solid additives are weigh out 1.6480 6 0.0005 g of the dried NaCl, dissolve in
relatively insoluble, but may be satisfactorily burned when covered with water, and dilute to 1 L.
a layer of white oil. A2.6.2.5 Sulfuric Acid (1 + 2)—Mix 1 volume of concen-
NOTE A2.5—The practice of running alternately samples high and low trated sulfuric acid (H2SO4, sp. gr 1.84) with 2 volumes of
in chlorine content should be avoided whenever possible. It is difficult to water.
rinse the last traces of chlorine from the walls of the bomb and the
tendency for residual chlorine to carry over from sample to sample has
A2.6.3 Collection of Chlorine Solution—Remove the
been observed in a number of laboratories. When a sample high in sample cup with clean forceps and place in a 400-mL beaker.
chlorine has preceded one low in chlorine content, the test on the Wash down the walls of the bomb shell with a fine stream of
low-chlorine sample should be repeated and one or both of the low values methanol from a wash bottle, and pour the washings into the
thus obtained should be considered suspect if they do not agree within the beaker. Rinse any residue into the beaker. Next, rinse the bomb
limits of repeatability of this method. cover and terminals into the beaker. Finally, rinse both inside
A2.5.2.2 Addition of Oxygen—Place the sample cup in and outside of the sample crucible into the beaker. Washings
position and arrange the nylon thread, or wisp of cotton so that should equal but not exceed 100 mL. Add methanol to make
the end dips into the sample. Assemble the bomb and tighten 100 mL.
the cover securely. Admit oxygen (Caution, Note A2.6) slowly A2.6.4 Determination of Chlorine—Add 5 mL of H2SO4
(to avoid blowing the sample from the cup) until a pressure is (1:2) to acidify the solution (solution should be acid to litmus
reached as indicated in Table A2.1. and clear of white Na2CO3 precipitate). Add 100 mL of
acetone. Place the electrodes in the solution, start the stirrer (if
NOTE A2.6—Caution: Do not add oxygen or ignite the sample if the
bomb has been jarred, dropped, or tilted. mechanical stirrer is to be used), and begin titration. If titration
is manual, set the pH meter on the expanded millivolt scale and
A2.5.2.3 Combustion—Immerse the bomb in a cold-water note the reading. Add exactly 0.1 mL of AgNO3 solution from
bath. Connect the terminals to the open electrical circuit. Close the buret. Allow a few seconds stirring; then record the new
the circuit to ignite the sample. Remove the bomb from the millivolt reading. Subtract the second reading from the first.
bath after immersion for at least ten minutes. Release the Continue the titration, noting each amount of AgNO3 solution
pressure at a slow, uniform rate such that the operation requires and the amount of difference between the present reading and
not less than 1 min. Open the bomb and examine the contents. the last reading. Continue adding 0.1-mL increments, making
If traces of unburned oil or sooty deposits are found, discard readings and determining differences between readings until a
the determination, and thoroughly clean the bomb before again maximum difference between readings is obtained. The total
putting it in use (Note A2.3). amount of AgNO3 solution required to produce this maximum
A2.6 Analysis, Method A, Potentiometric Titration differential is the end point. Automatic titrators continuously
Procedure stir the sample, add titrant, measure the potential difference,
calculate the differential, and plot the differential on a chart.
A2.6.1 Apparatus:
The maximum differential is taken as the end point.
A2.6.1.1 Silver Billet Electrode.
A2.6.1.2 Glass Electrode, pH measurement type. NOTE A2.8—For maximum sensitivity, 0.00282 N AgNO3 solution may
A2.6.1.3 Buret, 25-mL capacity, 0.05-mL graduations. be used with the automatic titrator. This dilute reagent should not be used
with large samples or where chlorine content may be over 0.1 % since
A2.6.1.4 Millivolt Meter, or expanded scale pH meter ca-
these tests will cause end points of 10 mL or higher. The large amount of
pable of measuring 0 to 220 mV. water used in such titrations reduces the differential between readings,
making the end point very difficult to detect. For chlorine contents over
TABLE A2.1 Gage Pressures 1 % in samples of 0.8 g or larger, 0.282 N AgNO3 solution will be required
Capacity of Bomb, Gage Pressure, atm (MPa) to avoid exceeding the 10-mL water dilution limit.
mL minA max A2.6.5 Blank—Make blank determinations with the amount
300 to 350 38 (3.85) 40 (4.05) of white oil used but omitting the sample. (Liquid samples
350 to 400 35 (3.55) 37 (3.75)
400 to 450 30 (3.04) 32 (3.24)
normally require only 0.15 to 0.25 g of white oil while solids
450 to 500 27 (2.74) 29 (2.94) require 0.7 to 0.8 g.) Follow normal procedure, making two or
A
The minimum pressures are specified to provide sufficient oxygen for com- three test runs to be sure the results are within the limits of
plete combustion and the maximum pressures present a safety requirement. repeatability for the test. Repeat this blank procedure whenever
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new batches of reagents or white oil are used. The purpose of A2.7.2.2 Dry Gelatin Mixture. 10
the blank run is to measure the chlorine in the white oil, the A2.7.2.3 Nitric Acid.
reagents, and that introduced by contamination. A2.7.2.4 Sodium Chloride Solution—100 meq C/1. Dry a
A2.6.6 Standardization—Silver nitrate solutions are not quantity of NaCl for 2 h at 130 to 150°C. Weigh out 5.8440 6
permanently stable, so the true activity should be checked 0.0005 g of dried NaCl in a closed container, dissolve in water,
when the solution is first made up and then periodically during and dilute to 1 L.
the life of the solution. This is done by titration of a known A2.7.3 Reagent Preparation:
NaCl solution as follows: Prepare a mixture of the amounts of NOTE A2.9—The normal reagent preparation process has been slightly
the chemicals (Na2CO3 solution, H2SO4 solution, acetone, and changed, due to the interference from the 50 mL of water required to wash
methanol) specified for the test. Pipet in 5.0 mL of 0.0282-N the bomb. This modified process eliminates the interference and does not
alter the quality of the titration.
NaCl solution and titrate to the end point. Prepare and titrate a
similar mixture of all the chemicals except the NaCl solution, A2.7.3.1 Gelatin Solution—A typical preparation is: Add
thus obtaining a reagent blank reading. Calculate the normality approximately 1 L of hot distilled or deionized water to the 6.2
of the AgNO3 solution as follows: g of dry gelatin mixture contained in one vial supplied by the
equipment manufacturer. Gently heat with continuous mixing
5.0 3 NNaCl
NAgNO3 5 V 2 V (A2.1) until the gelatin is completely dissolved.
A B
A2.7.3.2 Divide into aliquots each sufficient for one day’s
where: analyses. (Thirty millilitres is enough for approximately eleven
NAgNO3 = normality of the AgNO3 solution, titrations.) Keep the remainder in a refrigerator, but do not
NNaCl = normality of the NaCl solution, freeze. The solution will keep for about 6 months in the
VA = millilitres of AgNO3 solution used for the refrigerator. When ready to use, immerse the day’s aliquot in
titration including the NaCl solution, and hot water to liquefy the gelatin.
VB = millilitres of AgNO3 solution used for the A2.7.3.3 Glacial Acetic Acid-Nitric Acid Solution—A typi-
titration of the reagents only. cal ratio is 12.5 to 1 (12.5 parts CH3COOH to 1 part HNO3).
A2.6.7 Calculation—Calculate the chlorine content of the A2.7.3.4 Mix enough gelatin solution and of acetic acid-
sample as follows: nitric acid mixture for one titration. (A typical mixture is 2.5
~VS 2 VB! 3 N 3 3.545 mL of gelatin solution and 5.4 mL of acetic-nitric acid
Chlorine, weight % 5 W (A2.2) mixture.)
NOTE A2.10—The solution may be premixed in a larger quantity for
where: convenience, but may not be useable after 24 h.
VS = millilitres of AgNO3 solution used by the sample,
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VB = millilitres of AgNO3 solution used by the blank, A2.7.3.5 Run at least three blank values and take an average
N = normality of the AgNO3 solution, and according to the operating manual of the titrator. Determine
W = grams of sample used. separate blanks for both 5 drops of mineral oil and 20 drops of
A2.6.8 Precision and Accuracy: mineral oil.
A2.6.8.1 The following criteria should be used for judging A2.7.4 Titration:
A2.7.4.1 Weigh to the nearest 0.1 g and record the weight of
the acceptability of results:
the 100-mL beaker.
A2.6.8.1.1 Repeatability—Results by the same analyst A2.7.4.2 Remove the sample crucible from the cover as-
should not be considered suspect unless they differ by more sembly support ring using a clean forceps, and, using a wash
than 0.006 % or 10.5 % of the value determined, whichever is bottle, rinse both the inside and the outside with water into the
higher. 100-mL beaker.
A2.6.8.1.2 Reproducibility—Results by different laborato- A2.7.4.3 Empty the bomb shell into the 100-mL beaker.
ries should not be considered suspect unless they differ by Wash down the sides of the bomb shell with water, using a
more than 0.013 % or 21.3 % of the value detected, whichever wash bottle.
is higher. A2.7.4.4 Remove the cover assembly from the cover assem-
A2.6.8.1.3 Accuracy—The average recovery of the method bly support, and, using the wash bottle, rinse the under side, the
is 86 % to 89 % of the actual amount present. platinum wire, and the terminals into the same 100-mL beaker.
The total amount of washings should be 50 6 1 g.
A2.7 Analysis, Method B, Coulometric Titration A2.7.4.5 Add specified amounts of gelatin mixture and
acetic acid-nitric acid mixture, or gelatin mix-acetic acid-nitric
A2.7.1 Apparatus: acid mixture, if this was premixed, into the 100-mL beaker that
A2.7.1.1 Coulometric Chloride Titrator. contains the 50 g of washings including the decomposed
A2.7.1.2 Beakers, two, 100-mL, or glazed crucibles (pref- sample.
erably with 11⁄2 in.-outside diameter bottom).
A2.7.1.3 Refrigerator.
10
May be purchased from the equipment supplier. A typical mixture consists of
A2.7.2 Reagents: 6 g of gelatin powder, 0.1 g of thymol blue, water-soluble, and 0.1 g of thymol,
A2.7.2.1 Acetic Acid, Glacial. reagent grade, crystal.
at 303-397-2295.
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A2.7.4.6 Titrate using a coulometric titrimeter, according to A2.7.6 Precision and Accuracy:
operating manual procedure. A2.7.6.1 Duplicate results by the same operator can be
A2.7.5 Calculations—Calculate the chloride ion concentra- expected to exhibit the following relative standard deviations:
tion in the sample as follows: Approximate % Chlorine RSD, %
~P 2 B! 3 M
Chlorine, weight % 5 W (A2.3) 1.0 and above 0.10
0.1 2.5
0.003 5.9
where:
P = counter reading obtained with the sample, A2.7.6.2 The method can be expected to report values that
B = average counter reading obtained with average of the vary from the true value by the following amounts:
three blank readings, 0.1 % chlorine and above 62%
M = standardization constant. This is dependent on the 0.001 to 0.01 % chlorine 69%.
instrument range setting in use and the reading
obtained with a known amount of the 100 meq of Cl A2.7.6.3 If bromine is present, 36.5 % of the true amount
per litre of solution, and will be reported. If iodine is present, 20.7 % of the true amount
W = weight of sample used, g. will be reported. Fluorine will not be detected.
A3. METHOD FOR MEASURING TOTAL FLUORINE CONTENT IN COMBUSTIBLE

LIQUID PENETRANT MATERIALS
A3.1 Scope and Application by the combustion process or products. Materials used in the
A3.1.1 This method covers the determination of fluorine in bomb assembly, such as the head gasket and leadwire insula-
combustible liquid penetrant materials, liquid or solid, that do tion, shall be resistant to heat and chemical action, and shall not
not contain appreciable amounts of interfering elements, or undergo any reaction that will affect the fluorine content of the
have any insoluble residue after combustion. Its range of liquid in the bomb.
applicability is 1 to 200 000 ppm. A3.4.2 Sample Cup, nickel, 20 mm in outside diameter at
A3.1.2 The measure of the fluorine content employs the the bottom, 28 mm in outside diameter at the top, and 16 mm
fluoride selective ion electrode. in height; or platinum, 24 mm in outside diameter at the
bottom, 27 mm in outside diameter at the top, 12 mm in height,
A3.2 Summary of Method and weighing 10 to 11 g.
A3.2.1 The sample is oxidized by combustion in a bomb A3.4.3 Firing Wire, platinum, approximately No. 26 B & S
containing oxygen under pressure (Caution, see A3.2.1.1). The gage.
fluorine compounds thus liberated are absorbed in a sodium A3.4.4 Ignition Circuit (Note A3.1), capable of supplying
citrate solution and the amount of fluorine present is deter- sufficient current to ignite the nylon thread or cotton wicking
mined potentiometrically through the use of a fluoride selective without melting the wire.
ion electrode. NOTE A3.1—Caution: The switch in the ignition circuit shall be of a
A3.2.1.1 Safety—Strict adherence to all of the provisions type that remains open, except when held in closed position by the
prescribed hereinafter ensures against explosive rupture of the operator.
bomb, or a blow-out, provided the bomb is of proper design A3.4.5 Nylon Sewing Thread, or Cotton Wicking, white.
and construction and in good mechanical condition. It is A3.4.6 Funnel, polypropylene (Note A3.2).
desirable, however, that the bomb be enclosed in a shield of A3.4.7 Volumetric Flask, polypropylene, 100-mL (Note
steel plate at least 1⁄2 in. (12.7 mm) thick, or equivalent A3.2).
protection be provided against unforeseeable contingencies. A3.4.8 Beaker, polypropylene, 150-mL (Note A3.2).
A3.4.9 Pipet, 100-µL, Eppendorf-type (Note A3.2).
A3.3 Interferences A3.4.10 Magnetic Stirrer and TFE-coated magnetic stirring
A3.3.1 Silicon, calcium, aluminum, magnesium, and other bar.
metals forming precipitates with fluoride ion will interfere if A3.4.11 Fluoride Specific Ion Electrode and suitable refer-
they are present in sufficient concentration to exceed the ence electrode.
solubility of their respective fluorides. Insoluble residue after A3.4.12 Millivolt Meter capable of measuring to 0.1 mV.
combustion will entrain fluorine even if otherwise soluble.
NOTE A3.2—Glassware should never be used to handle a fluoride
solution as it will remove fluoride ions from solution or on subsequent use
A3.4 Apparatus carry fluoride ion from a concentrated solution to one more dilute.
A3.4.1 Bomb, having a capacity of not less than 300 mL, so
constructed that it will not leak during the test, and that A3.5 Reagents
quantitative recovery of the liquids from the bomb may be A3.5.1 Purity of Reagents—Reagent grade chemicals shall
readily achieved. The inner surface of the bomb may be made be used in all tests. Unless otherwise indicated, it is intended
of stainless steel or any other material that will not be affected that all reagents shall conform to the specifications of the
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Committee on Analytical Reagents of the American Chemical TABLE A3.1 Gage Pressures
Society, where such specifications are available.9 Other grades Gage Pressure atm (MPa)
Capacity of Bomb, mL
may be used, provided it is first ascertained that the reagent is minA max
of sufficiently high purity to permit its use without lessening 300 to 350 38 40
the accuracy of the determination. 350 to 400 35 37
A3.5.2 Purity of Water—Unless otherwise indicated, all 400 to 450 30 32
450 to 500 27 29
references to water shall be understood to mean Type I reagent A
The minimum pressures are specified to provide sufficient oxygen for com-
water conforming to Specification D 1193. plete combustion and the maximum pressures present a safety requirement.
A3.5.3 Fluoride Solution, Stock (2000 ppm)—Dissolve
4.42006 0.0005 g of predried (at 130 to 150°C for 1 h, then
A3.6.3 Combustion—Immerse the bomb in a cold-water
cooled in a desiccator) sodium fluoride in distilled water and
bath. Connect the terminals to the open electrical circuit. Close
dilute to 1 L.
the circuit to ignite the sample. Remove the bomb from the
A3.5.4 Oxygen, free of combustible material and halogen
bath after immersion for at least 10 min. Release the pressure
compounds, available at a pressure of 40 atm (4.05 MPa).
at a slow, uniform rate such that the operation requires not less
A3.5.5 Sodium Citrate Solution—Dissolve 27 g of sodium
than 1 min. Open the bomb and examine the contents. If traces
citrate dihydrate in water and dilute to 1 L.
of unburned oil or sooty deposits are found, discard the
A3.5.6 Sodium Hydroxide Solution (5 N)—Dissolve 200 g
determination, and thoroughly clean the bomb before again
of sodium hydroxide (NaOH) pellets in water and dilute to 1 L;
putting it in use.
store in a polyethylene container.
A3.6.4 Collection of Fluorine Solution—Remove the
A3.5.7 Wash Solution (Modified TISAB, Total Ionic Strength
sample cup with clean forceps and rinse with wash solution
Adjustment Buffer)—To 300 mL of distilled water, add 32 mL
into a 100-mL volumetric flask. Rinse the walls of the bomb
of glacial acetic acid, 6.6 g of sodium citrate dihydrate, and
shell with a fine stream of wash solution from a wash bottle,
32.15 g of sodium chloride. Stir to dissolve and then adjust the
and add the washings to the flask. Next, rinse the bomb cover
pH to 5.3 using 5 N NaOH solution. Cool and dilute to 1 L.
and terminals into the volumetric flask. Finally, add wash
A3.5.8 White Oil, refined.
solution to bring the contents of the flask to the line.
A3.6 Decomposition Procedure
A3.7 Procedure
A3.6.1 Preparation of Bomb and Sample—Cut a piece of
firing wire approximately 100 mm in length. Coil the middle A3.7.1 Ascertain the slope (millivolts per ten-fold change in
section (about 20 mm) and attach the free ends to the terminals. concentration) of the electrode as described by the manufac-
Arrange the coil so that it will be above and to one side of the turer.
sample cup. Place 10 mL of sodium citrate solution in the A3.7.2 Obtain a blank solution by performing the procedure
bomb, place the cover on the bomb, and vigorously shake for without a sample.
15 s to distribute the solution over the inside of the bomb. Open A3.7.3 Immerse the fluoride and reference electrodes in
the bomb, place the sample-filled sample cup in the terminal solutions and obtain the equilibrium reading to 0.1 mV. (The
holder, and insert a short length of thread between the firing condition of the electrode determines the length of time
wire and the sample. The sample weight used should not necessary to reach equilibrium. This may be as little as 5 min
exceed 1 g. If the sample is a solid, add a few drops of white or as much as 20 min.)
oil at this time to ensure ignition of the sample. A3.7.4 Add 100 µL of stock fluoride solution and obtain the
reading after the same length of time necessary for A3.7.3.
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 A3.8 Calculation
samples containing over 2 % chlorine, the sample weight be based on the
following table: A3.8.1 Calculate the fluorine content of the sample as
Chlorine Sample White Oil
follows:
Content, %
2 to 5
weight, g
0.4
weight, g
0.4
Fluorine, ppm 5
2 3 1024
F
10DE1/S 2 1 2
2 3 1024
10DE2/S 2 1 G 3 106
5 to 10 0.2 0.6 W
10 to 20 0.1 0.7 (A3.1)
20 to 50 0.05 0.7
Caution: Do not use more than 1 g total of sample and white where:
D E1 = millivolt change in sample solution on addition of
oil or other fluorine-free combustible material.
100 µL of stock fluoride solution,
A3.6.2 Addition of Oxygen—Place the sample cup in posi-
D E2 = millivolt change in blank solution on addition of
tion and arrange the nylon thread, or wisp of cotton so that the
100 µL of the stock fluoride solution,
end dips into the sample. Assemble the bomb and tighten the S = slope of fluoride electrode as determined in A3.7.1,
cover securely. Admit oxygen (Caution, Note A3.4) slowly (to and
avoid blowing the sample from the cup) until a pressure is W = grams of sample.
reached as indicated in Table A3.1.
NOTE A3.4—Caution: Do not add oxygen or ignite the sample if the
A3.9 Precision and Bias
bomb has been jarred, dropped, or tilted. A3.9.1 Repeatability—The results of two determinations by
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at 303-397-2295.
E 165
the same analyst should not be considered suspect unless they unless they differ by 6.7 ppm or 129.0 % of the amount
differ by more than 1.1 ppm (0.00011 %) or 8.0 % of the detected, whichever is greater.
amount detected, whichever is greater. A3.9.3 Bias—The average recovery of the method is 62 to
A3.9.2 Reproducibility—The results of two determinations 64 % of the amount actually present although 83 to 85 %
by different laboratories should not be considered suspect recoveries can be expected with proper technique.
A4. DETERMINATION OF ANIONS BY ION CHROMATOGRAPHY WITH CONDUCTIVITY MEASUREMENT
A4.1 Scope and Application a higher scale setting and an electronic integrator.
A4.1.1 This method is condensed from ASTM procedures
and APHA Method 429 and optimized for the analysis of A4.3 Apparatus
detrimental substances in organic based materials. It provides a A4.3.1 Bomb, having a capacity of not less than 300 mL, so
single instrumental technique for rapid, sequential measure- constructed that it will not leak during the test, and that
ment of common anions such as bromide, chloride, fluoride, quantitative recovery of the liquids from the bomb may be
nitrate, nitrite, phosphate, and sulfate. readily achieved. The inner surface of the bomb may be made
of stainless steel or any other material that will not be affected
A4.2 Summary of Method by the combustion process or products. Materials used in the
A4.2.1 The material must be put in the form of an aqueous bomb assembly, such as the head gasket and leadwire insula-
solution before analysis can be attempted. The sample is tion, shall be resistant to heat and chemical action, and shall not
oxidized by combustion in a bomb containing oxygen under undergo any reaction that will affect the chlorine content of the
pressure. The products liberated are absorbed in the eluant liquid in the bomb.
present in the bomb at the time of ignition. This solution is A4.3.2 Sample Cup, platinum, 24 mm in outside diameter at
washed from the bomb, filtered, and diluted to a known the bottom, 27 mm in outside diameter at the top, 12 mm in
volume. height outside, and weighing 10 to 11 g; opaque fused silica,
--``,,```,````,`,``,`,``,``,`-`-`,,`,,`,`,,`---
A4.2.1.1 A filtered aliquot of sample is injected into a wide-form with an outside diameter of 29 mm at the top, a
stream of carbonate-bicarbonate eluant and passed through a height of 19 mm, and a 5-mL capacity (Note A4.1), or nickel
series of ion exchangers. The anions of interest are separated (Kawin capsule form), top diameter of 28 mm, 15 mm in
on the basis of their relative affinities for a low capacity, height, and 5-mL capacity.
strongly basic anion exchanger (guard and separator column). NOTE A4.1—Fused silica crucibles are much more economical and
The separated anions are directed onto a strongly acidic cation longer lasting than platinum. After each use, they should be scrubbed out
exchanger (suppressor column) where they are converted to with fine, wet emery cloth, heated to dull red heat over a burner, soaked
their highly conductive acid form and the carbonate- in hot water for 1 h then dried and stored in a desiccator before reuse.
bicarbonate eluant is converted to weakly conductive carbonic A4.3.3 Firing Wire, platinum, approximately No. 26 B and
acid. The separated anions in their acid form are measured by S gage.
conductivity. They are identified on the basis of retention time A4.3.4 Ignition Circuit (Note A4.2), capable of supplying
as compared to standards. Quantitation is by measurement of sufficient current to ignite the nylon thread or cotton wicking
peak area or peak height. Blanks are prepared and analyzed in without melting the wire.
a similar fashion.
A4.2.2 Interferences—Any substance that has a retention 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
time coinciding with that of any anion to be determined will
operator.
interfere. For example, relatively high concentrations of low-
molecular-weight organic acids interfere with the determina- A4.3.5 Nylon Sewing Thread, or Cotton Wicking, white.
tion of chloride and fluoride. A high concentration of any one A4.3.6 Ion Chromatograph, including an injection valve, a
ion also interferes with the resolution of others. Sample sample loop, guard, separator, and suppressor columns, a
dilution overcomes many interferences. To resolve uncertain- temperature-compensated small-volume conductivity cell (6
ties of identification or quantitation use the method of known µL or less), and a strip chart recorder capable of full-scale
additions. Spurious peaks may result from contaminants in response of 2 s or less. An electronic peak integrator is
reagent water, glassware, or sample processing apparatus. optional. The ion chromatograph shall be capable of delivering
Because small sample volumes are used, scrupulously avoid 2 to 5 mL eluant/min at a pressure of 1400 to 6900 kPa.
contamination. A4.3.7 Anion Separator Column, with styrene
A4.2.3 Minimum Detectable Concentration—The mini- divinylbenzene-based low-capacity pellicular anion-exchange
mum detectable concentration of an anion is a function of resin capable of resolving Br−, Cl−, F−, NO3−, NO2−, PO43−,
sample size and conductivity scale used. Generally, minimum and SO42−; 4 3 250 mm.
detectable concentrations are in the range of 0.05 mg/L for F− A4.3.8 Guard Column, identical to separator column except
and 0.1 mg/L for Br−, Cl−, NO3−, NO2−, PO43−, and SO42− with 4 3 50 mm, to protect separator column from fouling by
a 100-µL sample loop and a 10-µmho full-scale setting on the particulates or organics.
conductivity detector. Similar values may be achieved by using A4.3.9 Suppressor Column, high-capacity cation-exchange
at 303-397-2295.
E 165
resin capable of converting eluant and separated anions to their firing wire approximately 100 mm in length. Coil the middle
acid forms. section (about 20 mm) and attach the free ends to the terminals.
A4.3.10 Syringe, minimum capacity of 2 mL and equipped Arrange the coil so that it will be above and to one side of the
with a male pressure fitting. sample cup. Place 5 mL of Na2CO3/NaHCO3 solution in the
bomb, place the cover on the bomb, and vigorously shake for
A4.4 Reagents 15 s to distribute the solution over the inside of the bomb. Open
A4.4.1 Purity of Reagents—Reagent grade chemicals shall the bomb, place the sample-filled sample cup in the terminal
be used in all tests. Unless otherwise indicated, it is intended holder, and insert a short length of thread between the firing
that all reagents shall conform to the specifications of the wire and the sample. The sample weight used should not
--``,,```,````,`,``,`,``,``,`-`-`,,`,,`,`,,`---
Committee on Analytical Reagents of the American Chemical exceed 1 g. If the sample is a solid, add a few drops of white
Society, where such specifications are available.9 Other grades oil at this time to ensure ignition of the sample.
may be used provided it is first ascertained that the reagent has
NOTE A4.3—Use of sample weights containing over 20 mg of chlorine
sufficiently high purity to permit its use without lessening the
may cause corrosion of the bomb. To avoid this it is recommended that for
accuracy of the determination. samples containing over 2 % chlorine, the sample weight be based on the
A4.4.2 Deionized or Distilled Water, free from interferences following:
at the minimum detection limit of each constituent and filtered Chlorine Sample White Oil
through a 0.2-µm membrane filter to avoid plugging columns. content, % weight, g weight, g
A4.4.3 Eluant Solution, sodium bicarbonate-sodium car-
2 to 5 0.4 0.4
bonate, 0.003M NaHCO3− 0.0024M Na2CO3: dissolve 1.008 g 5 to 10 0.2 0.6
NaHCO3 and 1.0176 g Na2CO3 in water and dilute to 4 L. 10 to 20 0.1 0.7
A4.4.4 Regenerant Solution 1, H2SO4, 1 N, use this regen- 20 to 50 0.05 0.7
CAUTION: Do not use more than 1 g total of sample and white oil or other
erant when suppressor is not a continuously regenerated one. fluorine-free combustible material.
A4.4.5 Regenerant Solution 2, H2SO4, 0.025 N, dilute 2.8
mL conc H2SO4 to 4 L or 100 mL regenerant solution 1 to 4 L. A4.5.2 Addition of Oxygen—Place the sample cup in posi-
Use this regenerant with continuous regeneration fiber suppres- tion and arrange the nylon thread, or wisp of cotton so that the
sor system. end dips into the sample. Assemble the bomb and tighten the
A4.4.6 Standard Anion Solutions, 1000 mg/L, prepare a cover securely. Admit oxygen (Caution, Note A4.4) slowly (to
series of standard anion solutions by weighing the indicated avoid blowing the sample from the cup) until a pressure is
amount of salt, dried to a constant weight at 105°C, to 1000 reached as indicated in Table A4.1.
mL. Store in plastic bottles in a refrigerator; these solutions are NOTE A4.4—Caution: Do not add oxygen or ignite the sample if the
stable for at least one month. bomb has been jarred, dropped, or tilted.
Anion Salt Amount, A4.5.3 Combustion—Immerse the bomb in a cold-water
g/L
bath. Connect the terminals to the open electrical circuit. Close
Cl− NaCl 1.6485 the circuit to ignite the sample. Remove the bomb from the
F− NaF 2.2100 bath after immersion for at least 10 min. Release the pressure
Br− NaBr 1.2876
NO3− NaNO3 1.3707 at a slow, uniform rate such that the operation requires not less
NO2− NaNO2 1.4998 than 1 min. Open the bomb and examine the contents. If traces
PO43− KH2PO4 1.4330 of unburned oil or sooty deposits are found, discard the
SO42− K2SO4 1.8141
determination, and thoroughly clean the bomb before again
A4.4.7 Combined Working Standard Solution, High putting it in use.
Range—Combine 10 mL of the Cl−, F−, NO3−, NO2−, and A4.5.4 Collection of Solution—Remove the sample cup
PO43− standard anion solutions, 1 mL of the Br−, and 100 mL with clean forceps and rinse with deionized water and filter the
of the SO42− standard solutions, dilute to 1000 mL, and store in washings into a 100-mL volumetric flask. Rinse the walls of
a plastic bottle protected from light; contains 10 mg/L each of the bomb shell with a fine stream of deionized water from a
Cl−, F−, NO3−, NO2−, and PO43−, 1 mg Br−/L, and 100 mg wash bottle, and add the washings through the filter paper to
SO42−/L. Prepare fresh daily. the flask. Next, rinse the bomb cover and terminals and add the
A4.4.8 Combined Working Standard Solution, Low washings through the filter into the volumetric flask. Finally,
Range—Dilute 100 mL combined working standard solution, add deionized water to bring the contents of the flask to the
high range, to 1000 mL and store in a plastic bottle protected line. Use aliquots of this solution for the ion chromatography
from light; contains 1.0 mg/L each Cl−, F−, NO3−, NO2−, and (IC) analysis.
PO43−, 0.1 mg Br−/L, and 10 mg SO42−/L. Prepare fresh daily. TABLE A4.1 Gage Pressures
A4.4.9 Alternative Combined Working Standard
Gage Pressures, atm
Solutions—Prepare appropriate combinations according to an- Capacity of Bomb, mL
mmA max
ion concentration to be determined. If NO2− and PO43− are not
included, the combined working standard is stable for one 300 to 350 38 40
350 to 400 35 37
month. 400 to 450 30 32
450 to 500 27 29
A4.5 Decomposition Procedure A
The minimum pressures are specified to provide sufficient oxygen for com-
A4.5.1 Preparation of Bomb and Sample—Cut a piece of plete combustion and the maximum pressures present a safety requirement.
at 303-397-2295.
E 165
A4.6 Procedure Record the peak height or area and retention time to permit
A4.6.1 System Equilibration—Turn on ion chromatograph calculation of the calibration factor, F.
and adjust eluant flow rate to approximate the separation A4.6.3 Sample Analysis—Remove sample particulates, if
achieved in Fig. A4.1 (2 to 3 mL/min). Adjust detector to necessary, by filtering through a prewashed 0.2-µm-pore-diam
desired setting (usually 10 µmho) and let system come to membrane filter. Using a prewashed syringe of 1 to 10 mL
equilibrium (15 to 20 min). A stable base line indicates capacity equipped with a male luer fitting inject sample or
equilibrium conditions. Adjust detector offset to zero-out standard. Inject enough sample to flush sample loop several
eluant conductivity; with the fiber suppressor adjust the regen- times: for 0.1 mL sample loop inject at least 1 mL. Switch ion
eration flow rate to maintain stability, usually 2.5 to 3 mL/min. chromatograph from load to inject mode and record peak
A4.6.1.1 Set up the ion chromatograph in accordance with heights and retention times on strip chart recorder. After the
the manufacturer’s instructions. last peak (SO42−) has appeared and the conductivity signal has
A4.6.2 Calibration—Inject standards containing a single returned to base line, another sample can be injected.
anion or a mixture and determine approximate retention times. A4.6.4 Regeneration—For systems without fiber suppressor
Observed times vary with conditions but if standard eluant and regenerate with 1 N H2SO4 in accordance with the manufac-
anion separator column are used, retention always is in the turer’s instructions when the conductivity base line exceeds
order F−, Cl−, NO2−, PO43−, Br−, NO3−, and SO42−. Inject at 300 µmho when the suppressor column is on line.
least three different concentrations for each anion to be A4.7 Calculation
measured and construct a calibration curve by plotting peak
A4.7.1 Calculate concentration of each anion, in mg/L, by
height or area against concentration on linear graph paper.
referring to the appropriate calibration curve. Alternatively,
Recalibrate whenever the detector setting is changed. With a
when the response is shown to be linear, use the following
system requiring suppressor regeneration, NO2− interaction
equation:
with the suppressor may lead to erroneous NO2− results; make
this determination only when the suppressor is at the same C5H3F3D (A4.1)
stage of exhaustion as during standardization or recalibrate
frequently. In this type of system the water dip (see NoteNote where:
A4.4) may shift slightly during suppressor exhaustion and with C = mg anion/L,
a fast run column this may lead to slight interference for F− or H = peak height or area,
Cl−. To eliminate this interference, analyze standards that F = response factor − concentration of standard/height (or
bracket the expected result or eliminate the water dip by area) of standard, and
diluting the sample with eluant or by adding concentrated D = dilution factor for those samples requiring dilution.
eluant to the sample to give the same HCO3−/CO32− concen-
A4.8 Precision and Bias
tration as in the eluant. If sample adjustments are made, adjust
standards and blanks identically. A4.8.1 Samples of reagent water to which were added the
common anions were analyzed in 15 laboratories with the
NOTE A4.5—Water dip occurs because water conductivity in sample is results shown in Table A4.2.
less than eluant conductivity (eluant is diluted by water).
A4.6.2.1 If linearity is established for a given detector TABLE A4.2 Precision and Accuracy Observed for Anions at
Various Concentration Levels in Reagent Water
setting, it is acceptable to calibrate with a single standard.
Single-
Overall Significant
Amount Amount Operator
Anion Precision, Bias 95 %
Added, mg/L Found, mg/L Precision,
mg/L Level
mg/L
F− 0.48 0.49 0.05 0.03 No
F− 4.84 4.64 0.52 0.46 No
Cl 0.76 0.86 0.38 0.11 No
Cl− 17 17.2 0.82 0.43 No
Cl 455 471 46 13 No
NO2 0.45 0.09 0.09 0.04 Yes, neg
NO2 21.8 19.4 1.9 1.3 Yes, neg
Br− 0.25 0.25 0.04 0.02 No
Br− 13.7 12.9 1.0 0.6 No
PO43− 0.18 0.10 0.06 0.03 Yes, neg
PO43− 0.49 0.34 0.15 0.17 Yes, neg
NO3− 0.50 0.33 0.16 0.03 No
NO3− 15.1 14.8 1.15 0.9 No
SO42− 0.51 0.52 0.07 0.03 No
SO42− 43.7 43.5 2.5 2.2 No
FIG. A4.1 Typical Anion Profile
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at 303-397-2295.
E 165
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--``,,```,````,`,``,`,``,``,`-`-`,,`,,`,`,,`---
at 303-397-2295.

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