This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles

for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.

A Designation: E165/E165M - 23
�u117
INTERNATIONAL

Standard Practice for

Liquid Penetrant Testing for General Industry 1

This standard is issued under the fixed designation E l65/El65M; 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* therefore, each system shall be used independently of the other.

2 Combining values from the two systems may result in non­
1 . 1 This practice covers procedures for penetrant examina­
tion of materials. Penetrant testing is a nondestructive testing conformance with the standard.
method for detecting discontinuities that are open to the surface 1 . 5 This standard does not purport to address all of the
such as cracks, seams, laps, cold shuts, shrinkage, laminations, safety concerns, if any, associated with its use. It is the
through leaks, or lack of fusion and is applicable to in-process, responsibility of the user of this standard to establish appro­
final, and maintenance examinations. It can be effectively used priate safety, health, and environmental practices and deter­
in the examination of nonporous, metallic materials, ferrous mine the applicability of regulatory limitations prior to use.
and nonferrous metals, and of nonmetallic materials such as 1 .6 This international standard was developed in accor­
nonporous glazed or fully densified ceramics, as well as certain dance with internationally recognized principles on standard­
nonporous plastics, and glass. ization established in the Decision on Principles for the
Development of International Standards, Guides and Recom­
1 .2 This practice also provides a reference:
mendations issued by the World Trade Organization Technical
1 .2. 1 By which a liquid penetrant examination process
Barriers to Trade (TBT) Committee.
recommended or required by individual organizations can be
reviewed to ascertain its applicability and completeness.
2. Referenced Documents
1 .2.2 For use in the preparation of process specifications and
procedures dealing with the liquid penetrant testing of parts 2. 1 ASTM Standards:3
and materials. Agreement by the customer requesting penetrant D 1 29 Test Method for Sulfur in Petroleum Products (Gen-
testing is strongly recommended. All areas of this practice may eral High Pressure Decomposition Device Method)
be open to agreement between the cognizant engineering D329 Specification for Acetone
organization and the supplier, or specific direction from the D770 Specification for Isopropyl Alcohol
cognizant engineering organization. D 1 1 93 Specification for Reagent Water
1 .2.3 For use in the organization of facilities and personnel D 1 552 Test Method for Sulfur in Petroleum Products by
concerned with liquid penetrant testing. High Temperature Combustion and Infrared (IR) Detec­
tion or Thermal Conductivity Detection (TCD)
1 .3 This practice does not indicate or suggest criteria for
D4327 Test Method for Anions in Water by S uppressed Ion
evaluation of the indications obtained by penetrant testing. It
Chromatography
should be pointed out, however, that after indications have
D69 1 9 Test Method for Determination of Dissolved Alkali
been found, they must be interpreted or classified and then
and Alkaline Earth Cations and Ammonium in Water and
evaluated. For this purpose there must be a separate code,
Wastewater by Ion Chromatography
standard, or a specific agreement to define the type, size,
E433 Reference Photographs for Liquid Penetrant Inspec­
location, and direction of indications considered acceptable,
tion
and those considered unacceptable.
E5 1 6 Practice for Testing Thermal Conductivity Detectors
1 .4 Units-The values stated in either SI units or inch­ Used in Gas Chromatography
pound units are to be regarded separately as standard. The E543 Specification for Agencies Performing Nondestructive
values stated in each system may not be exact equivalents; Testing
E l 208 Practice for Fluorescent Liquid Penetrant Testing
1 This practice is under the jurisdiction of ASTM Committee E07 on Nonde­ Using the Lipophilic Post-Emulsification Process
structive Testing and is the direct responsibility of Subcommittee E07.03 on Liquid
Penetrant and Magnetic Particle Methods.
Current edition approved July I, 2023. Published August 2023. Originally
approved in 1960. Last previous edition approved in 2018 as E l65/E 165M - 18. 3 For referenced ASTM standards, visit the ASTM website, www.astm.org, or
DOI: I0.1520/E0 165_E0165M-23. contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
2 For ASME Boiler and Pressure Vessel Code applications see related Recom­ Standards volume information, refer to the standard's Document Summary page on
mended Test Method SE -165 in the Code. the ASTM website.

*A Summary of Changes section appears at the end of this standard

Copyright ©ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
 0 E165/E165M - 23

E 1 209 Practice for Fluorescent Liquid Penetrant Testing 5. Significance and Use
Using the Water-Washable Process 5 . 1 Liquid penetrant testing methods indicate the presence,
E l 2 1 0 Practice for Fluorescent Liquid Penetrant Testing location, and to a limited extent, the nature and magnitude of
Using the Hydrophilic Post-Emulsification Process the detected discontinuities. Each of the various penetrant
E 1 2 1 9 Practice for Fluorescent Liquid Penetrant Testing methods has been designed for specific uses such as critical
Using the Solvent-Removable Process service items, volume of parts, portability, or localized areas of
E 1 220 Practice for Visible Penetrant Testing Using Solvent­ examination. The method selected will depend accordingly on
Removable Process the design and service requirements of the parts or materials
E l 3 1 6 Terminology for Nondestructive Examinations being tested.
E l 4 1 8 Practice for Visible Penetrant Testing Using the
Water-Washable Process 6. Classification of Penetrant Materials and Methods
E2297 Guide for Use of UV-A and Visible Light S ources and
6. 1 Liquid penetrant testing methods and materials are
Meters used in the Liquid Penetrant and Magnetic Particle
classified in accordance with AMS 2644 as listed in Table 1 .
Methods
E3022 Practice for Measurement of Emission Characteris­ 6.2 Fluorescent Penetrant Testing (Type !)-Fluorescent
tics and Requirements for LED UV-A Lamps Used m penetrant testing utilizes penetrants that fluoresce brilliantly
Fluorescent Penetrant and Magnetic Particle Testing when excited by UV-A radiation. The sensitivity of fl uorescent
2.2 APHA Standard: 4 penetrants depends on their ability to be retained in the various
429 Method for the Examination of Water and Wastewater size discontinuities during processing, and then to bleed out
2.3 SAE Standards: 5 into the developer coating and produce indications that will
AMS 2644 Inspection Material, Penetrant fluoresce. Fluorescent indications are many times brighter than
QPL-AMS-2644 Qualified Products of Inspection Materials, their surroundings when viewed under appropriate UV-A
Penetrant illumination.
6.3 Visible Penetrant Testing (Type /l)-Visible penetrant
3. Terminology
testing uses a penetrant that can be seen in visible light. The
3 . 1 The definitions relating to liquid penetrant testing, penetrant is usually red, so that resultant indications produce a
which appear in Terminology E 1 3 1 6, shall apply to the terms definite contrast with the white background of the developer.
used in this practice. Visible penetrant indications must be viewed under adequate
NOTE I-Throughout this practice, the term blacklight has been
visible light.
changed to UV-A to conform with the latest terminology in Terminology
E l 3 1 6. Blacklight can mean a broad range of ultraviolet radiation - 7. Materials
fluorescent penetrant testing uses only UV-A light.
7 . 1 Liquid Penetrant Testing Materials consist of fl uores­
4. Summary of Practice cent or visible penetrants, emulsifiers (oil-base and water­
base ), removers (water and solvent), and developers (dry
4. 1 Liquid penetrant may consist of visible or fluorescent
powder, aqueous, and nonaqueous). A family of liquid pen­
material. The liquid penetrant is applied evenly over the
etrant testing materials consists of the applicable penetrant and
surface being examined and allowed to enter open discontinui­
emulsifier, as recommended by the manufacturer. Any liquid
ties. After a suitable dwell time, the excess surface penetrant is
penetrant, remover, and developer listed in QPL-AMS-2644
removed. A developer is applied to draw the entrapped pen­
can be used, regardless of the manufacturer. Penetrants and
etrant out of the discontinuity and stain the developer. The test
emulsifiers shall be from the same family; use of a penetrant
surface is then examined to determine the presence or absence
and emulsifier from different manufacturers or family groups is
of indications.
prohibited.
Norn 4-Refer to 9. 1 for special requirements for sulfur, halogen, and
NOTE 2-The developer may b e omitted b y agreement between the
contracting parties.
alkali metal content.
NOTE 3-Fluorescent penetrant examination shall not follow a visible
penetrant examination unless the procedure has been qualified in accor­
dance with 1 0.2, because visible dyes may cause deterioration or
TABLE 1 Classification of Penetrant Testing Types and Methods
quenching of fluorescent dyes.
Type I-Fluorescent Penetrant Testing
4.2 Processing parameters, such as surface precleaning,
Method A-Water-washable (see Practice E1 209)
penetrant dwell time, and excess penetrant removal methods, Method A(W)-Water Washable Penetrant (penetrant containing
are dependent on the specific materials used, the nature of the >20 % water) (see Practice E1 209)
Method B-Post-emulsifiable, lipophilic (see Practice E1 208)
part under examination (that is, size, shape, surface condition,
Method C-Solvent removable (see Practice E1 2 1 9)
alloy), and type of discontinuities expected. Method 0-Post-emulsifiable, hydrop hilic (see Practice E1 2 1 0)
Type II-Visible Penetrant Testing
Method A-Water-washable (see Practice E1 4 1 8)
4 Available from American Public Health Association, Publication Office, 1015 Method A(W)-Water Washable Penetrant (penetrant containing
Fifteenth Street, NW, Washington, DC 20005. >20 % water) (see Practice E 1 4 1 8)
5 Available from Society of Automotive E ngineers (SAE), 400 Commonwealth Method C-Solvent removable (see Practice E1220)
Dr., Warrendale, PA 15096-000 I, http://www.sae.org.

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 0 E165/E165M - 23

NoTE 5-While approved penetrant materials will not adversely affect 7.4 Solvent Removers-Solvent removers function by dis­
common metallic materials, some plastics or rubbers may be swollen or solving the penetrant, making it possible to wipe the surface
stained by certain penetrants.
clean and free of excess penetrant.
7.2 Penetrants: 7 . 5 Developers-Developers form a translucent or white
7.2. 1 Post-Emulsifiable Penetrants are insoluble in water absorptive coating that aids in bringing the penetrant out of
and cannot be removed with water rinsing alone. They are surface discontinuities through blotting action, thus increasing
formulated to be selectively removed from the surface using a the visibility of the indications.
separate emulsifier. Properly applied and given a proper 7 . 5 . 1 Dry Powder Developers-Dry powder developers are
emulsification time, the emulsifier combines with the excess used as supplied, that is, free-flowing, non-caking powder (see
surface penetrant to form a water-washable mixture, which can 8.8. 1 ). Care should be taken not to contaminate the developer
be rinsed from the surface, leaving the surface free of excessive with fluorescent penetrant, as the contaminated developer
fluorescent background. Proper emulsification time must be specks can appear as penetrant indications.
experimentally established and maintained to ensure that 7 . 5 .2 Aqueous Developers-Aqueous developers are nor­
over-emulsification does not result in loss of indications. mally supplied as dry powder particles to be either suspended
(water suspendable) or dissolved (water soluble) in water. The
7 .2.2 Water-Washable Penetrants are formulated to be di­
concentration, use, and maintenance shall be in accordance
rectly water-washable from the surface of the test part, after a
with manufacturer' s recommendations. Water soluble develop­
suitable penetrant dwell time. Because the emulsifier is formu­
ers shall not be used with Type II penetrants or Type I, Method
lated into the penetrant or the penetrant is water-based (pen­
A or Method A(W) (penetrant containing >20 % water) pen­
etrant containing >20 % water), water-washable penetrants can
etrants.
be washed out of discontinuities if the rinsing step is too long
or too vigorous. It is therefore extremely important to exercise NOTE 6-Aqueous developers may cause stripping of indications if not
properly applied and controlled. The procedure should be qualified in
proper control in the removal of excess surface penetrant to
accordance with I0.2.
ensure against overwashing. Some penetrants are less resistant
7 . 5 . 3 Nonaqueous Wet Developers-Nonaqueous wet devel­
to overwashing than others, so caution should be exercised.
opers are supplied as suspensions of developer particles in a
7.2.3 Solvent-Removable Penetrants are formulated so that nonaqueous solvent carrier ready for use as supplied.
excess surface penetrant can be removed by wiping until most Nonaqueous, wet developers are sprayed on to form a thin
of the penetrant has been removed. The remaining traces coating on the surface of the part when dried. This thin coating
should be removed with the solvent remover (see 8.6.4). To serves as the developing medium.
prevent removal of penetrant from discontinuities, care should
NoTE 7-This type of developer is intended for application by spray
be taken to avoid the use of excess solvent. Flushing the only.
surface with solvent to remove the excess penetrant is prohib­
ited as the penetrant indications could easily be washed away. 8. Procedure

8. 1 The following processing parameters apply to both

7.3 Emulsifiers:
fluorescent and visible penetrant testing methods.
7 .3 . 1 Lipophilic Emulsifiers are oil-miscible liquids used to
8.2 Temperature Limits-The temperature of the penetrant
emulsify the post-emulsified penetrant on the surface of the
materials and the surface of the part to be processed shall be
part, rendering it water-washable. The individual characteris­
between 40 °F and 1 25 °F [4 °C and 52 °C] or the procedure
tics of the emulsifier and penetrant, and the geometry/surface
must be qualified at the temperature used as described in 1 0.2.
roughness of the part material contribute to determining the
8.3 Examination Sequence-Final penetrant examination
emulsification time.
shall be performed after the completion of all operations that
7.3.2 Hydrophilic Emulsifiers are water-miscible liquids
could cause surface-connected discontinuities or operations
used to emulsify the excess post-emulsified penetrant on the
that could expose discontinuities not previously open to the
surface of the part, rendering it water-washable. These water­
surface. Such operations include, but are not limited to,
base emulsifiers (detergent-type removers) are supplied as
grinding, welding, straightening, machining, and heat treating.
concentrates to be diluted with water and used as a dip or spray.
Satisfactory examination results can usually be obtained on
The concentration, use, and maintenance shall be in accordance surfaces in the as-welded, as-rolled, as-cast, as-forged, or
with manufacturer' s recommendations. ceramics in the densified condition.
7.3.2.1 Hydrophilic emulsifiers function by displacing the 8 . 3 . 1 Sutface Treatment-Final penetrant testing may be
excess penetrant film from the surface of the part through performed prior to treatments that can smear the surface but not
detergent action. The force of the water spray or air/mechanical by themselves cause surface discontinuities. S uch treatments
agitation in an open dip tank provides the scrubbing action include, but are not limited to, vapor blasting, deburring,
while the detergent displaces the film of penetrant from the part sanding, buffing, sand blasting, or lapping. Performance of
surface. The individual characteristics of the emulsifier and final penetrant testing after such surface treatments necessitates
penetrant, and the geometry and surface roughness of the part that the part(s) be etched to remove smeared metal from the
material contribute to determining the emulsification time. surface prior to testing unless otherwise agreed by the con­
Emulsification concentration shall be monitored weekly using tracting parties. Note that final penetrant testing shall always
a suitable refractometer. precede surface peening.

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 0 E165/E165M - 23

NoTE 8-Sand or shot blasting can close discontinuities, so extreme should be conducted prior to use. Electrostatic spray applica­
care should be taken to avoid masking discontinuities. Under certain tion can eliminate excess liquid build-up of penetrant on the
circumstances, however, grit blasting with certain air pressures, mediums,
part, minimize overspray, and minimize the amount of pen­
or both, may be acceptable without subsequent etching when agreed by
the contracting parties. etrant entering hollow-cored passages which might serve as
NOTE 9-Surface preparation of structural or electronic ceramics for penetrant reservoirs, causing severe bleedout problems during
penetrant testing by grinding, sand blasting, and etching is not recom­ examination. Aerosol sprays are conveniently portable and
mended because of the potential for damage.
suitable for local application.
8.4 Precleaning-The success of any penetrant testing pro­
NoTE 1 1-With spray applications, it is important that there be proper
cedure is greatly dependent upon the surrounding surface and
ventilation. This is generally accomplished through the use of a properly
discontinuity being free of any contaminant (solid or liquid) designed spray booth and exhaust system.
that might interfere with the penetrant process. All parts or
8 . 5 . 1 Penetrant Dwell Time-After application, allow ex­
areas of parts to be examined must be clean and dry before the
cess penetrant to drain from the part (care should be taken to
penetrant is applied. If only a section of a part, such as a weld,
prevent pools of penetrant from forming on the part), while
including the heat affected zone is to be examined, all
allowing for proper penetrant dwell time (see Table 2) . The
contaminants shall be removed from the area being examined
length of time the penetrant must remain on the part to allow
as defined by the contracting parties. "Clean" is intended to
proper penetration should be as recommended by the penetrant
mean that the surface must be free of rust, scale, welding flux,
manufacturer. Table 2, however, provides a guide for selection
weld spatter, grease, paint, oily films, dirt, and so forth, that
of penetrant dwell times for a variety of materials, forms, and
might interfere with the penetrant process. All of these con­
types of discontinuities. The maximum dwell time shall not
taminants can prevent the penetrant from entering discontinui­
exceed that recommended by the manufacturer; if no maximum
ties (see Annex A l on Cleaning of Parts and Materials).
is provided, the maximum dwell shall not exceed 2 h unless
8 .4 . 1 Drying after Cleaning-It is essential that the surface
penetrant is reapplied as required.
of parts be thoroughly dry after cleaning, since any liquid
residue will hinder the entrance of the penetrant into disconti­ 8.6 Penetrant Removal
nuities. Drying may be accomplished by warming the parts in 8.6. 1 Water Washable (Method A and Method A(W)):
drying ovens, with infrared lamps, forced hot air, or exposure 8.6. 1 . 1 Removal of Water Washable Penetrant-After the
to ambient temperature. required penetrant dwell time, the excess penetrant on the
NOTE 1 0-Residues from cleaning processes such as strong alkalies, surface being examined must be removed with water. It can be
pickling solutions, and chromates, in particular, may adversely react with removed manually with a coarse spray or wiping the part
the penetrant and reduce its sensitivity and performance. surface with a dampened rag, automatic or semi-automatic
8.5 Penetrant Application-After the part has been cleaned, water-spray equipment, or by water immersion. For immersion
dried, and is within the specified temperature range, the rinsing, parts are completely immersed in the water bath with
penetrant is applied to the surface to be examined so that the air or mechanical agitation.
entire part or area under examination is completely covered (a) The temperature of the water shall be maintained within
with penetrant. Application methods include dipping, brushing, the range of 50 °F to 1 00 °F [ 1 0 °C to 38 °C].
flooding, or spraying. Small parts are quite often placed in (b) Spray-rinse water pressure shall not exceed 40 psi
suitable baskets and dipped into a tank of penetrant. On larger [275 kPa] . When hydro-air pressure spray guns are used, the air
parts, and those with complex geometries, penetrant can be pressure should not exceed 25 psi [ 1 72 kPa].
applied effectively by brushing or spraying. Both conventional
NoTE 1 2-0verwashing should be avoided. Excessive washing can
and electrostatic spray guns are effective means of applying cause penetrant to be washed out of discontinuities; spray nozzles should
liquid penetrants to the part surfaces. Not all penetrant mate­ be kept a minimum of 1 2 in. [30 cm] from the surface when no physical
rials are suitable for electrostatic spray applications, so tests limitations exist. With fluorescent penetrant methods perform the manual

TABLE 2 Recommended Minimum Dwell Times

Type of Dwell TimesA (minutes)

Material Form
Discontinuity Penetrant8 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 ° F t o 1 25 ° F [1 0 °C to 52 °C]. For temperatures between 40 ° F and 50 ° F [4.4 °C and 1 0 °C], recommend a minimum dwell time of 20 min.
8 Maximum penetrant dwell time in accordance with 8.5.1 .
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 .8.4.

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 0 E165/E165M - 23

rinsing operation under UV-A light so that it can be determined when the rinsing of the part(s). The water spray pressure shall not exceed
surface penetrant has been adequately removed.
40 psi [275 kPa] when manual or hydro air spray guns are used.
8.6.2 Lipophilic Emulsification (Method B): When hydro-air pressure spray guns are used, the air pressure
8.6.2. 1 Application of Lipophilic Emulsifier-After the re­ shall not exceed 25 psi [ 1 72 kPa] . Water free of contaminants
quired penetrant dwell time, the excess penetrant on the part that could clog spray nozzles or leave a residue on the part(s)
must be emulsified by immersing or flooding the parts with the is recommended.
required emulsifier (the emulsifier combines with the excess 8.6.3.3 Application of Emulsifier-The residual surface pen­
surface penetrant and makes the mixture removable by water etrant on part(s) must be emulsified by immersing the part(s) in
rinsing). Lipophilic emulsifier shall not be applied by spray or an agitated hydrophilic emulsifier bath or by spraying the
brush and the part or emulsifier shall not be agitated while part(s) with water/emulsifier solutions thereby rendering the
being immersed. After application of the emulsifier, the parts remaining residual surface penetrant water-washable for the
shall be drained and positioned in a manner that prevents the final rinse station. The emulsification time begins as soon as the
emulsifier from pooling on the part(s).
emulsifier is applied. The length of time that the emulsifier is
8.6.2.2 Emulsification Time-The emulsification time be­ allowed to remain on a part and in contact with the penetrant
gins as soon as the emulsifier is applied. The length of time that is dependent on the type of emulsifier employed and the
the emulsifier is allowed to remain on a part and in contact with
surface roughness. The emulsification time should be deter­
the penetrant is dependent on the type of emulsifier employed
mined experimentally for each specific application. The sur­
and the surface roughness. Nominal emulsification time should
face finish (roughness of the part) is a significant factor in
be as recommended by the manufacturer. The actual emulsifi­
determining the emulsification time necessary for an emulsi­
cation time must be determined experimentally for each
fier. Contact emulsification time should be kept to the least
specific application. The surface finish (roughness) of the part
possible time consistent with an acceptable background and
is a significant factor in the selection of and in the emulsifica­
shall not exceed 2 min.
tion time of an emulsifier. Contact time shall be kept to the
(a) Immersion- For immersion application, parts shall be
minimum time to obtain an acceptable background and shall
completely immersed in the emulsifier bath. The hydrophilic
not exceed 3 min.
emulsifier concentration shall be as recommended by the
8.6.2.3 Post Rinsing-Effective post rinsing of the emulsi­
manufacturer and the bath or part shall be gently agitated by air
fied penetrant from the surface can be accomplished using
or mechanically throughout the cycle. The minimum time to
either manual, semi-automated, or automated water immersion
obtain an acceptable background shall be used, but the dwell
or spray equipment or combinations thereof.
time shall not be more than 2 min unless approved by the
8.6.2.4 Immersion-For immersion post rinsing, parts are
contracting parties.
completely immersed in the water bath with air or mechanical
(b) Spray Application- For spray applications, all part
agitation. The amount of time the part is in the bath should be
surfaces should be evenly and uniformly sprayed with a
the minimum required to remove the emulsified penetrant. In
addition, the temperature range of the water should be 50 °F to water/emulsifier solution to effectively emulsify the residual
1 00 °F [ 1 0 °C to 38 °C] . Any necessary touch-up rinse after an penetrant on part surfaces to render it water-washable. The
immersion rinse shall meet the requirements of 8.6.2.5 . concentration of the emulsifier for spray application should be
in accordance with the manufacturer' s recommendations, but it
8.6.2.5 Spray Post Rinsing-Effective post rinsing follow­
ing emulsification can also be accomplished by either manual shall not exceed 5 %. The water spray pressure should be less
or automatic water spray rinsing. The water temperature shall than 40 psi [275 kpa]. The nozzle shall produce a coarse spray
be between 50 °F and 1 00 °F [ 1 0 °C and 38 °C]. The water pattern similar to that used in rinsing. Contact with the
spray pressure shall not exceed 40 psi [275 kPa] when manual emulsifier shall be kept to the minimum time to obtain an
spray guns are used. When hydro-air pressure spray guns are acceptable background and shall not exceed 2 min. The water
used, the air pressure should not exceed 25 psi [ 1 72 kPa] . temperature shall be maintained between 50 °F and 1 00 °F
8.6.2.6 Rinse Effectiveness-If the emulsification and final [ 1 0 °C and 3 8 °C] .
rinse step is not effective, as evidenced by excessive residual 8 . 6 . 3 . 4 Post-Rinsing of Hydrophilic Emulsified
surface penetrant after emulsification and rinsing; thoroughly Penetrants-Effective post-rinsing of emulsified penetrant
reclean and completely reprocess the part. from the surface can be accomplished using either manual or
8.6.3 Hydrophilic Emulsification (Method D): automated water spray, water immersion, or combinations
8.6.3 . 1 Application of Hydrophilic Remover-Following the thereof. The total rinse time shall not exceed 2 min regardless
required penetrant dwell time, the parts may be prerinsed with of the number of rinse methods used.
water prior to the application of hydrophilic emulsifier. This (a) Immersion Post-Rinsing- If an agitated immersion
prerinse allows for the removal of excess surface penetrant rinse is used, the amount of time the part(s) is (are) in the bath
from the parts prior to emulsification so as to minimize shall be the minimum required to remove the emulsified
penetrant contamination in the hydrophilic emulsifier bath, penetrant and shall not exceed 2 min. In addition, the tempera­
thereby extending its life. It is not necessary to prerinse a part ture range of the water shall be within 50 °F and 1 00 °F [ 1 0 °C
if a spray application of emulsifier is used. and 38 °C] . Be aware that a touch-up rinse may be necessary
8.6.3.2 Prerinsing Contro ls-Effective prerinsing is accom­ after immersion rinse, but the total wash time still shall not
plished by manual, semi-automated, or automated water exceed 2 min.
spray
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 0 E165/E165M - 23

(b) Spray Post-Rinsing- Effective post-rinsing following tapping the part, or by blowing with low-pressure dry, clean,
emulsification can also be accomplished by manual, semi­ compressed air not exceeding 5 psi [34 kPa]. Dry developers
automatic, or automatic water spray. The water spray pressure shall not be used with Type II penetrant.
shall not exceed 40 psi [275 kPa] when manual or hydro-air 8.8.2 Aqueous Developers (Forms B and CJ-Water soluble
spray guns are used. When hydro-air pressure spray guns are developers (Form B) are prohibited for use with Type II
used, the air pressure shall not exceed 25 psi [ 1 72 kPa] . The penetrants or Type I, Method A penetrants. Water suspendable
water temperature shall be between 50 °F and 1 00 °F [ 1 0 °C developers (Form C) can be used with both Type I and Type II
and 38 °C]. The spray rinse time shall be less than 2 min, penetrants. Aqueous developers shall be applied to the part
unless otherwise specified. immediately after the excess penetrant has been removed and
8.6.3.5 Rinse Effectiveness-If the emulsification and final prior to drying. Aqueous developers shall be prepared and
rinse steps are not effective, as evidenced by excessive residual maintained in accordance with the manufacturer ' s instructions
surface penetrant after emulsification and rinsing, thoroughly and applied in such a manner as to ensure complete, even, part
reclean, and completely reprocess the part. coverage. Aqueous developers may be applied by spraying,
8.6.4 Removal of Solvent-Removable Penetrant (Method flowing, or immersing the part in a prepared developer bath.
CJ-After the required penetrant dwell time, the excess pen­ Immerse the parts only long enough to coat all of the part
etrant is removed by wiping with a dry, clean, lint-free surfaces with the developer since indications may leach out if
cloth/towel. Then use a clean lint-free cloth/towel lightly the parts are left in the bath too long. After the parts are
moistened with solvent to remove the remaining traces of removed from the developer bath, allow the parts to drain.
surface penetrant as determined by examination under UV-A Drain all excess developer from recesses and trapped sections
lighting for fluorescent methods and visible light for visible to eliminate pooling of developer, which can obscure discon­
methods. Perform a final wipe using a dry, clean cloth to tinuities. Dry the parts in accordance with 8.7. The dried
remove any solvent residues that might remain. Gentle wiping developer coating appears as a translucent or white coating on
must be used to avoid removing penetrant from any disconti­ the part.
nuity. On smooth surfaces, an alternate method of removal can 8.8.3 Nonaqueous Wet Developers (Forms D and £)-After
be done by wiping with a clean, dry cloth. Flushing the surface the excess penetrant has been removed and the surface has
with solvent following the application of the penetrant and been dried, apply nonaqueous wet developer by spraying in
prior to developing is prohibited. such a manner as to ensure complete part coverage with a thin,
even film of developer. The developer shall be applied in a
8.7 Drying-Regardless of the type and method of penetrant
manner appropriate to the type of penetrant being used. For
used, drying the surface of the part(s) is necessary prior to
visible dye, the developer must be applied thickly enough to
applying dry or nonaqueous developers or following the
application of the aqueous developer. Drying time will vary provide a contrasting background. For fluorescent dye, the
developer must be applied thinly to produce a translucent
with the type of drying used and the size, nature, geometry, and
covering. Dipping or flooding parts with nonaqueous develop­
number of parts being processed.
ers is prohibited, because the solvent action of these types of
8.7 . 1 Drying Parameters-Components shall be air dried at
developers can flush or dissolve the penetrant from within the
room temperature or in a drying oven. Room temperature
discontinuities.
drying can be aided by the use of fans. Oven temperatures shall
not exceed 1 60 °F [7 1 °C] . Drying time shall only be that NOTE 13-The vapors from the volatile solvent carrier in the developer
necessary to adequately dry the part. Components shall be may be hazardous. Proper ventilation should be provided at all times, but
removed from the oven after drying. Components should not especially when the developer is applied inside a closed area.

be placed in the oven with pooled water or pooled aqueous 8. 8.4 Developing Time-The length of time the developer is
solutions/suspensions. to remain on the part prior to examination shall be not less than
1 0 min. Developing time begins immediately after the appli­
8.8 Developer Application-There are various modes of
cation of dry powder developer or as soon as the wet (aqueous
effective application of the various types of developers such as
or nonaqueous) developer coating is dry (that is, the water or
dusting, immersing, flooding, or spraying. The developer form,
solvent carrier has evaporated to dryness). The maximum
the part size, configuration, and surface roughness will influ­
permitted developing times shall be 4 h for dry powder
ence the choice of developer application.
developer (Form A), 2 h for aqueous developer (Forms B and
8.8. 1 Dry Powder Developer (Form A)-Dry powder devel­
C), and 1 h for nonaqueous developer (Forms D and E).
opers shall be applied after the part is dry in such a manner as
to ensure complete coverage of the area of interest. Parts can be 8.9 Examination-After the applicable development time,
immersed in a container of dry developer or in a fluid bed of perform examination of the parts under visible light or UV-A
dry developer. They can also be dusted with the powder radiation as appropriate. It may be helpful to observe the bleed
developer through a hand powder bulb or a conventional or out during the development time as an aid in interpreting
electrostatic powder gun. It is common and effective to apply indications. LED UV-A sources, with the exception of Bore­
dry powder in an enclosed dust chamber, which creates an scope LED UV-A sources, shall meet the requirements of
effective and controlled dust cloud. Other means suited to the Practice E3022.
size and geometry of the specimen may be used, provided the 8.9 . 1 UV-A Radiance Examination-Examine parts tested
powder is applied evenly over the entire surface being exam­ with Type I fluorescent penetrant under UV-A irradiance in a
ined. Excess developer powder may be removed by shaking or darkened area. Ambient visible light shall not exceed 2 fc

6
 0 E165/E165M - 23

[2 1 .5 Ix] . The ambient light measurement shall be made with a 8. 1 0 Post Cleaning-Post cleaning is necessary when re­
suitable visible light sensor at the examination surface, with sidual penetrant or developer could interfere with subsequent
visible light sources off. processing or with service requirements. It is particularly
important where residual penetrant testing materials might
NoTE 1 4-Because the fluorescent constituents in the penetrant will
eventually fade with direct exposure to UV-A sources, direct exposure of
combine with other factors in service to produce corrosion and
the part under test to UV-A radiation should be minimized when not prior to vapor degreasing or heat treating the part as these
removing excess penetrant or evaluating indications. processes can bake the developer onto the part. A suitable
8.9. 1 . 1 UV-A Radiance Level Control-UV-A sources shall technique, such as a simple water rinse, water spray, machine
2 wash, solvent soak, or ultrasonic cleaning may be employed
provide a minimum irradiance of 1 000 µW/cm , at a distance
of 1 5 in. [38. l cm] . The intensity shall be checked daily to (see Annex A l for further information on post cleaning). It is
ensure the required output (see Guide E2297 for more infor­ recommended that if developer removal is necessary, it should
mation). Reflectors and filters shall also be checked daily for be carried out as promptly as possible after examination so that
cleanliness and integrity. Cracked or broken ultraviolet filters the developer does not adhere to the part.
shall be replaced immediately. LED UV-A sources used to
examine parts shall be checked daily (or before use if not used 9. Special Requirements
daily) to ensure that all elements are operational. If any diode 9 . 1 Impurities:
element is not operational the condition shall be corrected or 9 . 1 . 1 When using penetrant materials on austenitic stainless
the unit replaced. The operational check should be performed steels, titanium, nickel-base, or other high-temperature alloys,
by placing a white sheet of paper over the lamp and then the need to restrict certain impurities such as sulfur, halogens,
viewing the transmitted light from each diode. LED UV-A and alkali metals must be considered. These impurities may
sources are at full intensity at power-on, and the intensity may cause embrittlement or corrosion, particularly at elevated
decrease as the lamp stabilizes. temperatures. Any such evaluation shall also include consider­
NOTE 1 5-Certain high-intensity UV-A sources may emit unacceptable ation of the form in which the impurities are present. Some
amounts of visible light, which can cause fluorescent indications to penetrant materials contain significant amounts of these impu­
disappear. Care should be taken to only use bulbs suitable for fluorescent rities in the form of volatile organic solvents that normally
penetrant examination purposes.
evaporate quickly and usually do not cause problems. Other
8.9. 1 .2 UV-A Source Warm- Up-Unless otherwise specified materials may contain impurities, which are not volatile and
by the manufacturer, allow the UV-A source to warm up for a may react with the part, particularly in the presence of moisture
minimum of 10 min prior to use or measurement of its or elevated temperatures.
intensity. LED UV-A sources do not require warmup. 9. 1 .2 Because volatile solvents leave the surface quickly
8.9. 1 . 3 Visual Adaptation-Personnel examining parts after without reaction under normal examination procedures, pen­
penetrant processing shall be in the darkened area for at least etrant materials are normally subjected to an evaporation
1 min before examining parts. Longer times may be necessary procedure to remove the solvents before the materials are
under some circumstances. Photochromic or tinted lenses shall analyzed for impurities. The residue from this procedure is
not be worn during the processing and examination of parts. then analyzed in accordance with Test Method D l 552 or Test
8.9.2 Visible Light Examination-Examine parts tested with Method Dl29 decomposition followed by Test Method E5 1 6,
Type II visible penetrant under either natural or artificial visible Method B (Turbidimetric Method) for sulfur. The residue may
light. Proper illumination is required to ensure adequate also be analyzed by Annex A2 on Methods for Measuring Total
sensitivity of the examination. A minimum light intensity at the Chlorine Content in Combustible Liquid Penetrant Materials
examination surface of 1 00 fc [ 1 076 Ix] is required (see Guide (for halogens other than fluorine) and Annex A3 on Method for
E2297 for more information). Measuring Total Fluorine Content in Combustible Liquid
8.9.3 Housekeeping-Keep the examination area free of Penetration Materials (for fluorine). An alternative procedure,
interfering debris, including fluorescent residues and objects. Annex A4 on Determination of Anions by Ion
8.9.4 Indication Verification-If allowed by the specific Chromatography, provides a single instrumental technique for
procedure, indications may be evaluated by wiping the indica­ rapid sequential measurement of common anions such as
tion with a solvent-dampened swab, brush, or lint-free cloth chloride, fluoride, and sulfate (see Test Method D4327) . Alkali
allowing the area to dry, and redeveloping the area. Redevel­ metals in the residue are determined by flame photometry,
opment time shall be a minimum of 10 min, except nonaqueous atomic absorption spectrophotometry, or ion chromatography
redevelopment time should be a minimum of 3 min. If the (see Test Method D69 1 9).
indication does not reappear, the original indication may be
NoTE 1 6-Some current standards require impurity levels of sulfur and
considered false. This procedure may be performed up to two halogens to not exceed 1 % of any one suspect element. This level,
times for any given original indication. Unless prohibited by however, may be unacceptable for some applications, so the actual
the Purchaser, Specification D770 isopropyl alcohol and Speci­ maximum acceptable impurity level must be decided between supplier and
fication D329 acetone are commonly accepted solvents. user on a case by case basis.

8.9.5 Evaluation-All indications found during examination 9 . 2 Elevated-Temperature or Low-Temperature

shall be evaluated in accordance with acceptance criteria as Examination-Where penetrant examination is performed on
specified. Reference Photographs of indications are noted in parts that must be maintained at elevated or lowered tempera­
E433. ture during testing, special penetrant materials and processing

7
 0 E165/E165M - 23

techniques may be required. Such examination requires quali­ it displays the characteristics of the discontinuities encountered
fication in accordance with 1 0.2 and the manufacturer' s rec­ in product examination.
ommendations shall be observed. 1 0.2. 1 Requalification of the procedure to be used may be
required when a change is made to the procedure or when
10. Qualification and Requalification
material substitution is made.
1 0. 1 Personnel Qualification-If specified in the contractual
1 0. 3 Nondestructive Testing Agency Qualification-If a
agreement, personnel performing examinations to this practice
nondestructive testing agency as described in Practice E543 is
shall be qualified in accordance with a nationally or interna­
used to perform the examination, the agency should meet the
tionally recognized NDT personnel qualification practice or
requirements of Practice E543.
standard and certified by the employer or certifying agency, as
applicable. The practice or standard used shall be identified in 1 0.4 Requalification may be required when a change or
the contractual agreement between the using parties. substitution is made in the type of penetrant materials or in the
procedure (see 1 0.2).
1 0.2 Procedure Qualification-Qualification of procedures
using times, conditions, or materials differing from those
11. Keywords
specified in this general practice or for new materials may be
performed by any of several methods and should be agreed 1 1 . 1 fluorescent liquid penetrant examination; hydrophilic
upon by the contracting parties. A test piece containing one or emulsification; lipophilic emulsification; liquid penetrant ex­
more discontinuities of the smallest relevant size is generally amination; nondestructive examination; post-emulsified; sol­
used. When agreed upon by the contracting parties, the test vent removable; visible liquid penetrant examination; water­
piece may contain real or simulated discontinuities, providing washable; ultraviolet light; UV-A; visible light

ANNEXES

(Mandatory Information)

Al. CLEANING OF PARTS AND MATERIALS

Al.1 Choice of Cleaning Method general, inorganic soils. Some cleaning solvents are fl ammable
and can be toxic. Observe all manufacturers' instructions and
A 1 . 1 . 1 The choice of a suitable cleaning method is based on
precautionary notes.
such factors as: (1) type of contaminant to be removed since no
A l . 1 . 1 .3 Vapor Degreasing-Vapor degreasing is a pre­
one method removes all contaminants equally well; (2) effect
ferred method of removing oil or grease-type soils from the
of the cleaning method on the parts; (3) practicality of the
surface of parts and from open discontinuities. It will not
cleaning method for the part (for example, a large part cannot
remove inorganic-type soils (dirt, corrosion, salts, etc.), and
be put into a small degreaser or ultrasonic cleaner); and (4)
may not remove resinous soils (plastic coatings, varnish, paint,
specific cleaning requirements of the purchaser. The following
etc.). Because of the short contact time, degreasing may not
cleaning methods are recommended:
completely clean out deep discontinuities and a subsequent
A 1 . 1 . 1 . 1 Detergent Cleaning-Detergent cleaners are non­ solvent soak is recommended.
flammable water-soluble compounds containing specially se­
A l . 1 . 1 .4 Alkaline Cleaning:
lected surfactants for wetting, penetrating, emulsifying, and
(a) Alkaline cleaners are nonflammable water solutions
saponifying various types of soils, such as grease and oily containing specially selected detergents for wetting,
films, cutting and machining fluids, and unpigmented drawing penetrating, emulsifying, and saponifying various types of
compounds, etc. Detergent cleaners may be alkaline, neutral, or soils. Hot alkaline solutions are also used for rust removal and
acidic in nature, but must be noncorrosive to the item being descaling to remove oxide scale which can mask surface
examined. The cleaning properties of detergent solutions discontinuities. Alkaline cleaner compounds must be used in
facilitate complete removal of soils and contamination from the accordance with the manufacturers' recommendations. Parts
surface and void areas, thus preparing them to absorb the cleaned by the alkaline cleaning process must be rinsed
penetrant. Cleaning time should be as recommended by the completely free of cleaner and thoroughly dried prior to the
manufacturer of the cleaning compound. penetrant testing process (part temperature at the time of
A l . 1 . 1 .2 Solvent Cleaning-There are a variety of solvent penetrant application shall not exceed 1 25 °F [52 °C]).
cleaners that can be effectively utilized to dissolve such soils as (b) Steam cleaning is a modification of the hot-tank alka­
grease and oily films, waxes and sealants, paints, and in line cleaning method, which can be used for preparation of
general, organic matter. These solvents should be residue-free, large, unwieldy parts. It will remove inorganic soils and many
especially when used as a hand-wipe solvent or as a dip-tank organic soils from the surface of parts, but may not reach to the
degreasing solvent. Solvent cleaners are not recommended for bottom of deep discontinuities, and a subsequent solvent soak
the removal of rust and scale, welding flux and spatter, and in is recommended.

8
 0 E165/E165M - 23

A l . 1 . 1 .5 Ultrasonic Cleaning-This method adds ultrasonic A l . 1 . 1 .8 Acid Etching-Inhibited acid solutions (pickling
agitation to solvent or detergent cleaning to improve cleaning solutions) are routinely used for descaling part surfaces.
efficiency and decrease cleaning time. It should be used with Descaling is necessary to remove oxide scale, which can mask
water and detergent if the soil to be removed is inorganic (rust, surface discontinuities and prevent penetrant from entering.
dirt, salts, corrosion products, etc.), and with organic solvent if Acid solutions/etchants are also used routinely to remove
the soil to be removed is organic (grease and oily films, etc.). smeared metal that peens over surface discontinuities. Such
After ultrasonic cleaning, parts must be rinsed completely free etchants should be used in accordance with the manufacturers'
of cleaner, thoroughly dried, and cooled to at least 1 25 °P recommendations.
(52 °C], before application of penetrant. NoTE A l . 1-Etched parts and materials should be rinsed completely
free of etchants, the surface neutralized and thoroughly dried by heat prior
A l . 1 . 1 .6 Paint Removal-Paint films can be effectively
to application of penetrants. Acids and chromates can adversely affect the
removed by bond release solvent paint remover or fluorescence of fluorescent materials.
disintegrating-type hot-tank alkaline paint strippers. In most NoTE A 1 .2-Whenever there is a possibility of hydrogen embrittlement
cases, the paint film must be completely removed to expose the as a result of acid solution/etching, the part should be baked at a suitable
temperature for an appropriate time to remove the hydrogen before further
surface of the metal. Solvent-type paint removers can be of the
processing. After baking, the part shall be cooled to a temperature below
high-viscosity thickened type for spray or brush application or 1 25 °F [52 °CJ before applying penetrants.
can be of low viscosity two-layer type for dip-tank application.
A l . 1 . 1 .9 Air Firing of Ceramics-Heating of a ceramic part
B oth types of solvent paint removers are generally used at
in a clean, oxidizing atmosphere is an effective way of
ambient temperatures, as received. Hot-tank alkaline strippers
removing moisture or light organic soil, or both. The maximum
should be used in accordance with the manufacturer' s instruc­
temperature that will not cause degradation of the properties of
tions. After paint removal, the parts must be thoroughly rinsed
the ceramic should be used.
to remove all contamination from the void openings, thor­
oughly dried, and cooled to at least 1 25 °P [52 °C] before Al.2 Post Cleaning
application of penetrant. A l .2. 1 Removal of Developer-Dry powder developer can
A l . 1 . 1 .7 Mechanical Cleaning and Surface Conditioning­ be effectively removed with an air blow-off (free of oil) or it
Metal-removing processes such as filing, buffing, scraping, can be removed with water rinsing. Wet developer coatings can
mechanical milling, drilling, reaming, grinding, liquid honing, be removed effectively by water rinsing or water rinsing with
sanding, lathe cutting, tumble or vibratory deburring, and detergent either by hand or with a mechanical assist (scrub
abrasive blasting, including abrasives such as glass beads, brushing, machine washing, etc.). The soluble developer coat­
sand, aluminum oxide, ligno-cellulose pellets, metallic shot, ings simply dissolve off of the part with a water rinse.
etc. , are often used to remove such soils as carbon, rust and A l .2.2 Residual penetrant may be removed through solvent
scale, and foundry adhering sands, as well as to deburr or action. Solvent soaking ( 1 5 min minimum), and ultrasonic
produce a desired cosmetic effect on the part. These processes solvent cleaning (3 min minimum) techniques are recom­
may decrease the effectiveness of the penetrant testing by mended. In some cases, it is desirable to vapor degrease, then
smearing or peening over metal surfaces and filling disconti­ follow with a solvent soak. The actual time required in the
nuities open to the surface, especially for soft metals such as vapor degreaser and solvent soak will depend on the nature of
aluminum, titanium, magnesium, and beryllium alloy. the part and should be determined experimentally.

A2. METHODS FOR MEASURING TOTAL CHLORINE CONTENT IN COMBUSTIBLE LIQUID

PENETRANT MATERIALS

A2.1 Scope and Application A2.2 Summary of Methods

A2. 1 . 1 These methods cover the determination of chlorine A2.2. 1 The sample is oxidized by combustion in a bomb
in combustible liquid penetrant materials, liquid or solid. Its containing oxygen under pressure (see A2.2. l . l ). The chlorine
range of applicability is 0.00 1 % to 5 % using either of the compounds thus liberated are absorbed in a sodium carbonate
alternative titrimetric procedures. The procedures assume that solution and the amount of chloride present is determined
bromine or iodine will not be present. If these elements are titrimetrically either against silver nitrate with the end point
present, they will be detected and reported as chlorine. The full detected potentiometrically (Method A) or coulometrically
amount of these elements will not be reported. Chromate with the end point detected by current flow increase
interferes with the procedures, causing low or nonexistent end (Method B).
points. The method is applicable only to materials that are A2.2. 1 . 1 Safety-Strict adherence to all of the provisions
totally combustible. prescribed hereinafter ensures against explosive rupture of the

9
 0 E165/E165M - 23
bomb, or a blow-out, provided the bomb is of proper design A2.5 Sample Preparation
and construction and in good mechanical condition. It is A2. 5 . 1 Penetrants, Developers, Emulsifiers, Magnetic Oils:
desirable, however, that the bomb be enclosed in a shield of
A2.5 . 1 . 1 Weigh 50 g of test material into a 150 mm petri
steel plate at least 1/2 in. [ 1 2.7 mm] thick, or equivalent
dish.
protection be provided against unforeseeable contingencies.
A2. 5 . 1 .2 Place the 1 5 0 mm petri dish into a 1 94 °P [90 °C]
A2.3 Apparatus
to 2 1 2 °P [ 1 00 °C] oven for 60 min.
A2.5 . 1 .3 Allow the test material to cool to room tempera­
A2.3 . 1 Bomb, having a capacity of not less than 300 mL, so ture.
constructed that it will not leak during the test, and that
A2.5.2 Solvent Cleaners:
quantitative recovery of the liquids from the bomb may be
A2.5.2. 1 Take the tare weight of an aluminum dish.
readily achieved. The inner surface of the bomb may be made
A2.5.2.2 Weigh 1 00 g of the cleaner into the aluminum
of stainless steel or any other material that will not be affected
dish.
by the combustion process or products. Materials used in the
bomb assembly, such as the head gasket and leadwire A2.5.2.3 Place the aluminum dish on a hot plate in a fume
insulation, shall be resistant to heat and chemical action, and hood.
shall not undergo any reaction that will affect the chlorine A2.5.2.4 Let the material evaporate until the dish is nearly
content of the liquid in the bomb. dry.
A2.5.2.5 Place the dish into a preheated oven from 1 94 °P
A2.3.2 Sample Cup, platinum, 24 mm in outside diameter at [90 °C] to 2 1 2 °P [ 1 00 °C] for 1 0 min.
the bottom, 27 mm in outside diameter at the top, 1 2 mm in A2.5.2.6 Take the dish out of the oven and allow to cool.
height outside and weighing 10 g to 1 1 g, opaque fused silica, A2.5.2.7 Reweigh the dish and record weight.
wide-form with an outside diameter of 29 mm at the top, a NoTE A2.3-For Cleaners-If the residue is less than 50 ppm, report
height of 1 9 mm, and a 5 mL capacity (Note A2.l), or nickel the residue weight. If the weight is greater than 50 ppm, proceed with the
(Kawin capsule form), top diameter of 28 mm, 1 5 mm in bomb procedure.
height, and 5 mL capacity.
A2.6 Decomposition
NOTE A2. l -Fused silica crucibles are much more economical and A2.6. l Reagents and Materials:
longer-lasting than platinum. After each use, they should be scrubbed out
A2.6. l . 1 Oxygen, free of combustible material and halogen
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. compounds, available at a pressure of 40 atm [4.05 MPa].
A2.6. 1 .2 Sodium Carbonate Solution (50 g Na2C03/L) or
Potassium Carbonate/Bicarbonate Solution (0. 1 84 g K2C03 +
A2.3 .3 Firing Wire, platinum, approximately No. 26 B & S

0. 15 g KHC03)/L-For the Sodium Carbonate Solution, dis­

gauge.
A2.3.4 Ignition Circuit (Note A2.2), capable of supplying solve 50 g of anhydrous Na2C03 (or 58.5 g of Na2C03·20) or
sufficient current to ignite the nylon thread or cotton wicking 1 35 g of Na2C03· 1 0H20 in water and dilute to 1 L. For the
without melting the wire. Potassium Carbonate/Bicarbonate Solution, dissolve 0. 184 g of
anhydrous K2C03 and 0. 1 5 g of KHC03 in water and dilute to
NOTE A2.2-The switch in the ignition circuit should be of a type that
remains open, except when held in closed position by the operator. one liter.
A2.6. 1 . 3 White Oil, refined.
A2.3.5 Nylon Sewing Thread, or Cotton Wicking, white.
A2.6.2 Procedure:
A2.4 Purity of Reagents A2.6.2. l Preparation of Bomb and Sample-Cut a piece of
A2.4. 1 Reagent grade chemicals shall be used in all tests. firing wire approximately 1 00 mm in length. Coil the middle
section (about 20 mm) and attach the free ends to the terminals.
Unless otherwise indicated, it is intended that all reagents shall
conform to the specifications of the Committee on Analytical Arrange the coil so that it will be above and to one side of the
Reagents of the American Chemical Society, where such sample cup. Place 5 mL of Na2C03 or K2C03 solution in the
bomb (Note A2.4), place the cover on the bomb, and vigor­
specifications are available. 6 Other grades may be used pro­
vided it is first ascertained that the reagent is of sufficiently ously shake for 1 5 s to distribute the solution over the inside of
high purity to permit its use without lessening the accuracy of the bomb. Open the bomb, place the sample-filled sample cup
in the terminal holder, and insert a short length of thread
the determination.
between the firing wire and the sample. Use of a sample weight
A2.4.2 Unless otherwise indicated, references to water shall containing over 20 mg of chlorine may cause corrosion of the
be understood to mean referee grade reagent water conforming bomb. The sample weight should not exceed 0.4 g if the
to Specification D 1 193 . expected chlorine content is 2.5 % or above. If the sample is
solid, not more than 0.2 g should be used. Use 0.8 g of white
oil with solid samples. If white oil will be used (Note A2.5),
6 ACS Reagent Chemicals, Specifications and Procedures fo r Reagents and add it to the sample cup by means of a dropper at this time (see
Standard-Grade Reference Materials, American Chemical Society, Washington, Note A2.6 and Note A2.7).
DC. For suggestions on the testing of reagents not listed by the American Chemical
Society, see Analar Standards fo r Laboratory Chemicals, BDH Ltd., Poole, Dorset, Norn A2.4-After repeated use of the bomb for chlorine determination,
U.K., and the United States Pharmacopeia and Natio nal Fo rmulary, U.S. Pharma­ a film may be noticed on the inner surface. This dullness should be
copeial Convention, Inc. (USPC), Rockville, MD. removed by periodic polishing of the bomb. A satisfactory method for

10
 0 E165/E165M - 23

doing this is to rotate the bomb in a lathe at about 300 rpm and polish the NoTE A2.8-An automatic titrator is highly recommended in place of
inside surface with Grit No. 210 or equivalent paper coated with a light items A2.7. l .3 and A2.7. l .4. Repeatability and sensitivity of the method
machine oil to prevent cutting, and then with a paste of grit-free chromic are much enhanced by the automatic equipment while much tedious effort
oxide and water. This procedure will remove all but very deep pits and put is avoided.
a high polish on the surface. Before using the bomb, it should be washed
A2.7.2 Reagents and Materials:
with soap and water to remove oil or paste left from the polishing
operation. Bombs with porous or pitted surfaces should never be used A2.7.2. l Acetone, chlorine-free.
because of the tendency to retain chlorine from sample to sample. It is A2.7.2.2 Methanol, chlorine-free.
recommended to not use more than 1 g total of sample and white oil or A2.7.2.3 Silver Nitrate Solution (0.0282 NJ-Dissolve
other chlorine-free combustible material.
4.79 1 0 g ::!:: 0.0005 g of silver nitrate (AgN03) in water and
NoTE A2.5-If the sample is not readily miscible with white oil, some
other nonvolatile, chlorine-free combustible diluent may be employed in
dilute to 1 L.
place of white oil. However, the combined weight of sample and A2.7.2.4 Sodium Chloride Solution (0. 0282 N)-Dry a few
nonvolatile diluent shall not exceed 1 g. Some solid additives are grams of sodium chloride (NaCl) for 2 h at 1 30 °C to 1 50 °C,
relatively insoluble, but may be satisfactorily burned when covered with weigh out 1 .6480 g ::!:: 0.0005 g of the dried NaCl, dissolve in
a layer of white oil.
water, and dilute to 1 L.
A2.7.2.5 Sulfuric Acid ( 1 + 2)-M ix 1 volume of concen­
NoTE A2.6-The practice of running alternately samples high and low
in chlorine content should be avoided whenever possible. It is difficult to
rinse the last traces of chlorine from the walls of the bomb and the trated sulfuric acid (H2S04, sp. gr 1 .84) with 2 volumes of
tendency for residual chlorine to carry over from sample to sample has water.
been observed in a number of laboratories. When a sample high in
chlorine has preceded one low in chlorine content, the test on the A2.7 .3 Collection of Chlorine Solution-Remove the
low-chlorine sample should be repeated and one or both of the low values sample cup with clean forceps and place in a 400 mL beaker.
thus obtained should be considered suspect if they do not agree within the Wash down the walls of the bomb shell with a fine stream of
limits of repeatability of this method. methanol from a wash bottle, and pour the washings into the
A2.6.2.2 Addition of Oxygen-Place the sample cup in beaker. Rinse any residue into the beaker. Next, rinse the bomb
position and arrange the nylon thread, or wisp of cotton so that cover and terminals into the beaker. Finally, rinse both inside
the end dips into the sample. Assemble the bomb and tighten and outside of the sample crucible into the beaker. Washings
the cover securely. Admit oxygen (see Note A2.7) slowly (to should equal but not exceed 1 00 mL. Add methanol to make
avoid blowing the sample from the cup) until a pressure is 1 00 mL.
reached as indicated in Table A2. 1 . A2.7.4 Determination of Chlorine-Add 5 mL of H2S04
NoTE A2.7-It is recommended to not add oxygen or ignite the sample ( 1 :2) to acidify the solution (solution should be acid to litmus
if the bomb has been jarred, dropped, or tilted. and clear of white Na2C03 precipitate). Add 100 mL of
A2.6.2.3 Combustion-Immerse the bomb in a cold-water acetone. Place the electrodes in the solution, start the stirrer (if
bath. Connect the terminals to the open electrical circuit. Close mechanical stirrer is to be used), and begin titration. If titration
the circuit to ignite the sample. Remove the bomb from the is manual, set the pH meter on the expanded millivolt scale and
bath after immersion for at least 1 0 min. Release the pressure note the reading. Add exactly 0. 1 mL of AgN03 solution from
at a slow, uniform rate such that the operation requires not less the buret. Allow a few seconds stirring; then record the new
than 1 min. Open the bomb and examine the contents. If traces millivolt reading. Subtract the second reading from the first.
of unburned oil or sooty deposits are found, discard the Continue the titration, noting each amount of AgN03 solution
determination, and thoroughly clean the bomb before again and the amount of difference between the present reading and
putting it in use (Note A2.4). the last reading. Continue adding 0. 1 mL increments, making
readings and determining differences between readings until a
A2.7 Analysis, Method A, Potentiometric Titration Proce- maximum difference between readings is obtained. The total
dure amount of AgN03 solution required to produce this maximum
A2.7 . 1 Apparatus: differential is the end point. Automatic titrators continuously
A2. 7 . 1 . 1 Silver Billet Electrode. stir the sample, add titrant, measure the potential difference,
A2.7. l .2 Glass Electrode, pH measurement type. calculate the differential, and plot the differential on a chart.
A2.7. l .3 Buret, 25 mL capacity, 0.05 mL graduations. The maximum differential is taken as the end point.
A2.7. l .4 Millivolt Meter, or expanded scale pH meter ca- NOTE A2.9-For maximum sensitivity, 0.00282 N AgN03 solution may
pable of measuring 0 mV to 220 mV. 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
these tests will cause end points of IO mL or higher. The large amount of
water used in such titrations reduces the differential between readings,
TABLE A2.1 Gauge Pressu res making the end point very difficult to detect. For chlorine contents over
Gauge Pressure, atm [MPa] I % in samples of 0.8 g or larger, 0.282 N AgN03 solution will be required
Capacity of Bomb,
ml
to avoid exceeding the 1 0 mL water dilution limit.
max
300 to 350 38 [3.85] 40 [4.05] A2.7.5 Blank-Make blank determinations with the amount
350 to 400 35 [3.55] 37 [3.75] of white oil used but omitting the sample. (Liquid samples
400 to 450 30 [3.04] 32 [3.24]
normally require only 0. 1 5 g to 0.25 g of white oil while solids
450 to 500 27 [2.74] 29 [2.94]
require 0.7 g to 0.8 g.) Follow normal procedure, making two
A The minimum pressures are specified to provide sufficient oxygen for complete
combustion and the maximum pressures present a safety requirement.
or three test runs to be sure the results are within the limits of
repeatability for the test. Repeat this blank procedure whenever

11
 0 E165/E165M - 23

new batches of reagents or white oil are used. The purpose of A2.8.2.2 Dry Gelatin Mixture. 7
the blank run is to measure the chlorine in the white oil, the A2.8.2.3 Nitric Acid.
reagents, and that introduced by contamination. A2.8.2.4 Sodium Chloride Solution- 1 00 meq C/l . Dry a
quantity of NaCl for 2 h at 1 30 °C to 1 50 °C. Weigh out
A2. 7 .6 Standardization-Silver nitrate solutions are not per­
5 .8440 g ::!:: 0.0005 g of dried NaCl in a closed container,
manently stable, so the true activity should be checked when
dissolve in water, and dilute to 1 L.
the solution is first made up and then periodically during the
life of the solution. This is done by titration of a known NaCl A2.8.3 Reagent Preparation:
solution as follows: Prepare a mixture of the amounts of the NoTE A2. 1 0-The normal reagent preparation process has been slightly
chemicals (Na2C03 solution, H2S04 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 elimjnates the interference and does not
NaCl solution and titrate to the end point. Prepare and titrate a alter the quality of the titration.

similar mixture of all the chemicals except the NaCl solution, A2. 8.3. 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
of the AgN03 solution as follows: 6.2 g of dry gelatin mixture contained in one vial supplied by
the equipment manufacturer. Gently heat with continuous
5 .0 x NNaCI
NAgN03 = vA - vB
(A2. l ) mixing until the gelatin is completely dissolved.
A2.8.3.2 Divide into aliquots each sufficient for one day ' s
where: analyses. (Thirty millilitres i s enough for approximately eleven
NAgN03 normality of the AgN03 solution, titrations.) Keep the remainder in a refrigerator, but do not
NNaCI normality of the NaCl solution, freeze. The solution will keep for about six months in the
VA millilitres of AgN03 solution used for the titra­ refrigerator. When ready to use, immerse the day ' s aliquot in
tion including the NaCl solution, and hot water to liquefy the gelatin.
millilitres of AgN03 solution used for the titra­ A2. 8.3.3 Glacial Acetic Acid-Nitric Acid Solution-A typi­
tion of the reagents only. cal ratio is 1 2. 5 to 1 ( 1 2.5 parts CH3COOH to 1 part HN03 ).
A2.7.7 Calculation-Calculate the chlorine content of the A2.8.3.4 Mix enough gelatin solution and of acetic acid­
sample as follows: nitric acid mixture for one titration. (A typical mixture is
2.5 mL of gelatin solution and 5.4 mL of acetic-nitric acid
( V5 - V8) x N x 3.545
Chlorine, weight % = (A2.2) mixture.)
W
NoTE A2. 1 1 -The solution may be premixed in a larger quantity for
where: convenience, but may not be useable after 24 h.
Vs millilitres of AgN03 solution used by the sample, A2.8.3.5 Run at least three blank values and take an average
Vs millilitres of AgN03 solution used by the blank, according to the operating manual of the titrator. Determine
N normality of the AgN03 solution, and
separate blanks for both five drops of mineral oil and 20 drops
w grams of sample used.
of mineral oil.
A2.7.8 Precision and Accuracy: A2.8.4 Titration:
A2.7.8 . l The following criteria should be used for judging A2.8.4. 1 Weigh to the nearest 0. 1 g and record the weight of
the acceptability of results: the 1 00 mL beaker.
A2.7.8. l . l Repeatab ility-Results by the same analyst A2.8.4.2 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 1 0.5 % of the value determined, whichever is bottle, rinse both the inside and the outside with water into the
higher. 1 00 mL beaker.
A2.7.8 . l .2 Reproducibility-Results by different laborato­ A2.8.4. 3 Empty the bomb shell into the 1 00 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 0.0 1 3 % or 2 1 . 3 % of the value detected, whichever wash bottle.
is higher. A2.8.4.4 Remove the cover assembly from the cover assem­
A2.7.8 . l . 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 1 00 mL beaker.
The total amount of washings should be 50 g ::!:: 1 g.
A2.8 Analysis, Method B, Coulometric Titration A2.8.4.5 Add specified amounts of gelatin mixture and
acetic acid-nitric acid mixture, or gelatin mix-acetic acid-nitric
A2.8. l Apparatus:
acid mixture, if this was premixed, into the 1 00 mL beaker that
A2.8. l . 1 Coulometric Chloride Titrator.
contains the 50 g of washings including the decomposed
A2.8. l .2 Beakers, two, 1 00 mL, or glazed crucibles (pref- sample.
erably with 1 1/2 in. outside diameter bottom).
A2.8. l .3 Refrigerator.
7 May be purchased from the equipment supplier. A typical mixture consists of
A2.8.2 Reagents: 6 g of gelatin powder, 0.1 g of thymol blue, water-soluble, and 0. 1 g of thymol,
A2.8.2. 1 Acetic Acid, Glacial. reagent grade, crystal.

12
 0 E165/E165M - 23

A2.8.4.6 Titrate using a coulometric titrimeter, according to A2.8.6 Precision and Accuracy:
operating manual procedure. A2.8.6. 1 Duplicate results by the same operator can be
A2.8.5 Calculations-Calculate the chloride ion concentra­ expected to exhibit the following relative standard deviations:
tion in the sample as follows: Approximate % Chlorine RSD, %

(P - B) x M
Chlorine, weight %
1 . 0 and above 0.10
= (A2.3)
W 0.1 2.5
0.003 5.9
where:
A2.8.6.2 The method can be expected to report values that
P counter reading obtained with the sample,
vary from the true value by the following amounts:
B average counter reading obtained with average of the
three blank readings, 0.1 % chlorine and above ±2 %
0.001 to 0.01 % chlorine ±9 %.
M standardization constant. This is dependent on the
instrument range setting in use and the reading obtained A2.8.6.3 If bromine is present, 36.5 % of the true amount
with a known amount of the 1 00 meq of Cl per litre of will be reported. If iodine is present, 20. 7 % of the true amount
solution, and will be reported. Fluorine will not be detected.
W weight of sample used, g.

A3. METHOD FOR MEASURING TOTAL FLUORINE CONTENT IN COMBUSTIBLE

LIQUID PENETRANT MATERIALS

A3.1 Scope and Application A3.4. l . 1 Weigh 5 0 g of test material into a 1 50 mm petri
dish.
A3 . 1 . 1 This method covers the determination of fluorine in
A3.4. l .2 Place the 1 50 mm petri dish into a 1 94 °P [90 °C]
combustible liquid penetrant materials, liquid or solid, that do
to 2 1 2 °P [ 1 00 °C] oven for 60 min.
not contain appreciable amounts of interfering elements, or
A3.4. l .3 Allow the test material to cool to room tempera­
have any insoluble residue after combustion. Its range of
ture.
applicability is 1 ppm to 200 000 ppm.
A3.4.2 Solvent Cleaners:
A3 . l .2 The measure of the fluorine content employs the
A3.4.2. l Take the tare weight of an aluminum dish.
fluoride selective ion electrode.
A3.4.2.2 Weigh 1 00 g of the cleaner into the aluminum dish.
A3.2 Summary of Method A3.4.2.3 Place the aluminum dish on a hot plate in a fume
hood.
A3 .2. l The sample is oxidized by combustion in a bomb
A3.4.2.4 Let the material evaporate until the dish is nearly
containing oxygen under pressure (see A3.2. l . 1 ). The fluorine
dry.
compounds thus liberated are absorbed in a sodium citrate
A3.4.2.5 Place the dish into a preheated oven from 1 94 °P
solution and the amount of fluorine present is determined
[90 °C] to 2 1 2 °P [ 1 00 °C] for 10 min.
potentiometrically through the use of a fluoride selective ion
A3.4.2.6 Take the dish out of the oven and allow to cool.
electrode.
A3.4.2.7 Reweigh the dish and record weight.
Norn A3.l-For Cleaners-If the residue is less than 50 ppm, report
A3 .2. l . 1 Safety-Strict adherence to all of the provisions
prescribed hereinafter ensures against explosive rupture of the the residue weight. If the weight is greater than 50 ppm, proceed with the
bomb, or a blow-out, provided the bomb is of proper design bomb procedure.
and construction and in good mechanical condition. It is
A3.5 Apparatus
desirable, however, that the bomb be enclosed in a shield of
steel plate at least 1/2 in. [ 1 2.7 mm] thick, or equivalent A3 . 5 . 1 Bomb, having a capacity of not less than 300 mL, so
protection be provided against unforeseeable contingencies. constructed that it will not leak during the test, and that
quantitative recovery of the liquids from the bomb may be
A3.3 Interferences
readily achieved. The inner surface of the bomb may be made
A3 .3 . 1 Silicon, calcium, aluminum, magnesium, and other of stainless steel or any other material that will not be affected
metals forming precipitates with fluoride ion will interfere if by the combustion process or products. Materials used in the
they are present in sufficient concentration to exceed the bomb assembly, such as the head gasket and leadwire
solubility of their respective fluorides. Insoluble residue after insulation, shall be resistant to heat and chemical action, and
combustion will entrain fluorine even if otherwise soluble. shall not undergo any reaction that will affect the fluorine
content of the liquid in the bomb.
A3.4 Sample Preparation
A3.5.2 Sample Cup, nickel, 20 mm in outside diameter at
A3 .4. 1 Penetrants, Developers, Emulsifiers, Magnetic Oils: the bottom, 28 mm in outside diameter at the top, and 1 6 mm

13
 0 E165/E165M - 23

in height; or platinum, 24 mm in outside diameter at the A3.6.8 White Oil, refined.

bottom, 27 mm in outside diameter at the top, 1 2 mm in height,
and weighing 10 g to 1 1 g. A3. 7 Decomposition Procedure

A3 .5.3 Firing Wire, platinum, approximately No. 26 B & S A3 . 7 . 1 Preparation of Bomb and Sample-Cut a piece of
gauge. firing wire approximately 1 00 mm in length. Coil the middle
section (about 20 mm) and attach the free ends to the terminals.
A3 . 5 .4 Ignition Circuit, capable of supplying sufficient cur­ Arrange the coil so that it will be above and to one side of the
rent to ignite the nylon thread or cotton wicking without sample cup. Place 1 0 mL of sodium citrate solution in the
melting the wire. (Warning-The switch in the ignition circuit bomb, place the cover on the bomb, and vigorously shake for
should be of a type that remains open, except when held in 1 5 s to distribute the solution over the inside of the bomb. Open
closed position by the operator.) the bomb, place the sample-filled sample cup in the terminal
A3 . 5 .5 Nylon Sewing Thread, or Cotton Wicking, white. holder, and insert a short length of thread between the firing
wire and the sample. The sample weight used should not
A3 .5.6 Funnel, polypropylene (Note A3 .2).
exceed 1 g. If the sample is a solid, add a few drops of white
A3 .5.7 Volumetric Flask, polypropylene, 1 00 mL (Note oil at this time to ensure ignition of the sample.
A3.2).
NoTE A3.3-Use of sample weights containing over 20 mg of chlorine
A3 . 5 .8 Beaker, polypropylene, 1 5 0 mL (Note A3.2). may cause corrosion of the bomb. To avoid this it is recommended that for
samples containing over 2 % chlorine, the sample weight be based on the
A3 .5.9 Pipet, 1 00 µL, Eppendorf-type (Note A3.2).
following table:
A3 .5 . 1 0 Magnetic Stirrer and TFE-coated magnetic stirring Chlorine Sample White Oil
bar. Content, % weight, g weight, g

A3 .5 . 1 1 Fluoride Specific Ion Electrode and suitable refer­ 2 to 5 0.4 0.4

ence electrode. >5 to 1 0 0.2 0.6
> 1 0 to 20 0.1 0.7
A3 .5 . 1 2 Millivolt Meter capable of measuring to 0. 1 mV. >20 to 50 0.05 0.7

Do not use more than 1 g total of sample and white oil or

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 other fluorine-free combustible material.
carry fluoride ion from a concentrated solution to one more dilute. A3.7.2 Addition of Oxygen-Place the sample cup in posi­
A3.6 Reagents
tion and arrange the nylon thread, or wisp of cotton so that the
end dips into the sample. Assemble the bomb and tighten the
A3 .6. 1 Purity of Reagents-Reagent grade chemicals shall cover securely. Admit oxygen (see the Warning below) slowly
be used in all tests. Unless otherwise indicated, it is intended (to avoid blowing the sample from the cup) until a pressure is
that all reagents shall conform to the specifications of the reached as indicated in Table A3 . 1 . (Warning-It is recom­
Committee on Analytical Reagents of the American Chemical mended to not add oxygen or ignite the sample if the bomb has
Society, where such specifications are available. 6 Other grades been jarred, dropped, or tilted.)
may be used, provided it is first ascertained that the reagent is
of sufficiently high purity to permit its use without lessening A3.7.3 Combustion-Immerse the bomb in a cold-water
the accuracy of the determination. bath. Connect the terminals to the open electrical circuit. Close
the circuit to ignite the sample. Remove the bomb from the
A3 .6.2 Purity of Water-Unless otherwise indicated, all bath after immersion for at least 1 0 min. Release the pressure
references to water shall be understood to mean Type I reagent at a slow, uniform rate such that the operation requires not less
water conforming to Specification D l 1 93 . than 1 min. Open the bomb and examine the contents. If traces
A3.6.3 Fluoride Solution, Stock (2000 ppm)-Dissolve of unburned oil or sooty deposits are found, discard the
4.4200 g ::'::: 0.0005 g of predried (at 1 30 °C to 1 50 °C for 1 h, determination, and thoroughly clean the bomb before again
then cooled in a desiccator) sodium fluoride in distilled water putting it in use.
and dilute to 1 L. A 3 . 7 .4 Collection of Fluorine Solution- Remove the
A3 .6.4 Oxygen, free of combustible material and halogen sample cup with clean forceps and rinse with wash solution
compounds, available at a pressure of 40 atm [4.05 MPa]. into a 1 00 mL volumetric flask. Rinse the walls of the bomb
shell with a fine stream of wash solution from a wash bottle,
A3 .6.5 Sodium Citrate Solution-Dissolve 27 g of sodium
citrate dihydrate in water and dilute to 1 L.
TABLE A3.1 Gauge Pressures
A3 .6.6 Sodium Hydroxide Solution (5 NJ-Dissolve 200 g
Gauge Pressure aim [M Pa]
of sodium hydroxide (NaOH) pellets in water and dilute to 1 L; Capacity of Bomb, ml
minA max
store in a polyethylene container.
300 to 350 38 40
A3 .6.7 Wash Solution (Modified TISAB, Total Ionic Strength >350 to 400 35 37
>400 to 450 30 32
Adjustment Buffer)-To 300 mL of distilled water, add 32 mL
>450 to 500 27 29
of glacial acetic acid, 6.6 g of sodium citrate dihydrate, and
A The minimum pressures are specified to provide sufficient oxygen for complete
32. 1 5 g of sodium chloride. Stir to dissolve and then adjust the combustion and the maximum pressures present a safety requirement.
pH to 5 . 3 using 5 N NaOH solution. Cool and dilute to 1 L.

14
 0 E165/E165M - 23

and add the washings to the fl.ask. Next, rinse the bomb cover where:
and terminals into the volumetric fl.ask. Finally, add wash L1 E1 millivolt change in sample solution on addition of
solution to bring the contents of the flask to the line. 1 00 µL of stock fluoride solution,
millivolt change in blank solution on addition of
A3.8 Procedure
1 00 µL of the stock fluoride solution,
A3 . 8 . 1 Ascertain the slope (millivolts per ten-fold change in s slope of fluoride electrode as determined in A3.8 . 1 ,
concentration) of the electrode as described by the manufac­ and
turer. w grams of sample.
A3 .8.2 Obtain a blank solution by performing the procedure A3. 1 0 Precision and Bias
without a sample.
A3 . 1 0. l Repeatability-The results of two determinations
A3 .8.3 Immerse the fluoride and reference electrodes in
by the same analyst should not be considered suspect unless
solutions and obtain the equilibrium reading to 0. 1 m V. (The
condition of the electrode determines the length of time they differ by more than 1 . 1 ppm (0.000 1 1 %) or 8.0 % of the
necessary to reach equilibrium. This may be as little as 5 min amount detected, whichever is greater.
or as much as 20 min.) A3 . 10.2 Reproducibility-The results of two determinations
A3 . 8 .4 Add 1 00 µL of stock fluoride solution and obtain the by different laboratories should not be considered suspect
reading after the same length of time necessary for A3 .8.3. unless they differ by 6.7 ppm or 1 29.0 % of the amount
detected, whichever is greater.
A3.9 Calculation
A3 . 10.3 Bias-The average recovery of the method is 62 %
A3 .9. l Calculate the fluorine content of the sample as
to 64 % of the amount actually present although 83 % to 85 %
follows:
recoveries can be expected with proper technique.
[ 2 x 10-4 2 x 1 0-4 ]
l Ot-. E , IS - l l Ot-.£2/S - l
Fluorine, ppm = x 1 06
W
(A3. l )

A4. DETERMINATION OF ANIONS BY ION CHROMATOGRAPHY WITH CONDUCTIVITY MEASUREMENT

A4.1 Scope and Application acid. The separated anions i n their acid form are measured by
conductivity. They are identified on the basis of retention time
A4. 1 . 1 This method is condensed from ASTM procedures
as compared to standards. Quantitation is by measurement of
and APHA Method 429 and optimized for the analysis of
peak area or peak height. Blanks are prepared and analyzed in
detrimental substances in organic based materials. It provides a
a similar fashion.
single instrumental technique for rapid, sequential measure­
ment of common anions such as bromide, chloride, fluoride, A4.2.2 Interferences-Any substance that has a retention
nitrate, nitrite, phosphate, and sulfate. time coinciding with that of any anion to be determined will
interfere. For example, relatively high concentrations of low­
A4.2 Summary of Method molecular-weight organic acids interfere with the determina­
A4.2. 1 The material must be put in the form of an aqueous tion of chloride and fluoride. A high concentration of any one
solution before analysis can be attempted. The sample is ion also interferes with the resolution of others. Sample
oxidized by combustion in a bomb containing oxygen under dilution overcomes many interferences. To resolve uncertain­
pressure. The products liberated are absorbed in the eluant ties of identification or quantitation use the method of known
present in the bomb at the time of ignition. This solution is additions. Spurious peaks may result from contaminants in
washed from the bomb, filtered, and diluted to a known reagent water, glassware, or sample processing apparatus.
volume. Because small sample volumes are used, scrupulously avoid
contamination.
A4.2. l . 1 A filtered aliquot of sample is injected into a
stream of carbonate-bicarbonate eluant and passed through a A4.2.3 Minimum Detectable Concentration-The minimum
series of ion exchangers. The anions of interest are separated detectable concentration of an anion is a function of sample
on the basis of their relative affinities for a low capacity, size and conductivity scale used. Generally, minimum detect­
strongly basic anion exchanger (guard and separator column). able concentrations are in the range of 0.05 mg/L for F- and
The separated anions are directed onto a strongly acidic cation 0. 1 mg;L for Br-, Cl-, N03-, N02-, PO/-, and S o/- with a
exchanger (suppressor column) where they are converted to 1 00 µL sample loop and a 1 0 µmho full-scale setting on the
their highly conductive acid form and the carbonate­ conductivity detector. Similar values may be achieved by using
bicarbonate eluant is converted to weakly conductive carbonic a higher scale setting and an electronic integrator.

15
 0 E165/E165M - 23

A4.3 Apparatus Committee on Analytical Reagents of the American Chemical

6
Society, where such specifications are available. Other grades
A4. 3 . l Bomb, having a capacity of not less than 300 mL, so
may be used provided it is first ascertained that the reagent has
constructed that it will not leak during the test, and that
quantitative recovery of the liquids from the bomb may be sufficiently high purity to permit its use without lessening the
accuracy of the determination.
readily achieved. The inner surface of the bomb may be made
of stainless steel or any other material that will not be affected A4.4.2 Deionized or Distilled Water, free from interferences
by the combustion process or products. Materials used in the at the minimum detection limit of each constituent and filtered
bomb assembly, such as the head gasket and leadwire through a 0.2 µm membrane filter to avoid plugging columns.
insulation, shall be resistant to heat and chemical action, and A4 .4.3 Eluant Solution, sodium bicarbonate-sodium
shall not undergo any reaction that will affect the chlorine carbonate, 0.003M NaHC03_ 0.0024M Na2C03 : dissolve
content of the liquid in the bomb. 1 .008 g NaHC03 and 1 .0176 g Na2C03 in water and dilute to
A4.3.2 Sample Cup, platinum, 24 mm in outside diameter at 4 L.
the bottom, 27 mm in outside diameter at the top, 1 2 mm in A4.4.4 Regenerant Solution I, H2S04, 1 N, use this regen­
height outside, and weighing 10 g to 1 1 g; opaque fused silica, erant when suppressor is not a continuously regenerated one.
wide-form with an outside diameter of 29 mm at the top, a
height of 1 9 mm, and a 5 mL capacity (Note A4. l ), or nickel A4.4.5 Regenerant Solution 2, H2S04, 0.025 N, dilute
(Kawin capsule form), top diameter of 28 mm, 1 5 mm in 2.8 mL cone H2S04 to 4 L or 1 00 mL regenerant solution 1 to
height, and 5 mL capacity. 4 L. Use this regenerant with continuous regeneration fiber
suppressor system.
NOTE A4. 1 -Fused silica crucibles are much more economical and
longer lasting than platinum. After each use, they should be scrubbed out A4.4.6 Standard Anion Solutions, 1 000 mg;L, prepare a
with fine, wet emery cloth, heated to dull red heat over a burner, soaked series of standard anion solutions by weighing the indicated
in hot water for 1 h then dried and stored in a desiccator before reuse. amount of salt, dried to a constant weight at 1 05 °C, to
A4.3.3 Firing Wire, platinum, approximately No. 26 B and 1 000 mL. Store in plastic bottles in a refrigerator; these
S gauge. solutions are stable for at least one month.
Anion Salt Amou nt,
g/L
A4.3.4 Ignition Circuit (Note A4.2), capable of supplying
sufficient current to ignite the nylon thread or cotton wicking
without melting the wire. c1- NaCl 1 .6485
F- NaF 2.21 00
NOTE A4.2-The switch in the ignition circuit should be of a type that Br­ NaBr 1 .2876
remains open, except when held in closed position by the operator. N03- NaN03 1 .3707
No2- NaN02 1 .4998
A4.3.5 Nylon Sewing Thread, or Cotton Wicking, white. 3
P04 - KH2P04 1 .4330
so/- K2S04 1 .8 1 4 1
A4.3.6 Ion Chromatograph, including an injection valve, a
sample loop, guard, separator, and suppressor columns, a A4 .4.7 Combined Working Standard Solution, High
Range-Combine 1 0 mL of the Cl-, P-, N03-, N02-, and
PO/ - standard anion solutions, 1 mL of the Br-, and 100 mL
temperature-compensated small-volume conductivity cell

of the so/- standard solutions, dilute to 1 000 mL, and store in

(6 µL or less), and a strip chart recorder capable of full-scale
response of 2 s or less. An electronic peak integrator is
optional. The ion chromatograph shall be capable of delivering a plastic bottle protected from light; contains 10 mg/L each of
3
2 mL to 5 mL eluant/min at a pressure of 1400 kPa to 6900 Cl- , p-, N03-, N02-, and P04 -, 1 mg Br- IL, and 1 00 mg
2
kPa. S04 -/L. Prepare fresh daily.

A4 . 3 . 7 Anion Separator Column, with styrene A4.4.8 Combined Working Standard Solution, Low Range­
divinylbenzene-based low-capacity pellicular anion-exchange Dilute 1 00 mL combined working standard solution, high
resin capable of resolving Br-, c1-, P-, N03-, N02-, Po/ -, range, to 1000 mL and store in a plastic bottle protected from
and so/ -; 4 mm by 250 mm. light; contains 1 .0 mg/L each c1-, p-, N03-, No2-, and Po/-,
0. 1 mg BC/L, and 10 mg So/-/L. Prepare fresh daily.
A4. 3 . 8 Guard Column, identical to separator column except
4 mm by 50 mm, to protect separator column from fouling by A4.4.9 Alternative Combined Working Standard Solutions­
particulates or organics. Prepare appropriate combinations according to anion concen­
3
tration to be determined. If N02- and P04 - are not included,
A4.3.9 Suppressor Column, high-capacity cation-exchange the combined working standard is stable for one month.
resin capable of converting eluant and separated anions to their
acid forms. A4.5 Sample Preparation

A4. 3 . 1 0 Syringe, minimum capacity of 2 mL and equipped A4.5. 1 Penetrants, Developers, Emulsifiers, Magnetic Oils:
with a male pressure fitting. A4.5 . l . 1 Weigh 50 g of test material into a 1 50 mm petri
dish.
A4.4 Reagents
A4.5. 1 .2 Place the 1 5 0 mm petri dish into a 1 94 °P [90 °C]
A4.4. 1 Purity of Reagents-Reagent grade chemicals shall to 2 1 2 °P [ 1 00 °C] oven for 60 min.
be used in all tests. Unless otherwise indicated, it is intended A4.5. 1 .3 Allow the test material to cool to room tempera­
that all reagents shall conform to the specifications of the ture.

16
 6
•1.1117
E165/E165M - 23

A4.5.2 Solvent Cleaners: NoTE A4.5-It i s recommended to not add oxygen or ignite the sample
A4.5 .2. 1 Take the tare weight of an aluminum dish. if the bomb has been j arred, dropped, or tilted.

A4.5 .2.2 Weigh 1 00 g of the cleaner into the aluminum A4.6.3 Combustion-Immerse the bomb in a cold-water
dish. bath. Connect the terminals to the open electrical circuit. Close
A4.5.2.3 Place the aluminum dish on a hot plate in a fume the circuit to ignite the sample. Remove the bomb from the
hood. bath after immersion for at least 1 0 min. Release the pressure
A4.5 .2.4 Let the material evaporate until the dish is nearly at a slow, uniform rate such that the operation requires not less
dry. than 1 min. Open the bomb and examine the contents. If traces
A4.5 .2.5 Place the dish into a preheated oven from 1 94 °F of unburned oil or sooty deposits are found, discard the
(90 °C] to 2 1 2 °F ( 1 00 °C] for 1 0 min. determination, and thoroughly clean the bomb before again
A4.5 .2.6 Take the dish out of the oven and allow to cool. putting it in use.
A4.5 .2.7 Reweigh the dish and record weight. A4.6.4 Collection of Solution-Remove the sample cup
NOTE A4. 3-For Cleaners-If the residue is less than 50 ppm, report
with clean forceps and rinse with deionized water and filter the
the residue weight. If the weight is greater than 50 ppm, proceed with the
bomb procedure. washings into a 100 mL volumetric flask. Rinse the walls of the
bomb shell with a fine stream of deionized water from a wash
A4.6 Decomposition Procedure bottle, and add the washings through the filter paper to the
A4.6. 1 Preparation of Bomb and Sample-Cut a piece of flask. Next, rinse the bomb cover and terminals and add the
firing wire approximately 1 00 mm in length. Coil the middle washings through the filter into the volumetric flask. Finally,
section (about 20 mm) and attach the free ends to the terminals. add deionized water to bring the contents of the flask to the
Arrange the coil so that it will be above and to one side of the line. Use aliquots of this solution for the ion chromatography
sample cup. Place 5 mL of Na2C03/NaHC03 or K2C03 (IC) analysis.
solution in the bomb, place the cover on the bomb, and
A4. 7 Procedure
vigorously shake for 1 5 s to distribute the solution over the
inside of the bomb. Open the bomb, place the sample-filled A4.7. 1 System Equilibration-Turn on ion chromatograph
sample cup in the terminal holder, and insert a short length of and adjust eluant flow rate to approximate the separation
thread between the firing wire and the sample. The sample achieved in Fig. A4. 1 (2 mL/min to 3 mL/min). Adjust detec­
weight used should not exceed 1 g. If the sample is a solid, add tor to desired setting (usually 1 0 µmho) and let system come to
a few drops of white oil at this time to ensure ignition of the equilibrium ( 1 5 min to 20 min). A stable base line indicates
sample. equilibrium conditions. Adjust detector offset to zero-out
eluant conductivity; with the fiber suppressor adjust the regen­
NOTE A4 .4-Use of sample weights containing over 20 mg of chlorine
eration flow rate to maintain stability, usually 2.5 mL/min to 3
may cause corrosion of the bomb. To avoid this it is recommended that for
samples containing over 2 % chlorine, the sample weight be based on the mL/min.
following: A4.7 . 1 . 1 Set up the ion chromatograph in accordance with
Chlorine Sample White Oil the manufacturer' s instructions.
content, % weight, g weight, g
A4.7.2 Calibration-Inject standards containing a single
2 to 5 0.4 0.4 anion or a mixture and determine approximate retention times.
>5 to 1 0 0.2 0.6 Observed times vary with conditions but if standard eluant and
> 1 0 to 20 0.1 0.7
anion separator column are used, retention always is in the
order F-, Cl-, N02-, P04 -, Br-, N03-, and So/-. Inject at
>20 to 50 0.05 0.7 3
Warning-Do not use more than I g total of sample and white oil or least three different concentrations for each anion to be
other fluorine-free combustible material.
measured and construct a calibration curve by plotting peak
A4.6.2 Addition of Oxygen-Place the sample cup in posi­ height or area against concentration on linear graph paper.
tion and arrange the nylon thread, or wisp of cotton so that the
end dips into the sample. Assemble the bomb and tighten the
cover securely. Admit oxygen (see Note A4.5) slowly (to avoid
blowing the sample from the cup) until a pressure is reached as
indicated in Table A4. l .

TABLE A4.1 Gauge Pressu res

Gauge Pressures, aim
Capacity of Bomb, ml
mmA max
300 to 350 38 40
>350 to 400 35 37
>400 to 450 30 32
>450 to 500 27 29
0 10 15 20
A The minimum pressures are specified to provide sufficient oxygen for complete
Minutes
combustion and the maximum pressures present a safety requirement.
FIG. A4.1 Typical Anion Profile

17
 0 E165/E165M - 23

Recalibrate whenever the detector setting is changed. With a times: for 0. 1 mL sample loop inject at least 1 mL. Switch ion
system requiring suppressor regeneration, N02- interaction chromatograph from load to inject mode and record peak
with the suppressor may lead to erroneous N02- results; make heights and retention times on strip chart recorder. After the
2
this determination only when the suppressor is at the same last peak (S04 - ) has appeared and the conductivity signal has
stage of exhaustion as during standardization or recalibrate returned to base line, another sample can be injected.
frequently. In this type of system the water dip (see Note A4.6) A4.7.4 Regeneration-For systems without fiber suppressor
may shift slightly during suppressor exhaustion and with a fast regenerate with 1 N H2S04 in accordance with the manufac­
run column this may lead to slight interference for p- or c1- . turer' s instructions when the conductivity base line exceeds
To eliminate this interference, analyze standards that bracket 300 µmho when the suppressor column is on line.
the expected result or eliminate the water dip by diluting the
sample with eluant or by adding concentrated eluant to the A4.8 Calculation
sample to give the same HC03 -ico/- concentration as in the
A4.8. l Calculate concentration of each anion, in mg/L, by
eluant. If sample adj ustments are made, adjust standards and
referring to the appropriate calibration curve. Alternatively,
blanks identically. Both calibration and calculation of results
when the response is shown to be linear, use the following
may be performed either manually or via use of a computer and
equation:
appropriate software.
C = H x F xD (A4. l )
NOTE A4.6-Water dip occurs because water conductivity in sample is
less than eluant conductivity (eluant is diluted by water). where:
c mg anion/L,
A4.7 .2. 1 If linearity is established for a given detector
H peak height or area,
setting, it is acceptable to calibrate with a single standard.
F response factor - concentration of standard/height (or
Record the peak height or area and retention time to permit
area) of standard, and
calculation of the calibration factor, F.
D dilution factor for those samples requiring dilution.
A4.7.3 Sample Analysis-Remove sample particulates, if
A4.9 Precision and Bias
necessary, by filtering through a prewashed 0.2 µm-pore-diam
membrane filter. Using a prewashed syringe of 1 mL to 10 mL A4.9. l S amples of reagent water to which were added the
capacity equipped with a male luer fitting inject sample or common anions were analyzed in 1 5 laboratories with the
standard. Inject enough sample to flush sample loop several results shown in Table A4.2.

TABLE A4.2 Precision and Accuracy Observed for Anions at Various Concentration Levels in Reagent Water
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
c1- 17 1 7.2 0.82 0.43 No
Cl 455 471 46 13 No
N02 0.45 0.09 0.09 0.04 Yes, neg
N02 21 .8 1 9.4 1 .9 1 .3 Yes, neg
Bl 0.25 0.25 0.04 0.02 No
Bl 1 3.7 1 2.9 1 .0 0.6 No
P043- 0. 1 8 0.10 0.06 0.03 Yes, neg
3
P04 - 0.49 0.34 0.15 0.17 Yes, neg
N03- 0.50 0.33 0.16 0.03 No
N03- 1 5. 1 1 4.8 1 .1 5 0.9 No
so/- 0.51 0.52 0.07 0.03 No
so/- 43.7 43.5 2.5 2.2 No

18
 0 E165/E165M - 23

SUMMARY OF CHANGES

Committee E07 has identified the location of selected changes to this standard since the last issue
(E 1 65/E l 65M - 1 8) that may impact the use of this standard. (Approved July 1, 2023 .)

(1) Added D69 1 9 to 2. 1 . (6) Added D4327 to second to last sentence and changed
(2) Added Method A(W) to Table 1 . D4327 to D69 1 9 in last sentence of 9. 1 .2.
(3) Added Method A(W) information to 7 .2.2. (7) In 1 0 . 1 , changed "guide" to "practice" and "should" to
(4) Added reference to Method A(W) in 8.6. 1 . "shall," and added last sentence.
(5) In 8.9. 1 . 1 , changed intensity to irradiance, and removed (8) Added option to use K2C03 to A2.6.2. 1 and A4.6. l .
line voltage discussion sentence.

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