Se 165

ARTICLE 24, SE-165 2007 SECTION V
STANDARD TEST METHOD FOR

LIQUID PENETRANT EXAMINATION
SE-165
(Identical with ASTM Specification E 165-02)
1. Scope the responsibility of the user of this standard to establish

1.1 This test method covers procedures for penetrant appropriate safety and health practices and determine the
examination of materials. They are nondestructive testing applicability of regulatory limitations prior to use.
methods for detecting discontinuities that are open to the
surface such as cracks, seams, laps, cold shuts, laminations, 2. Referenced Documents
through leaks, or lack of fusion and are applicable to in- 2.1 ASTM Standards:
process, final, and maintenance examination. They can be
effectively used in the examination of nonporous, metallic D 129 Test Method for Sulfur in Petroleum Products (Gen-
materials, both ferrous and nonferrous, and of nonmetallic eral Bomb Method)
materials such as glazed or fully densified ceramics, certain D 516 Test Method for Sulfate Ion in Water
nonporous plastics, and glass.
D 808 Test Method for Chlorine in New and Used Petro-
1.2 This test method also provides a reference: leum Products (Bomb Method)
1.2.1 By which a liquid penetrant examination pro- D 1193 Specification for Reagent Water
cess recommended or required by individual organizations
can be reviewed to ascertain its applicability and com- D 1552 Test Method for Sulfur in Petroleum Products
pleteness. (High-Temperature Method)
1.2.2 For use in the preparation of process specifica- D 4327 Test Method for Anions in Water in Chemically
tions dealing with the liquid penetrant examination of mate- Suppressed Ion Chromatography
rials and parts. Agreement by the user and the supplier E 433 Reference Photographs for Liquid Penetrant
regarding specific techniques is strongly recommended. Inspection
1.2.3 For use in the organization of the facilities and E 543 Practice for Evaluating Agencies that Perform Non-
personnel concerned with the liquid penetrant examination. destructive Testing
1.3 This test method does not indicate or suggest criteria E 1208 Test Method for Fluorescent Liquid Penetrant
for evaluation of the indications obtained. It should be Examination Using the Lipophilic Post-Emulsification
pointed out, however, that after indications have been pro- Process
duced, they must be interpreted or classified and then evalu-
ated. For this purpose there must be a separate code or E 1209 Test Method for Fluorescent Liquid Penetrant
specification or a specific agreement to define the type, Examination Using the Water-Washable Process
size, location, and direction of indications considered E 1210 Test Method for Fluorescent Liquid Penetrant
acceptable, and those considered unacceptable. Examination Using the Hydrophilic Post-Emulsification
1.4 The values stated in inch-pound units are to be Process
regarded as the standard. SI units are provided for informa- E 1219 Test Method for Fluorescent Liquid Penetrant
tion only. Examination Using the Solvent-Removable Process
1.5 This standard does not purport to address all of E 1220 Test Method for Visible Penetrant Examination
the safety concerns, if any, associated with its use. It is Using the Solvent-Removable Process
444
--`,,```,,,,````-`-`,,`,,`,`,,`---
Copyright ASME International

Provided by IHS under license with ASME
No reproduction or networking permitted without license from IHS Not for Resale
2007 SECTION V ARTICLE 24, SE-165
E 1316 Terminology for Nondestructive Examinations TABLE 1

CLASSIFICATION OF PENETRANT EXAMINATION
E 1418 Test Method for Visible Penetrant Examination TYPES AND METHODS
Using the Water-Washable Process
Type I — Fluorescent Penetrant Examination
2.2 ASNT Documents: Method A — Water-washable (see Test Method E 1209)
Recommended Practice SNT-TC-1A for Nondestructive Method B — Post-emulsifiable, lipophilic (see Test Method E
1208)
Testing Personnel Qualification and Certification Method C — Solvent removable (see Test Method E 1219)
ANSI/ASNT CP-189 Standard for Qualification and Certi- Method D — Post-emulsifiable, hydrophilic (see Test Method E
1210)
fication of Nondestructive Testing Personnel
Type II — Visible Penetrant Examination
2.3 Military Standard: Method A — Water-washable (see Test Method E 1418)
Method C — Solvent removable (see Test Method E 1220)
MIL-STD-410 Nondestructive Testing Personnel Qualifi-
cation and Certification
2.4 APHA Standard: critical service items, volume of parts, portability or local-
ized areas of examination. The method selected will depend
429 Method for the Examination of Water and Waste-water accordingly on the service requirements.
NAS-410 Certification and Qualification of Nondestructive
Test Personnel 6. Classification of Penetrations and Methods
6.1 Liquid penetrant examination methods and types
3. Terminology are classified as shown in Table 1.
3.1 The definitions relating to liquid penetrant examina- 6.2 Fluorescent penetrant examination utilizes pene-
tion, which appear in Terminology E 1316, shall apply to trants that fluoresce brilliantly when excited by black light
the terms used in this standard. (see 8.9.1.2). The sensitivity of fluorescent penetrants
depends on their ability to be retained in the various size
discontinuities during processing, then to bleed out into
4. Summary of Test Method
the developer coating and produce indications that will
4.1 A liquid penetrant which may be a visible or a fluoresce. Fluorescent indications are many times brighter
fluorescent material is applied evenly over the surface than their surroundings when viewed under black light
being examined and allowed to enter open discontinuities. illumination.
After a suitable dwell time, the excess surface penetrant
is removed. A developer is applied to draw the entrapped 6.3 Visible penetrant examination uses a penetrant that
penetrant out of the discontinuity and stain the developer. can be seen in visible light. The penetrant is usually red,
The test surface is then examined to determine the presence so that the indications produce a definite contrast with the
or absence of indications. white background of the developer. The visible penetrant
process does not require the use of black light. However,
NOTE 1: The developer may be omitted by agreement between purchaser visible penetrant indications must be viewed under ade-
and supplier. quate white light (see 8.9.2.1).
NOTE 2: Caution — Fluorescent penetrant examination shall not follow
a visible penetrant examination unless the procedure has been qualified 7. Types of Materials
in accordance with 10.2, because visible dyes may cause deterioration
or quenching of fluorescent dyes.
7.1 Liquid penetrant examination materials (see Notes
3, 4, and 5) consist of fluorescent and visible penetrants,
4.2 Processing parameters, such as surface precleaning, emulsifiers (oil-base and water-base; fast and slow acting),
penetration time and excess penetrant removal methods, solvent removers and developers. A family of liquid pene-
are determined by the specific materials used, the nature trant examination materials consists of the applicable pene-
of the part under examination (that is, size, shape, surface trant and emulsifier or remover, as recommended by the
condition, alloy), and type of discontinuities expected. manufacturer. Intermixing of materials from various manu-
facturers is not recommended.
5. Significance and Use NOTE 3: Refer to 9.1 for special requirements for sulfur, halogen and
5.1 Liquid penetrant examination methods indicate the alkali metal content.
presence, location and, to a limited extent, the nature and NOTE 4: Caution — While approved penetrant materials will not
magnitude of the detected discontinuities. Each of the vari- adversely affect common metallic materials, some plastics or rubbers
ous methods has been designed for specific uses such as may be swollen or stained by certain penetrants.
445
7.2 Penetrants: 7.4 Solvent Removers function by dissolving the pene-

7.2.1 Post-Emulsifiable Penetrants are designed to trant, making it possible to wipe the surface clean and free
be insoluble in water and cannot be removed with water of excess penetrant as described in 8.6.4.
rinsing alone. They are designed to be selectively removed 7.5 Developers — Development of penetrant indications
from the surface using a separate emulsifier. The emulsifier, is the process of bringing the penetrant out of open disconti-
properly applied and given a proper emulsification time, nuities through blotting action of the applied developer,
combines with the excess surface penetrant to form a water- thus increasing the visibility of the indications.
washable mixture, which can be rinsed from the surface,
leaving the surface free of fluorescent background. Proper 7.5.1 Dry Powder Developers are used as supplied
emulsification time must be experimentally established and (that is, free-flowing, non-caking powder) in accordance
maintained to ensure that over-emulsification does not with 8.8.2. Care should be taken not to contaminate the
occur, resulting in loss of indications. developer with fluorescent penetrant, as the penetrant
specks can appear as indications.
7.2.2 Water-Washable Penetrants are designed to be
directly water-washable from the surface of the test part, 7.5.2 Aqueous Developers are normally supplied as
after a suitable penetrant dwell time. Because the emulsifier dry powder particles to be either suspended or dissolved
is “built-in” to the water-washable penetrant, it is extremely (soluble) in water. The concentration, use and maintenance
important to exercise proper process control in removal of shall be in accordance with manufacturer’s recommenda-
excess surface penetrant to ensure against overwashing. tions (see 8.8.3).
Water-washable penetrants can be washed out of disconti- NOTE 5: Caution — Aqueous developers may cause stripping of indica-
nuities if the rinsing step is too long or too vigorous. Some tions if not properly applied and controlled. The procedure should be
penetrants are less resistant to overwashing than others. qualified in accordance with 10.2.
7.2.3 Solvent-Removable Penetrants are designed so 7.5.3 Nonaqueous Wet Developers are supplied as
that excess surface penetrant can be removed by wiping suspensions of developer particles in a nonaqueous solvent
until most of the penetrant has been removed. The carrier ready for use as supplied. Nonaqueous, wet devel-
remaining traces should be removed with the solvent opers form a coating on the surface of the part when dried,
remover (see 8.6.4.1). To minimize removal of penetrant which serves as the developing medium (see 8.8.4).
from discontinuities, care should be taken to avoid the use
NOTE 6: Caution — This type of developer is intended for application
of excess solvent. Flushing the surface with solvent to by spray only.
remove the excess penetrant is prohibited.
7.5.4 Liquid Film Developers are solutions or colloi-
7.3 Emulsifiers: dal suspensions of resins/polymer in a suitable carrier.
7.3.1 Lipophilic Emulsifiers are oil-miscible liquids These developers will form a transparent or translucent
used to emulsify the excess oily penetrant on the surface of coating on the surface of the part. Certain types of film
the part, rendering it water-washable. The rate of diffusion developer may be stripped from the part and retained for
establishes the emulsification time. They are either slow- record purposes (see 8.8.5).
or fast-acting, depending on their viscosity and chemical
composition, and also the surface roughness of the area
8. Procedure
being examined (see 8.6.2).
8.1 The following general processing guidelines apply
7.3.2 Hydrophilic Emulsifiers are water-miscible liq- (see Figs. 2, 3, and 4) to both fluorescent and visible
uids used to emulsify the excess oily fluorescent penetrant penetrant examination methods (see Fig. 1).
on the surface of the part, rendering it water-washable
(see 8.6.3). These water-base emulsifiers (detergent-type 8.2 Temperature Limits — The temperature of the pene-
removers) are supplied as concentrates to be diluted with trant materials and the surface of the part to be processed
water and used as a dip or spray. The concentration, use and should be between 50 and 100°F (10 and 38°C). Where it is
maintenance shall be in accordance with manufacturer’s not practical to comply with these temperature limitations,
recommendations. qualify the procedure as described in 10.2 at the tempera-
ture of intended use and as agreed to by the contracting
7.3.2.1 Hydrophilic emulsifiers function by dis-
parties.
placing the excess penetrant film from the surface of the
part through detergent action. The force of the water spray 8.3 Surface Conditioning Prior to Penetrant Examina-
or air/mechanical agitation in an open dip tank provides tion — Satisfactory results usually may be obtained on
the scrubbing action while the detergent displaces the film surfaces in the as-welded, as-rolled, as-cast, or as-forged
of penetrant from the part surface. The emulsification time conditions (or for ceramics in the densified conditions).
will vary, depending on its concentration, which can be Sensitive penetrants are generally less easily rinsed away
monitored by the use of a suitable refractometer. and are therefore less suitable for rough surfaces. When
446
--`,,```,,,,````-`-`,,`,,`,`,,`---

FIG. 1 GENERAL PROCEDURE FLOWSHEET FOR PENETRANT EXAMINATION USING THE WATER-WASHABLE
PROCESS (TEST METHOD E 1209 FOR FLUORESCENT AND TEST METHOD E 1220 FOR VISIBLE LIGHT)
447
FIG. 2 TYPE 2 — POST EMULSIFIABLE PROCEDURES A-2 (FLUORESCENT) AND B-2 (VISIBLE)
448
--`,,```,,,,````-`-`,,`,,`,`,,`---
FIG. 3 SOLVENT-REMOVABLE PENETRANT EXAMINATION GENERAL PROCEDURE FLOWSHEET

(TEST METHOD E 1219 FOR FLUORESCENT AND TEST METHOD E 1220 FOR VISIBLE LIGHT)
449
only loose surface residuals are present, these may be range, the penetrant is applied to the surface to be examined
removed by wiping with clean lint-free cloths. However, so that the entire part or area under examination is com-
precleaning of metals to remove processing residuals such pletely covered with penetrant.
as oil, graphite, scale, insulating materials, coatings, and 8.5.1 Modes of Application — There are various
so forth, should be done using cleaning solvents, vapor modes of effective application of penetrant such as dipping,
degreasing or chemical removing processes. Surface condi- brushing, flooding, or spraying. Small parts are quite often
tioning by grinding, machining, polishing or etching shall placed in suitable baskets and dipped into a tank of pene-
follow shot, sand, grit or vapor blasting to remove the trant. On larger parts, and those with complex geometries,
peened skin and when penetrant entrapment in surface penetrant can be applied effectively by brushing or spray-
irregularities might mask the indications of unacceptable ing. Both conventional and electrostatic spray guns are
discontinuities or otherwise interfere with the effectiveness effective means of applying liquid penetrants to the part
of the examination. For metals, unless otherwise specified, surfaces. Electrostatic spray application can eliminate
etching shall be performed when evidence exists that previ- excess liquid build-up of penetrant on the part, minimize
ous cleaning, surface treatments or service usage have overspray, and minimize the amount of penetrant entering
produced a surface condition that degrades the effective- hollow-cored passages which might serve as penetrant res-
ness of penetrant examination. (See Annex A1.1.1.8 for ervoirs, causing severe bleedout problems during examina-
precautions.) tion. Aerosol sprays are conveniently portable and suitable
NOTE 7: When agreed between purchaser and supplier, grit blasting for local application.
without subsequent etching may be an acceptable cleaning method.
NOTE 11: Caution — Not all penetrant materials are suitable for electro-
NOTE 8: Caution — Sand or shot blasting may possibly close discontinu- static spray applications, so tests should be conducted prior to use.
ities and extreme care should be used with grinding and machining
operations to avoid masking discontinuities. NOTE 12: Warning — With spray applications, it is important that there
be proper ventilation. This is generally accomplished through the use of
NOTE 9: For structural or electronic ceramics, surface preparation by a properly designed spray booth and exhaust system.
grinding, sand blasting and etching for penetrant examination is not 8.5.2 Penetrant Dwell Time — After application,
recommended because of the potential for damage.
allow excess penetrant to drain from the part (care should
8.4 Removal of Surface Contaminants: be taken to prevent pools of penetrant from forming on
8.4.1 Precleaning — The success of any penetrant the part), while allowing for proper penetrant dwell time
examination procedure is greatly dependent upon the sur- (see Table 2). The length of time the penetrant must remain
rounding surface and discontinuity being free of any con- on the part to allow proper penetration should be as recom-
taminant (solid or liquid) that might interfere with the mended by the penetrant manufacturer. Table 2, however,
penetrant process. All parts or areas of parts to be examined provides a guide for selection of penetrant dwell times for
--`,,```,,,,````-`-`,,`,,`,`,,`---
must be clean and dry before the penetrant is applied. If a variety of materials, forms, and types of discontinuity.
only a section of a part, such as a weld, including the heat Unless otherwise specified, the dwell time shall not exceed
affected zone is to be examined, all contaminants shall be the maximum recommended by the manufacturer.
removed from the area being examined as defined by the
NOTE 13: For some specific applications in structural ceramics (for
contracting parties. “Clean” is intended to mean that the example, detecting parting lines in slip-cast material), the required pene-
surface must be free of rust, scale, welding flux, weld trant dwell time should be determined experimentally and may be longer
spatter, grease, paint, oily films, dirt, and so forth, that than that shown in Table 1 and its notes.
might interfere with the penetrant process. All of these
8.6 Penetrant Removal
contaminants can prevent the penetrant from entering dis-
continuities (see Annex or Cleaning of Parts and Materials). 8.6.1 Water Washable:
8.6.1.1 Removal of Excess Penetrants — After the
NOTE 10: Caution — Residues from cleaning processes such as strong
alkalies, pickling solutions and chromates, in particular, may adversely
required penetration time, the excess penetrant on the sur-
react with the penetrant and reduce its sensitivity and performance. face being examined must be removed with water, usually
a washing operation. It can be washed off manually, by
8.4.2 Drying after Cleaning — It is essential that the
the use of automatic or semi-automatic water-spray equip-
surface of parts be thoroughly dry after cleaning, since any
ment or by immersion. For immersion rinsing, parts are
liquid residue will hinder the entrance of the penetrant.
completely immersed in the water bath with air or mechani-
Drying may be accomplished by warming the parts in
cal agitation. Accumulation of water in pockets or recesses
drying ovens, with infrared lamps, forced hot air, or expo-
of the surface must be avoided. If the final rinse step is
sure to ambient temperature.
not effective, as evidenced by excessive residual surface
8.5 Penetrant Application — After the part has been penetrant after rinsing, dry (see 8.7) and reclean the part,
cleaned, dried, and is within the specified temperature then reapply the penetrant for the prescribed dwell time.
450
TABLE 2
RECOMMENDED MINIMUM DWELL TIMES
Dwell TimesA (minutes)

Type of
Material Form Discontinuity PenetrantB DeveloperC
Aluminum, magnesium, steel, brass castings and welds cold shuts, porosity, lack of fusion, 5 10
and bronze, titanium and high- cracks (all forms)
temperature alloys
wrought materials — extrusions, laps, cracks (all forms) 10 10
forgings, plate
Carbide-tipped tools lack of fusion, porosity, cracks 5 10
Plastic all forms cracks 5 10
Glass all forms cracks 5 10
Ceramic all forms cracks, porosity 5 10
A
For temperature range from 50 to 100°F (10 to 38°C) for fluorescent penetrants and 50 to 125°F (10 to 52°C) for visible penetrant.
B
Maximum penetrant dwell time in accordance with 8.5.2.
C
Development time begins as soon as wet developer coating has dried on surface of parts (recommended minimum). Maximum development
time in accordance with 8.8.6.
(a) The temperature of the water should be relatively factor in the selection of and in the emulsification time of
constant and should be maintained within the range of 50 an emulsifier. Contact time should be kept to the least
to 100°F (10 to 38°C). possible time consistent with an acceptable background
(b) Spray-rinse water pressure should not be greater and should not exceed the maximum time specified for the
than 40 psi (280 kPa). part or material.
(c) Rinse time should not exceed 120 s unless otherwise
specified by part of material specification. 8.6.2.3 Post Rinsing — Effective post rinsing of the
emulsified penetrant from the surface can be accomplished
--`,,```,,,,````-`-`,,`,,`,`,,`---
NOTE 14: Caution — Avoid overwashing. Excessive washing can cause

penetrant to be washed out of discontinuities. With fluorescent penetrant
using either manual, semi-automated, or automated water
methods perform the rinsing operation under black light so that it can immersion or spray equipment or combinations thereof.
be determined when the surface penetrant has been adequately removed.
8.6.1.2 Removal by Wiping — In special applica- 8.6.2.4 Immersion — For immersion post rinsing,
tions, penetrant removal may be performed by wiping the parts are completely immersed in the water bath with air
surface with a clean, absorbent material dampened with or mechanical agitation. The time and temperature should
water until the excess surface penetrant is removed, as be kept constant.
determined by examination under black light for fluores- (a) The maximum dip-rinse time should not exceed 120
cent methods and white light for visible methods. s unless otherwise specified by part or material specifi-
8.6.2 Lipophilic Emulsification: cation.
8.6.2.1 Application of Emulsifier — After the (b) The temperature of the water should be relatively
required penetration time, the excess penetrant on the part constant and should be maintained within the range of 50
must be emulsified by immersing or flooding the parts with to 100°F (10 to 38°C). Caution: A touch-up rinse may be
the required emulsifier (the emulsifier combines with the necessary after immersion.
excess surface penetrant and makes the mixture removable
with water rinsing). After application of the emulsifier, the 8.6.2.5 Spray Post Rinsing — Effective post rins-
parts are drained in a manner that prevents the emulsifier ing following emulsification can also be accomplished by
from pooling on the part(s). either manual or automatic water spray rinsing of the parts
8.6.2.2 Emulsification Dwell Time begins as soon as follows:
as the emulsifier has been applied. The length of time that (a) Control rinse water temperature within the range of
the emulsifier is allowed to remain on a part and in contact 50 to 100°F (10 to 38°C).
with the penetrant is dependent on the type of emulsifier
(b) Spray rinse water pressure should be in accordance
employed and the surface condition (smooth or rough).
with manufacturers’ recommendations.
Nominal emulsification time should be as recommended
by the manufacturer. The actual emulsification time must (c) The maximum spray rinse time should not exceed
be determined experimentally for each specific application. 120 s unless otherwise specified by part or materials speci-
The surface finish (roughness) of the part is a significant fication.
451
8.6.2.6 Rinse Effectiveness — If the emulsification should not exceed 120 s or the maximum time stipulated
and final rinse step is not effective, as evidenced by exces- by the part or material specification.
sive residual surface penetrant after emulsification and rins- (d) Emulsifier drain time begins immediately after parts
ing, dry (see 8.7) and reclean the part and reapply the have been withdrawn from the emulsifier tank and contin-
penetrant for the prescribed dwell time. ues until the parts are washed in the final rinse station
8.6.3 Hydrophilic Emulsification: (8.6.3.6). This drain time should be kept to a minimum to
avoid over emulsification and should not exceed 90 s.
8.6.3.1 Prerinsing — Directly after the required
penetration time, it is recommended that the parts be pre- 8.6.3.5 Spray Application — For spray application
rinsed with water prior to emulsification (8.6.3.3). This following the prerinse step, parts are emulsified by the
step allows for the removal of excess surface penetrant spray application of an emulsifier. All part surfaces should
from the parts prior to emulsification so as to minimize be evenly and uniformly sprayed to effectively emulsify
the degree of penetrant contamination in the hydrophilic the residual penetrant on part surfaces to render it water-
emulsifier bath, thereby extending its life. In addition, pre- washable.
rinsing of penetrated parts minimizes possible oily pene- (a) The concentration of the emulsifier for spray appli-
trant pollution in the final rinse step of this process. This cation should be in accordance with the manufacturer’s
is accomplished by collecting the prerinsings in a holding recommendations, but should not exceed 5%.
tank, separating the penetrant from water. (b) Temperature to be maintained at 50 to 100°F (10
to 38°C).
8.6.3.2 Prerinsing Controls — Effective prerinsing
is accomplished by either manual or automated water spray (c) The spray pressure should be 25 psi (175 kPa) max
rinsing of the parts as follows: for air and 40 psi (280 kPa) max for water.
(d) Contact time should be kept to the minimum consist-
(a) Water should be free of contaminants that could
ent with an acceptable background and should not exceed
clog spray nozzles or leave a residue on parts.
120 s or the maximum time stipulated by the part or mate-
(b) Control water temperature within the range of 50 to
rial specification.
100°F (10 to 38°C).
(c) Spray rinse at a water pressure of 25 to 40 psi (175 8.6.3.6 Post-Rinsing of Hydrophilic Emulsified
to 275 kPa). Parts — Effective post-rinsing of emulsified penetrant from
(d) Prerinse time should be the least possible time (nom- the surface can be accomplished using either manual, semi-
inally 60 s maximum) to provide a consistent residue of automated, or automated water immersion or spray equip-
penetrant on parts. Wash time is to be as specified by the ment or combinations thereof.
part or material specification. 8.6.3.7 Immersion Post-Rinsing — Parts are to be
(e) Remove water trapped in cavities using filtered shop completely immersed in the water bath with air or mechani-
air at a nominal pressure 25 psi (175 kPa) or a suction cal agitation.
device to remove water from pooled areas. (a) The temperature of the water should be relatively
8.6.3.3 Application of Emulsifier — After the constant and should be maintained within the range of 50
required penetration time and following the prerinse, the to 100°F (10 to 38°C).
residual surface penetrant on part(s) must be emulsified (b) The maximum dip rinse time should not exceed 120
by immersing the part(s) in a hydrophilic emulsifier bath s unless otherwise specified by part or material specifica-
(8.6.3.4) or by spraying the part(s) with the emulsifier tion. Caution: A touch-up rinse may be necessary after
(8.6.3.5) thereby rendering the remaining residual surface immersion.
penetrant water-washable in the final rinse station (8.6.3.6). 8.6.3.8 Spray Post-Rinsing — Following emulsi-
8.6.3.4 Immersion — For immersion application, fication parts can be post-rinsed by water spray rinsing as
parts are completely immersed in the emulsifier bath. The follows:
hydrophilic emulsifier should be gently agitated throughout (a) Control rinse water temperature within the range of
the contact cycle. 50 to 100°F (10 to 38°C).
(a) Bath concentration should be as recommended by (b) Spray rinse water pressure should be in accordance
the manufacturer. Most hydrophilic emulsifiers are used with manufacturer’s instructions.
within the range of 20 to 33% in water. Nominal use (c) The maximum spray rinse time should not exceed
concentration for immersion applications is 20%. 120 s unless otherwise specified by part or materials speci-
(b) Bath temperatures should be maintained between 50 fication.
and 100°F (10 to 38°C). 8.6.3.9 If the emulsification and final rinse steps
(c) Immersion contact time should be kept to the mini- are not effective, as evidenced by excessive residual surface
mum time consistent with an acceptable background and penetrant after emulsification and rinsing, dry (see 8.7) and
452
reclean the part and reapply the penetrant for the prescribed with low-pressure (5 to 10 psi) (34 to 70 kPa) dry, clean,
dwell time. compressed air.
8.6.4 Solvent-Removable Penetrants: NOTE 15: Caution — The air stream intensity should be established
8.6.4.1 Removal of Excess Penetrant — After the experimentally for each application.
required penetration time, the excess penetrant is removed 8.8.3 Aqueous Developers — Aqueous developers
insofar as possible, by using wipers of a dry, clean, lint- should be applied to the part immediately after the excess
free material and repeating the operation until most traces penetrant has been removed and prior to drying. Aqueous
of penetrant have been removed. Then using a lint-free developers should be prepared and maintained in accor-
material lightly moistened with solvent remover the dance with the manufacturer’s instructions and applied in
remaining traces are gently wiped to avoid removing pene- such a manner as to ensure complete, even, part coverage.
trant from discontinuities. Avoid the use of excess solvent. Caution should be exercised when using an aqueous devel-
If the wiping step is not effective, as evidenced by difficulty oper with water-washable penetrants to avoid possible
in removing the excess penetrant, dry the part (see 8.7), stripping of indications. Aqueous developers may be
and reapply the penetrant for the prescribed dwell time. applied by spraying (see Note 17), flowing, or immersing
Flushing the surface with solvent following the application the part. It is common to immerse the parts in a prepared
of the penetrant and prior to developing is prohibited. developer bath. Immerse parts only long enough to coat
8.7 Drying — Drying the surface of the part(s) is neces- all of the part surfaces with the developer (see Note 18).
sary prior to applying dry or nonaqueous developers or Then remove parts from the developer bath and allow to
following the application of the aqueous developer. Drying drain. Drain all excess developer from recesses and trapped
time will vary with the size, nature, and number of parts sections to eliminate pooling of developer, which can
under examination. obscure discontinuities. Dry the parts in accordance with
8.7. The dried developer coating appears as a translucent
8.7.1 Drying Parameters — Components shall be air
or white coating on the part.
dried at room temperature or in a drying oven. Oven tem-
peratures shall not exceed 160°F (71°C). Drying time shall NOTE 16: Caution — Atomized spraying is not recommended since a
only be that necessary to adequately dry the part. Compo- spotty film may result.
nents shall be removed from the oven immediately after
NOTE 17: Caution — If parts are left in the bath too long, indications
drying. Components shall not be placed in the oven with may leach out.
pooled water or pooled aqueous solutions/suspensions.
8.8.4 Nonaqueous Wet Developers — After the
8.7.2 Drying Time Limits — Do not allow parts to excess penetrant has been removed and the surface has
remain in the drying oven any longer than is necessary to been dried, apply developer by spraying in such a manner
dry the surface. Times over 30 min in the dryer may impair as to ensure complete part coverage with a thin, even film
the sensitivity of the examination. of developer. These types of developer carrier evaporate
8.8 Developer Application: very rapidly at normal room temperature and do not, there-
8.8.1 Modes of Application — There are various fore, require the use of a dryer (see Note 20). Dipping or
modes of effective application of the various types of devel- flooding parts with nonaqueous developers is prohibited,
opers such as dusting, immersing, flooding or spraying. since they may flush or dissolve the penetrant from within
The size, configuration, surface condition, number of parts the discontinuities because of the solvent action of these
to be processed, and so forth, will influence the choice of types of developers.
developer application. NOTE 18: Warning — The vapors from the evaporating, volatile solvent
8.8.2 Dry Powder Developer — Dry powder devel- developer carrier may be hazardous. Proper ventilation should be provided
in all cases, but especially when the surface to be examined is inside a
opers should be applied immediately after drying in such closed volume, such as a process drum or a small storage tank.
a manner as to ensure complete part coverage. Parts can
be immersed in a container of dry developer or in a fluid 8.8.5 Liquid Film Developers — Apply by spraying
bed of dry developer. They can also be dusted with the as recommended by the manufacturer. Spray parts in such
powder developer through a hand powder bulb or a conven- a manner as to ensure complete part coverage of the area
tional or electrostatic powder gun. It is common and effec- being examined with a thin, even film of developer.
tive to apply dry powder in an enclosed dust chamber, 8.8.6 Developing Time — The length of time the
which creates an effective and controlled dust cloud. Other developer is to remain on the part prior to examination
means suited to the size and geometry of the specimen should be not less than 10 min. Developing time begins
may be used, provided the powder is dusted evenly over immediately after the application of dry powder developer
the entire surface being examined. Excess powder may be and as soon as the wet (aqueous and nonaqueous) developer
removed by shaking or tapping the part, or by blowing coating is dry (that is, the solvent carrier has evaporated
453
--`,,```,,,,````-`-`,,`,,`,`,,`---

to dryness). The maximum permitted developing times in the sensitivity of the examination. A minimum light
are 2 h for aqueous developers and 1 h for nonaqueous intensity at the examination site of 100 fc (1000 Lx) is
developers. recommended.
8.9 Examination — Perform examination of parts after 8.9.3 Housekeeping — Keep the examination area
the applicable development time as specified in 8.8.6 to free of interfering debris, including fluorescent objects.
allow for bleedout of penetrant from discontinuities into Practice good housekeeping at all times.
the developer coating. It is good practice to observe the 8.9.4 Evaluation — Unless otherwise agreed, it is
bleedout while applying the developer as an aid in interpret- normal practice to interpret and evaluate the discontinuity
ing and evaluating indications. based on the size of the indication (see Referenced Photo-
8.9.1 Fluorescent Light Examination: graphs E 433).
8.9.1.1 Visible Ambient Light Level — Examine 8.10 Post Cleaning — Post cleaning is necessary in
fluorescent penetrant indications under black light in a those cases where residual penetrant or developer could
darkened area. Visible ambient light should not exceed 2 interfere with subsequent processing or with service
ft candles (20 Lx). The measurement should be made with requirements. It is particularly important where residual
a suitable photographic-type visible light meter on the sur- penetrant examination materials might combine with other
face being examined. factors in service to produce corrosion. A suitable tech-
8.9.1.2 Black Light Level Control — Black light nique, such as a simple water rinse, waterspray, machine
intensity, minimum of 1000 ␮W/cm2, should be measured wash, vapor degreasing, solvent soak, or ultrasonic clean-
on the surface being examined, with a suitable black light ing may be employed (see Annex on Post Cleaning). It is
meter. The black light wavelength shall be in the range of recommended that if developer removal is necessary, it
320 to 380 nm. The intensity should be checked weekly should be carried out as promptly as possible after examina-
to ensure the required output. Reflectors and filters should tion so that it does not “fix” on the part.
be checked daily for cleanliness and integrity. Cracked or NOTE 21: Caution — Developers should be removed prior to vapor
broken ultraviolet (UV) filters should be replaced immedi- degreasing. Vapor degreasing can bake the developer on parts.
ately. Defective bulbs, which radiate UV energy, must be
replaced before further use. Since a drop in line voltage 9. Special Requirements
can cause decreased black light output with consequent
9.1 Impurities:
inconsistent performance, a constant-voltage transformer
should be used when there is evidence of voltage fluctu- 9.1.1 When using penetrant materials on austenitic
ation. stainless steels, titanium, nickel-base or other high-temper-
ature alloys, the need to restrict impurities such as sulfur,
Caution: Certain high-intensity black light may emit unacceptable halogens and alkali metals must be considered. These
amounts of visible light, which will cause fluorescent indications to disap-
impurities may cause embrittlement or corrosion, particu-
pear. Care should be taken to use only bulbs certified by the supplier to
be suitable for such examination purposes. larly at elevated temperatures. Any such evaluation should
also include consideration of the form in which the impuri-
NOTE 19: The recommended minimum light intensity in 8.9.1.2 is ties are present. Some penetrant materials contain signifi-
intended for general usage. For critical examinations, higher intensity cant amounts of these impurities in the form of volatile
levels may be required.
organic solvents. These normally evaporate quickly and
8.9.1.3 Black Light Warm-Up — Allow the black usually do not cause problems. Other materials may contain
light to warm up for a minimum of 10 min prior to its use impurities which are not volatile and may react with the
or measurement of the intensity of the ultraviolet light part, particularly in the presence of moisture or elevated
emitted. temperatures.
8.9.1.4 Visual Adaptation — The examiner should 9.1.2 Because volatile solvents leave the surface
be in the darkened area for at least 1 min before examining quickly without reaction under normal examination proce-
parts. Longer times may be necessary under some circum- dures, penetrant materials are normally subjected to an
stances. evaporation procedure to remove the solvents before the
materials are analyzed for impurities. The residue from
NOTE 20: Caution — Photochromic lenses shall not be worn during
this procedure is then analyzed in accordance with Test
examination.
Method D 129, Test Method D 1552, or Test Method D 129
8.9.2 Visible Light Examination: decomposition followed by Test Method D 516, Method B
8.9.2.1 Visible Light Level — Visible penetrant (Turbidimetric Method) for sulfur. The residue may also
indications can be examined in either natural or artificial be analyzed by Test Method D 808 or Annex A2 on Meth-
light. Adequate illumination is required to ensure no loss ods for Measuring Total Chlorine Content in Combustible
--`,,```,,,,````-`-`,,`,,`,`,,`---
454
Liquid Penetrant Materials (for halogens other than fluo- conforming to the applicable edition of recommended Prac-
rine) and Annex A3 on Method for Measuring Total Fluo- tice SNT-TC-1A, ANSI/ASNT CP-189, NAS-410, or
rine Content in Combustible Liquid Penetration Materials MIL-STD-410.
(for fluorine). An alternative procedure, Annex A4 on
10.2 Procedure Qualification — Qualification of proce-
Determination of Anions by Ion Chromatography, provides
dures using times or conditions differing from those speci-
a single instrumental technique for rapid sequential mea-
fied or for new materials may be performed by any of
surement of common anions such as chloride, fluoride, and
several methods and should be agreed by the contracting
sulfate. Alkali metals in the residue are determined by
parties. A test piece containing one or more discontinuities
flame photometry or atomic absorption spectrophotometry.
of the smallest relevant size is used. The test piece may
NOTE 22: Some current standards indicate that impurity levels of sulfur contain real or simulated discontinuities, providing it dis-
and halogens exceeding 1% of any one suspect element may be considered plays the characteristics of the discontinuities encountered
excessive. However, this high a level may be unacceptable for some in product examination.
applications, so the actual maximum acceptable impurity level must be
--`,,```,,,,````-`-`,,`,,`,`,,`---
decided between supplier and user on a case by case basis. 10.3 Nondestructive Testing Agency Qualification — If
a nondestructive testing agency as described in Practice E
9.2 Evaluated-Temperature Examination — Where
543 is used to perform the examination, the agency shall
penetrant examination is performed on parts that must be
meet the requirements of Practice E 543.
maintained at elevated temperature during examination,
special materials and processing techniques may be 10.4 Requalification may be required when a change or
required. Such examination requires qualification in accor- substitution is made in the type of penetrant materials or
dance with 10.2. Manufacturer’s recommendations should in the procedure (see 10.2).
be observed.
11. Keywords
10. Qualification and Requalification 11.1 fluorescent liquid penetrant testing; hydrophilic
10.1 Personal Qualification — When required by user/ emulsification; lipophilic emulsification; liquid penetrant
supplier agreement, all examination personnel shall be testing; nondestructive testing; solvent removable; visible
qualified/certified in accordance with a written procedure liquid penetrant testing; water-washable methods
455
ANNEXES
(Mandatory Information)
A1. Cleaning of Parts and Materials A1.1.1.4 Alkaline Cleaning:

A1.1 Choice of Cleaning Method (a) Alkaline cleaners are nonflammable water solutions
containing specially selected detergents for wetting, pene-
A1.1.1 The choice of a suitable cleaning method is trating, emulsifying, and saponifying various types of soils.
based on such factors as: (1) type of contaminant to be Hot alkaline solutions are also used for rust removal and
removed since no one method removes all contaminants descaling to remove oxide scale which can mask surface
equally well; (2) effect of the cleaning method on the parts; discontinuities. Alkaline cleaner compounds must be used
(3) practicality of the cleaning method for the part (for in accordance with the manufacturers’ recommendations.
example, a large part cannot be put into a small degreaser Caution: Parts cleaned by the alkaline cleaning process
or ultrasonic cleaner); and (4) specific cleaning require- must be rinsed completely free of cleaner and thoroughly
ments of the purchaser. The following cleaning methods dried by heat prior to the penetrant inspection process [part
are recommended: temperature at the time of penetrant application shall not
A1.1.1.1 Detergent Cleaning — Detergent clean- exceed 125°F (52°C)].
ers are nonflammable water-soluble compounds containing (b) Steam cleaning is a modification of the hot-tank
specially selected surfactants for wetting, penetrating, alkaline cleaning method, which can be used for prepara-
emulsifying, and saponifying various types of soils, such tion of large, unwieldy parts. It will remove inorganic soils
as grease and oily films, cutting and machining fluids, and and many organic soils from the surface of parts, but may
--`,,```,,,,````-`-`,,`,,`,`,,`---
unpigmented drawing compounds, etc. Detergent cleaners not reach to the bottom of deep discontinuities, and a
may be alkaline, neutral, or acidic in nature, but must be subsequent solvent soak is recommended.
noncorrosive to the item being inspected. The cleaning A1.1.1.5 Ultrasonic Cleaning — This method adds
properties of detergent solutions facilitate complete ultrasonic agitation to solvent or detergent cleaning to
removal of soils and contamination from the surface and improve cleaning efficiency and decrease cleaning time. It
void areas, thus preparing them to absorb the penetrant. should be used with water and detergent if the soil to be
Cleaning time should average 10 to 15 min at 170 to 200°F removed is inorganic (rust, dirt, salts, corrosion products,
(77 to 93°C) with moderate agitation, using concentrations etc.), and with organic solvent if the soil to be removed
(generally 6 to 8 oz/gal or 45 to 60 kg/m3) recommended is organic (grease and oily films, etc.). After ultrasonic
by the manufacturer of the cleaning compound. cleaning, parts should be heated to remove the cleaning
A1.1.1.2 Solvent Cleaning — There are a variety fluid, then cooled to at least 125°F (52°C), before applica-
of solvent cleaners that can be effectively utilized to dis- tion of penetrant.
solve such soils as grease and oily films, waxes and seal- A1.1.1.6 Paint Removal — Paint films can be
ants, paints, and in general, organic matter. These solvents effectively removed by bond release solvent paint remover
should be residue-free, especially when used as a hand- or disintegrating-type hot-tank alkaline paint strippers. In
wipe solvent or as a dip-tank degreasing solvent. Solvent most cases, the paint film must be completely removed to
cleaners are not recommended for the removal of rust and expose the surface of the metal. Solvent-type paint
scale, welding flux and spatter, and in general, inorganic removers can be of the high-viscosity thickened type for
soils. Caution: Some cleaning solvents are flammable and spray or brush application or can be of low viscosity two-
can be toxic. Observe all manufacturers’ instructions and layer type for dip-tank application. Both types of solvent
precautionary notes. paint removers are generally used at ambient temperatures,
A1.1.1.3 Vapor Degreasing — Vapor degreasing as received. Hot-tank alkaline strippers are water-soluble
is a preferred method of removing oil or grease-type soils powder compounds generally used at 8 to 16 oz/gal (60
from the surface of parts and from open discontinuities. It to 120 kg/m3) of water at 180 to 200°F (82 to 93°C).
will not remove inorganic-type soils (dirt, corrosion, salts, After paint removal, the parts must be thoroughly rinsed
etc.), and may not remove resinous soils (plastic coatings, to remove all contamination from the void openings and
varnish, paint, etc.). Because of the short contact time, then thoroughly dried.
degreasing may not completely clean out deep discontinu- A1.1.1.7 Mechanical Cleaning and Surface Condi-
ities and a subsequent solvent soak is recommended. tioning — Metal-removing processes such as filing,
456
buffing, scraping, mechanical milling, drilling, reaming, A2. Methods for Measuring Total Chlorine Content
grinding, liquid honing, sanding, lathe cutting, tumble or in Combustible Liquid Penetrant Materials
vibratory deburring, and abrasive blasting, including abra- A2.1 Scope and Application
sives such as glass beads, sand, aluminum oxide, ligno-
cellulose pellets, metallic shot, etc., are often used to A2.1.1 These methods cover the determination of
remove such soils as carbon, rust and scale, and foundry chlorine in combustible liquid penetrant materials, liquid
or solid. Its range of applicability is 0.001 to 5% using
adhering sands, as well as to deburr or produce a desired
either of the alternative titrimetric procedures. The proce-
cosmetic effect on the part. These processes may decrease
dures assume that bromine or iodine will not be present.
the effectiveness of the penetrant examination by smearing
If these elements are present, they will be detected and
or peening over metal surfaces and filling discontinuities
reported as chlorine. The full amount of these elements will
open to the surface, especially for soft metals such as
not be reported. Chromate interferes with the procedures,
aluminum, titanium, magnesium, and beryllium alloy.
causing low or nonexistent end points. The method is appli-
A1.1.1.8 Acid Etching — Inhibited acid solutions cable only to materials that are totally combustible.
(pickling solutions) are routinely used for descaling part
A2.2 Summary of Methods
surfaces. Descaling is necessary to remove oxide scale,
which can mask surface discontinuities and prevent pene- A2.2.1 The sample is oxidized by combustion in
trant from entering. Acid solutions/etchants are also used a bomb containing oxygen under pressure (Caution, see
routinely to remove smeared metal that peens over surface A2.2.1.1). The chlorine compounds thus liberated are
discontinuities. Such etchants should be used in accordance absorbed in a sodium carbonate solution and the amount of
with the manufacturers’ recommendations. Caution: chloride present is determined titrimetrically either against
silver nitrate with the end point detected potiometrically
NOTE A1: Etched parts and materials must be rinsed completely free of (Method A) or coulometrically with the end point detected
etchants, the surface neutralized and thoroughly dried by heat prior to by current flow increase (Method B).
application of penetrants. Acids and chromates can adversely affect the
fluorescence of fluorescent materials. A2.2.1.1 Safety — Strict adherence to all of the
provisions prescribed hereinafter ensures against explosive
--`,,```,,,,````-`-`,,`,,`,`,,`---
NOTE A2 — Whenever there is a possibility of hydrogen embrittlement rupture of the bomb, or a blow-out, provided the bomb is
as a result of acid solution/etching, the part should be baked at a suitable of proper design and construction and in good mechanical
temperature for an appropriate time to remove the hydrogen before further condition. It is desirable, however, that the bomb be
processing. After baking, the part shall be cooled to a temperature below
125°F (52°C) before applying penetrants.
enclosed in a shield of steel plate at least 1⁄2 in. (12.7
mm) thick, or equivalent protection be provided against
A1.1.1.9 Air Firing of Ceramics — Heating of a unforeseeable contingencies.
ceramic part in a clean, oxidizing atmosphere is an effective
way of removing moisture or light organic soil or both. A2.3 Apparatus
The maximum temperature that will not cause degradation A2.3.1 Bomb, having a capacity of not less than 300
of the properties of the ceramic should be used. mL, so constructed that it will not leak during the test, and
that quantitative recovery of the liquids from the bomb
A1.2 Post Cleaning may be readily achieved. The inner surface of the bomb
A1.2.1 Removal of Developer — Dry powder devel- may be made of stainless steel or any other material that
oper can be effectively removed with an air blow-off (free will not be affected by the combustion process or products.
of oil) or it can be removed with water rinsing. Wet devel- Materials used in the bomb assembly, such as the head
oper coatings can be removed effectively by water rinsing gasket and leadwire insulation, shall be resistant to heat
or water rinsing with detergent either by hand or with a and chemical action, and shall not undergo any reaction
mechanical assist (scrub brushing, washing machine, etc.). that will affect the chlorine content of the liquid in the
The soluble developer coatings simply dissolve off of the bomb.
part with a water rinse. A2.3.2 Sample Cup, platinum, 24 mm in outside
A1.2.2 Residual penetrant may be removed through diameter at the bottom, 27 mm in outside diameter at the
solvent action. Vapor degreasing (10 min minimum), sol- top, 12 mm in height outside and weighing 10 to 11 g,
vent soaking (15 min minimum), and ultrasonic solvent opaque fused silica, wide-form with an outside diameter
of 29 mm at the top, a height of 19 mm, and a 5-mL
cleaning (3 min minimum) techniques are recommended.
capacity (Note 1), or nickel (Kawin capsule form), top
In some cases, it is desirable to vapor degrease, then follow
diameter of 28 mm, 15 mm in height, and 5-mL capacity.
with a solvent soak. The actual time required in the vapor
degreaser and solvent soak will depend on the nature of NOTE A2.1: Fused silica crucibles are much more economical and longer-
the part and should be determined experimentally. lasting than platinum. After each use, they should be scrubbed out with
457
fine, wet emery cloth, heated to dull red heat over a burner, soaked in TABLE A2.1
hot water for 1 h, then dried and stored in a desiccator before reuse. GAGE PRESSURES
A2.3.3 Firing Wire, platinum, approximately No. 26 Gage Pressure, atm (MPa)
B & S gage. Capacity of Bomb, mL minA max
A2.3.4 Ignition Circuit (Note A2.2), capable of sup-
300 to 350 38 (3.85) 40 (4.05)
plying sufficient current to ignite the nylon thread or cotton
350 to 400 35 (3.55) 37 (3.75)
wicking without melting the wire. 400 to 450 30 (3.04) 32 (3.24)
450 to 500 27 (2.74) 29 (2.94)
NOTE A2.2: Caution — The switch in the ignition circuit shall be of
a type that remains open, except when held in closed position by the A
The minimum pressures are specified to provide sufficient oxygen
operator. for complete combustion and the maximum pressures present a
safety requirement.
A2.3.5 Nylon Sewing Thread, or Cotton Wicking,
white.
A2.4 Purity of Reagents A2.4), add it to the sample cup by means of a dropper at
this time (Caution, see Notes A2.5 and A2.6).
A2.4.1 Reagent grade chemicals shall be used in all
tests. Unless otherwise indicated, it is intended that all NOTE A2.3: After repeated use of the bomb for chlorine determination,
reagents shall conform to the specifications of the Commit- a film may be noticed on the inner surface. This dullness should be
tee on Analytical Reagents of the American Chemical Soci- removed by periodic polishing of the bomb. A satisfactory method for
doing this is to rotate the bomb in a lathe at about 300 rpm and polish
ety, where such specifications are available. Other grades
the inside surface with Grit No. 2/0 or equivalent paper coated with a
may be used provided it is first ascertained that the reagent light machine oil to prevent cutting, and then with a paste of grit-free
is of sufficiently high purity to permit its use without less- chromic oxide and water. This procedure will remove all but very deep
ening the accuracy of the determination. pits and put a high polish on the surface. Before using the bomb, it should
be washed with soap and water to remove oil or paste left from the
A2.4.2 Unless otherwise indicated, references to polishing operation. Bombs with porous or pitted surfaces should never
water shall be understood to mean referee grade reagent be used because of the tendency to retain chlorine from sample to sample.
water conforming to Specification D 1193. Caution: Do not use more than 1 g total of sample and white oil or other
chlorine-free combustible material.
A2.5 Decomposition
A2.5.1 Reagents and Materials: NOTE A2.4: If the sample is not readily miscible with white oil, some
other nonvolatile, chlorine-free combustible diluent may be employed in
A2.5.1.1 Oxygen, free of combustible material and place of white oil. However, the combined weight of sample and nonvola-
halogen compounds, available at a pressure of 40 atm (4.05 tile diluent shall not exceed 1 g. Some solid additives are relatively
MPa). insoluble, but may be satisfactorily burned when covered with a layer
of white oil.
A2.5.1.2 Sodium Carbonate Solution (50 g
Na2CO3/L) — Dissolve 50 g of anhydrous Na2CO3 or 58.5 NOTE A2.5: The practice of running alternately samples high and low
g of Na2CO3 · H2O) or 135 g of Na2CO3 · 10H2O in water 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
and dilute to 1 L.
tendency for residual chlorine to carry over from sample to sample has
A2.5.1.3 White Oil, refined. been observed in a number of laboratories. When a sample high in chlorine
has preceded one low in chlorine content, the test on the low-chlorine
A2.5.2 Procedure: sample should be repeated and one or both of the low values thus obtained
A2.5.2.1 Preparation of Bomb and Sample — Cut should be considered suspect if they do not agree within the limits of
a piece of firing wire approximately 100 mm in length. repeatability of this method.
Coil the middle section (about 20 mm) and attach the free A2.5.2.2 Addition of Oxygen — Place the sample
ends to the terminals. Arrange the coil so that it will be cup in position and arrange the nylon thread, or wisp of
above and to one side of the sample cup. Place 5 mL of cotton so that the end dips into the sample. Assemble
Na2CO3 solution in the bomb (Note A2.3), place the cover the bomb and tighten the cover securely. Admit oxygen
on the bomb and vigorously shake for 15 s to distribute (Caution, Note A2.6) slowly (to avoid blowing the sample
the solution over the inside of the bomb. Open the bomb, from the cup) until a pressure is reached as indicated in
place the sample-filled sample cup in the terminal holder, Table A2.1.
and insert a short length of thread between the firing wire
and sample. Use of a sample weight containing over 20 Note A2.6: Caution — Do not add oxygen or ignite the sample if the
mg of chlorine may cause corrosion of the bomb. The bomb has been jarred, dropped, or tilted.
sample weight should not exceed 0.4 g if the expected A2.5.2.3 Combustion — Immerse the bomb in a
chlorine content is 2.5% or above. If the sample is solid, cold-water bath. Connect the terminals to the open electri-
not more than 0.2 g should be used. Use 0.8 g of white cal circuit. Close the circuit to ignite the sample. Remove
oil with solid samples. If white oil will be used (Note the bomb from the bath after immersion for at least ten
458
minutes. Release the pressure at a slow, uniform rate such amount of difference between the present reading and the
that the operation requires not less than 1 min. Open the last reading. Continue adding 0.1-mL increments, making
bomb and examine the contents. If traces of unburned oil readings and determining differences between readings
or sooty deposits are found, discard the determination, and until a maximum difference between readings is obtained.
thoroughly clean the bomb before again putting it in use The total amount of AgNO3 solution required to produce
(Note A2.3). this maximum differential is the end point. Automatic titra-
A2.6 Analysis, Method A, Potentiometric Titration tors continuously stir the sample, add titrant, measure the
Procedure potential difference, calculate the differential, and plot the
A2.6.1 Apparatus: differential on a chart. The maximum differential is taken
at the end point.
A2.6.1.1 Silver Billet Electrode.
A2.6.1.2 Glass Electrode, pH measurement type. NOTE A2.8: For maximum sensitivity, 0.00282 N AgNO3 solution may
be used with the automatic titrator. This dilute reagent should not be
A2.6.1.3 Buret, 25-mL capacity, 0.05-mL gradua- used with large samples or where chlorine content may be over 0.1%
tions. since these tests will cause end points of 10 mL or higher. The large
A2.6.1.4 Millivolt Meter, or expanded scale pH amount of water used in such titrations reduces the differential between
readings, making the end point very difficult to detect. For chlorine
meter capable of measuring 0 to 220 mV. contents over 1% in samples of 0.8 g or larger, 0.282 N AgNO3 solution
Note A2.7: An automatic titrator is highly recommended in place of items will be required to avoid exceeding the 10-mL water dilution limit.
A2.6.1.3 through A2.6.1.4. Repeatability and sensitivity of the method A2.6.5 Blank — Make blank determinations with the
are much enhanced by the automatic equipment while much tedious effort amount of white oil used but omitting the sample. (Liquid
is avoided.
samples normally require only 0.15 to 0.25 g of white oil
A2.6.2 Reagents and Materials: while solids require 0.7 to 0.8 g.) Follow normal procedure,
A2.6.2.1 Acetone, chlorine-free. making two or three test runs to be sure the results are
A2.6.2.2 Methanol, chlorine-free. within the limits of repeatability for the test. Repeat this
A2.6.2.3 Silver Nitrate Solution (0.0282 N) — Dis- blank procedure whenever new batches of reagents or white
solve 4.7910 ± 0.0005 g of silver nitrate (AgNO3) in water oil are used. The purpose of the blank run is to measure
and dilute to 1 L. the chlorine in the white oil, the reagents, and that intro-
duced by contamination.
A2.6.2.4 Sodium Chloride Solution (0.0282 N) —
Dry a few grams of sodium chloride (NaCl) for 2 h at 130 A2.6.6 Standardization — Silver nitrate solutions are
to 150°C, weigh out 1.6480 ± 0.0005 g of the dried NaCl, not permanently stable, so the true activity should be
dissolve in water, and dilute to 1 L. checked when the solution is first made up and then periodi-
cally during the life of the solution. This is done by titration
A2.6.2.5 Sulfuric Acid (1 + 2) — Mix 1 volume
of a known NaCl solution as follows: Prepare a mixture
of concentrated sulfuric acid (H2SO4,sp. gr 1.84) with 2
of the amounts of the chemicals (Na2CO3 solution, H2SO4
volumes of water.
solution, acetone, and methanol) specified for the test. Pipet
A2.6.3 Collection of Chlorine Solution — Remove in 5.0 mL of 0.0282-N NaCl solution and titrate to the
the sample cup with clean forceps and place in a 400-mL end point. Prepare and titrate a similar mixture of all the
beaker. Wash down the walls of the bomb shell with a chemicals except the NaCl solution, thus obtaining a
fine stream of methanol from a wash bottle, and pour the reagent blank reading. Calculate the normality of the
washings into the beaker. Rinse any residue into the beaker. AgNO3 solution as follows:
Next, rinse the bomb cover and terminals into the beaker.
Finally, rinse both inside and outside of the sample crucible 5.0 ⴛ NNaCl
NAgNO3 p
into the beaker. Washings should equal but not exceed 100 VA − V B
mL. Add methanol to make 100 mL. where:
A2.6.4 Determination of Chlorine — Add 5 mL of NAgNO3 p normality of the AgNO3 solution,
H2SO4 (1:2) to acidify the solution (solution should be NNaCl p normality of the NaCl solution,
acid to litmus and clear of white Na2CO3 precipitate). Add VA p millilitres of AgNO3 solution used for the titra-
100 mL of acetone. Place the electrodes in the solution, tion including the NaCl solution, and
start the stirrer (if mechanical stirrer is to be used), and VB p millilitres of AgNO3 solution used for the titra-
begin titration. If titration is manual, set the pH meter on tion of the reagents only.
the expanded millivolt scale and note the reading. Add
A2.6.7 Calculation — Calculate the chlorine content
exactly 0.1 mL of AgNO3 solution from the buret. Allow a
of the sample as follows:
few seconds stirring; then record the new millivolt reading.
Subtract the second reading from the first. Continue the (VS − VB) ⴛ N ⴛ 3.545
Chlorine, weight % p
titration, noting each amount of AgNO3 solution and the W
459
--`,,```,,,,````-`-`,,`,,`,`,,`---

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

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

Chlorine, weight % p
is: Add approximately 1 L or hot distilled or deionized W
water to the 6.2 g of dry gelatin mixture contained in one
vial supplied by the equipment manufacturer. Gently heat where:
with continuous mixing until the gelatin is completely dis- P p counter reading obtained with the sample,
solved. B p average counter reading obtained with average of
A2.7.3.2 Divide into aliquots each sufficient for the three blank readings,
one day’s analyses. (Thirty millilitres is enough for approx- M p standardization constant. This is dependent on the
imately eleven titrations.) Keep the remainder in a refriger- instrument range setting in use and the reading
ator, but do not freeze. The solution will keep for about 6 obtained with a known amount of the 100 meq
months in the refrigerator. When ready to use, immerse of Cl per litre of solution, and
the day’s aliquot in hot water to liquefy the gelatin. W p weight of sample used, g.
460
--`,,```,,,,````-`-`,,`,,`,`,,`---

A2.7.6 Precision and Accuracy: A3.4 Apparatus

A2.7.6.1 Duplicate results by the same operator A3.4.1 Bomb, having a capacity of not less than 300
can be expected to exhibit the following relative standard mL, so constructed that it will not leak during the test, and
deviations: that quantitative recovery of the liquids from the bomb
may be readily achieved. The inner surface of the bomb
Approximate % Chlorine RSD, %
1.0 and above 0.10 may be made of stainless steel or any other material that
0.1 2.5 will not be affected by the combustion process or products.
0.003 5.9 Materials used in the bomb assembly, such as the head
gasket and leadwire insulation, shall be resistant to heat
A2.7.6.2 The method can be expected to report and chemical action, and shall not undergo any reaction
values that vary from the true value by the following that will affect the fluorine content of the liquid in the
amounts: bomb.
0.1% chlorine and above ±2% A3.4.2 Sample Cup, nickel, 20 mm in outside diame-
0.001 to 0.01% chlorine ±9%. ter at the bottom, 28 mm in outside diameter at the top,
and 16 mm in height; or platinum, 24 mm in outside
A2.7.6.3 If bromine is present, 36.5% of the true diameter at the bottom, 27 mm in outside diameter at the
amount will be reported. If iodine is present, 20.7% of the top, 12 mm in height, and weighing 10 to 11 g.
true amount will be reported. Fluorine will not be detected.
A3.4.3 Firing Wire, platinum, approximately No. 26
B & S gage.
A3. Method for Measuring Total Fluorine Content A3.4.4 Ignition Circuit (Note A3.1), capable of sup-
in Combustible Liquid Penetrant Materials plying sufficient current to ignite the nylon thread or cotton
A3.1 Scope and Application wicking without melting the wire.
A3.1.1 This method covers the determination of flu- NOTE A3.1: Caution — The switch in the ignition circuit shall be of
orine in combustible liquid penetrant materials, liquid or a type that remains open, except when held in closed position by the
solid, that do not contain appreciable amounts of interfering operator.
elements, or have any insoluble residue after combustion. A3.4.5 Nylon Sewing Thread, or Cotton Wicking,
Its range of applicability is 1 to 200 000 ppm. white.
A3.1.2 The measure of the fluorine content employs A3.4.6 Funnel, polypropylene (Note A3.2).
the fluoride selective ion electrode. A3.4.7 Volumetric Flask, polypropylene, 100-mL
(Note A3.2).
A3.2 Summary of Method
A3.4.8 Beaker, polypropylene, 150-mL (Note A3.2).
A3.2.1 The sample is oxidized by combustion in
a bomb containing oxygen under pressure (Caution, see A3.4.9 Pipet, 100-␮L, Eppendorf-type (Note A3.2).
A3.2.1.1). The fluorine compounds thus liberated are A3.4.10 Magnetic Stirrer and TFE-coated magnetic
absorbed in a sodium citrate solution and the amount of stirring bar.
fluorine present is determined potentiometrically through A3.4.11 Fluoride Specific Ion Electrode and suitable
the use of a fluoride selective ion electrode. reference electrode.
A3.2.1.1 Safety — Strict adherence to all of the A3.4.12 Millivolt Meter capable of measuring to
provisions prescribed hereinafter ensures against explosive 0.1 mV.
rupture of the bomb, or a blow-out, provided the bomb is
NOTE A3.2: Glassware should never be used to handle a fluoride solution
of proper design and construction and in good mechanical
as it will remove fluoride ions from solution or on subsequent use carry
condition. It is desirable, however, that the bomb be fluoride ion from a concentrated solution to one more dilute.
enclosed in a shield of steel plate at least 1⁄2 in. (12.7
mm) thick, or equivalent protection be provided against A3.5 Reagents
unforeseeable contingencies. A3.5.1 Purity of Reagents — Reagent grade chemi-
cals shall be used in all tests. Unless otherwise indicated,
A3.3 Interferences it is intended that all reagents shall conform to the specifi-
A3.3.1 Silicon, calcium, aluminum, magnesium, and cations of the Committee on Analytical Reagents of the
other metals forming precipitates with fluoride ion will American Chemical Society, where such specifications are
interfere if they are present in sufficient concentration to available. Other grades may be used, provided it is first
exceed the solubility of their respective fluorides. Insoluble ascertained that the reagent is of sufficiently high purity
residue after combustion will entrain fluorine even if other- to permit its use without lessening the accuracy of the
wise soluble. determination.
461
--`,,```,,,,````-`-`,,`,,`,`,,`---

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

all references to water shall be understood to mean Type GAGE PRESSURES
I reagent water conforming to Specification D 1193. Gage Pressure, atm
A3.5.3 Fluoride Solution, Stock (2000 ppm) — Dis- (MPa)
solve 4.4200 ± 0.0005 g of predried (at 130 to 150°C for Capacity of Bomb, mL minA max
1 h, then cooled in a desiccator) sodium fluoride in distilled 300 to 350 38 40
water and dilute to 1 L. 350 to 400 35 37
A3.5.4 Oxygen, free of combustible material and 400 to 450 30 32
450 to 500 27 29
halogen compounds, available at a pressure of 40 atm (4.05
A
MPa). The minimum pressures are specified to provide sufficient oxygen
for complete combustion and the maximum pressures present a
A3.5.5 Sodium Citrate Solution — Dissolve 27 g of safety requirement.
sodium citrate dihydrate in water and dilute to 1 L.
A3.5.6 Sodium Hydroxide Solution (5 N) — Dissolve
200 g of sodium hydroxide (NaOH) pellets in water and so that the end dips into the sample. Assemble the bomb
dilute to 1 L; store in a polyethylene container. and tighten the cover securely. Admit oxygen (Caution,
A3.5.7 Wash Solution (Modified TISAB, Total Ionic Note A3.4) slowly (to avoid blowing the sample from the
Strength Adjustment Buffer) — To 300 mL of distilled cup) until a pressure is reached as indicated in Table A3.1.
water, add 32 mL of glacial acetic acid, 6.6 g of sodium
NOTE A3.4: Caution — Do not add oxygen or ignite the sample if the
citrate dihydrate, and 32.15 g of sodium chloride. Stir to bomb has been jarred, dropped, or tilted.
dissolve and then adjust the pH to 5.3 using 5 N NaOH
solution. Cool and dilute to 1 L. A3.6.3 Combustion — Immerse the bomb in a cold-
water bath. Connect the terminals to the open electrical
A3.5.8 White Oil, refined. circuit. Close the circuit to ignite the sample. Remove the
A3.6 Decomposition Procedure bomb from the bath after immersion for at least 10 min.
A3.6.1 Preparation of Bomb and Sample — Cut a Release the pressure at a slow, uniform rate such that the
piece of firing wire approximately 100 mm in length. Coil operation requires not less than 1 min. Open the bomb and
the middle section (about 20 mm) and attach the free ends examine the contents. If traces of unburned oil or sooty
to the terminals. Arrange the coil so that it will be above deposits are found, discard the determination, and thor-
and to one side of the sample cup. Place 10 mL of sodium oughly clean the bomb before again putting it in use.
citrate solution in the bomb, place the cover on the bomb, A3.6.4 Collection of Fluorine Solution — Remove
and vigorously shake for 15 s to distribute the solution the sample cup with clean forceps and rinse with wash
over the inside of the bomb. Open the bomb, place the solution into a 100-mL volumetric flask. Rinse the walls
sample-filled sample cup in the terminal holder, and insert of the bomb shell with a fine stream of wash solution from
a short length of thread between the firing wire and the a wash bottle, and add the washings to the flask. Next,
sample. The sample weight used should not exceed 1 g. rinse the bomb cover and terminals into the volumetric
If the sample is a solid, add a few drops of white oil at flask. Finally, add wash solution to bring the contents of
this time to ensure ignition of the sample. the flask to the line.
NOTE A3.3: Use of sample weights containing over 20 mg of chlorine A3.7 Procedure
may cause corrosion of the bomb. To avoid this it is recommended that
A3.7.1 Ascertain the slope (millivolts per ten-fold
for samples containing over 2% chlorine, the sample weight be based on
the following table: change in concentration) of the electrode as described by
Sample the manufacturer.
Chlorine Weight, White Oil
A3.7.2 Obtain a blank solution by performing the
Content, % g Weight, g
procedure without a sample.
2 to 5 0.4 0.4
5 to 10 0.2 0.6 A3.7.3 Immerse the fluoride and reference electrodes
10 to 20 0.1 0.7 in solutions and obtain the equilibrium reading to 0.1 mV.
20 to 50 0.05 0.7 (The condition of the electrode determines the length of
time necessary to reach equilibrium. This may be as little
Caution: Do not use more than 1 g total of sample and as 5 min or as much as 20 min.)
white oil or other fluorine-free combustible material. A3.7.4 Add 100 ␮L of stock fluoride solution and
A3.6.2 Addition of Oxygen — Place the sample cup obtain the reading after the same length of time necessary
in position and arrange the nylon thread, or wisp of cotton for A3.7.3.
462
--`,,```,,,,````-`-`,,`,,`,`,,`---

A3.8 Calculation low capacity, strongly basic anion exchanger (guard and
A3.8.1 Calculate the fluorine content of the sample separator column). The separated anions are directed onto
as follows: a strongly acidic cation exchanger (suppressor column)
where they are converted to their highly conductive acid
2 ⴛ 10−4 2 ⴛ 10−4
Fluorine, ppm p
− 冤
10⌬E1/S − 1 10⌬E2 /S − 1 冥
ⴛ 106
form and the carbonate-bicarbonate eluant is converted to
weakly conductive carbonic acid. The separated anions in
W their acid form are measured by conductivity. They are
where: identified on the basis of retention time as compared to
standards. Quantitation is by measurement of peak area or
⌬E1 p millivolt change in sample solution on addition peak height. Blanks are prepared and analyzed in a similar
of 100 ␮L of stock fluoride solution, fashion.
⌬E2 p millivolt change in blank solution on addition of
100 ␮L of the stock fluoride solution, A4.2.2 Interferences — Any substance that has a
S p slope of fluoride electrode as determined in retention time coinciding with that of any anion to be
A3.7.1, and determined will interfere. For example, relatively high con-
W p grams of sample. centrations of low-molecular-weight organic acids interfere
with the determination of chloride and fluoride. A high
A3.9 Precision and Bias concentration of any one ion also interferes with the resolu-
A3.9.1 Repeatability — The results of two determination of others. Sample dilution overcomes many interfer-
tions by the same analyst should not be considered suspect ences. To resolve uncertainties of identification or
unless they differ by more than 1.1 ppm (0.00011%) or quantitation use the method of known additions. Spurious
8.0% of the amount detected, whichever is greater. peaks may result from contaminants in reagent water, glass-
A3.9.2 Reproducibility — The results of two determi- ware, or sample processing apparatus. Because small sam-
nations by different laboratories should not be considered ple volumes are used, scrupulously avoid contamination.
suspect unless they differ by 6.7 ppm or 129.0% of the A4.2.3 Minimum Detectable Concentration — The
amount detected, whichever is greater. minimum detectable concentration of an anion is a function
A3.9.3 Bias — The average recovery of the method of sample size and conductivity scale used. Generally,
is 62 to 64% of the amount actually present although 83 minimum detectable concentrations are in the range of 0.05
to 85% recoveries can be expected with proper technique. mg/L for F− and 0.1 mg/L for Br−, Cl−, NO3−, NO2−, PO43−,
and SO42− with a 100-␮L sample loop and a 10-␮mho full-
scale setting on the conductivity detector. Similar values
A4. Determination of Anions by Ion may be achieved by using a higher scale setting and an
Chromatography With Conductivity electronic integrator.
Measurement
A4.3 Apparatus
A4.1 Scope and Application
A4.3.1 Bomb, having a capacity of not less than 300
A4.1.1 This method is condensed from ASTM proce- mL, so constructed that it will not leak during the test, and
dures and APHA Method 429 and optimized for the analy- that quantitative recovery of the liquids from the bomb
sis of detrimental substances in organic based materials. may be readily achieved. The inner surface of the bomb
It provides a single instrumental technique for rapid, may be made of stainless steel or any other material that
sequential measurement of common anions such as bro- will not be affected by the combustion process or products.
mide, chloride, fluoride, nitrate, nitrite, phosphate, and Materials used in the bomb assembly, such as the head
sulfate. gasket and leadwire insulation, shall be resistant to heat
A4.2 Summary of Method and chemical action, and shall not undergo any reaction
A4.2.1 The material must be put in the form of an that will affect the chlorine content of the liquid in the
aqueous solution before analysis can be attempted. The bomb.
sample is oxidized by combustion in a bomb containing A4.3.2 Sample Cup, platinum, 24 mm in outside
oxygen under pressure. The products liberated are absorbed diameter at the bottom, 27 mm in outside diameter at the
in the eluant present in the bomb at the time of ignition. top, 12 mm in height outside, and weighing 10 to 11 g;
This solution is washed from the bomb, filtered, and diluted opaque fused silica, wide-form with an outside diameter
to a known volume. of 29 mm at the top, a height of 19 mm, and a 5-mL
A4.2.1.1 A filtered aliquot of sample is injected capacity (Note A4.1), or nickel (Kawin capsule form), top
into a stream of carbonate-bicarbonate eluant and passed diameter of 28 mm, 15 mm in height, and 5-mL capacity.
through a series of ion exchangers. The anions of interest NOTE A4.1: Fused silica crucibles are much more economical and longer
are separated on the basis of their relative affinities for a lasting than platinum. After each use, they should be scrubbed out with
463
fine, wet emery cloth, heated to dull red heat over a burner, soaked in A4.4.4 Regenerant Solution 1, H2SO4, 1 N, use this
hot water for 1 h then dried and stored in a desiccator before reuse. regenerant when suppressor is not a continuously regener-
A4.3.3 Firing Wire, platinum, approximately No. 26 ated one.
B and S gage. A4.4.5 Regenerant Solution 2, H2SO4, 0.025 N, dilute
A4.3.4 Ignition Circuit (Note A4.2), capable of sup- 2.8 mL conc H2SO4 to 4 L or 100 mL regenerant solution
plying sufficient current to ignite the nylon thread or cotton 1 to 4 L. Use this regenerant with continuous regeneration
wicking without melting the wire. fiber suppressor system.
A4.4.6 Standard Anion Solutions, 100 mg/L, prepare
NOTE A4.2: Caution — The switch in the ignition circuit shall be of
a type that remains open, except when held in closed position by the a series of standard anion solutions by weighing the indi-
operator. cated amount of salt, dried to a constant weight at 105°C,
to 1000 mL. Store in plastic bottles in a refrigerator; these
A4.3.5 Nylon Sewing Thread, or Cotton Wicking,
solutions are stable for at least one month.
white. Amount,
A4.3.6 Ion Chromatograph, including an injection Anion Salt g/L
valve, a sample loop, guard, separator, and suppressor col- Cl− NaCl 1.6485
umns, a temperature-compensated small-volume conduc- F− NaF 2.2100
tivity cell (6 ␮L or less), and a strip chart recorder capable Br− NaBr 1.2876
of full-scale response of 2 s or less. An electronic peak NO3− NaNO3 1.3707
NO2− NaNO2 1.4998
integrator is optional. The ion chromatograph shall be capa- PO43− KH2PO4 1.4330
ble of delivering 2 to 5 mL eluant/ min at a pressure of SO42− K2SO4 1.8141
1400 to 6900 kPa.
A4.4.7 Combined Working Standard Solution, High
A4.3.7 Anion Separator Column, with styrene divi-
Range — Combine 10 mL of the Cl−, F−, NO3−, NO2−, and
nyl-benzene-based low-capacity pellicular anion-exchange
PO43− standard anion solutions, 1 mL of the Br−, and 100
resin capable of resolving Br−, Cl−, F−, NO3−, NO2−, PO43−,
mL of the SO42− standard solutions, dilute to 1000 mL,
and SO42−; 4 ⴛ 250 mm.
and store in a plastic bottle protected from light; contains
A4.3.8 Guard Column, identical to separator column 10 mg/L each of Cl−, F−, NO3−, NO2−, and PO43−, 1 mg
except 4 ⴛ 50 mm, to protect separator column from Br−/L, and 100 mg SO42−/L. Prepare fresh daily.
fouling by particulates or organics.
A4.4.8 Combined Working Standard Solution, Low
A4.3.9 Suppressor Column, high-capacity cation- Range — Dilute 100 mL combined working standard solu-
exchange resin capable of converting eluant and separated tion, high range, to 1000 mL and store in a plastic bottle
anions to their acid forms. protected from light; contains 1.0 mg/L each Cl−, F−, NO3−,
A4.3.10 Syringe, minimum capacity of 2 mL and NO2−, and PO43−, 0.1 mg Br−/L, and 10 mg SO42−/L. Pre-
equipped with a male pressure fitting. pare fresh daily.
A4.4.9 Alternative Combined Working Standard
A4.4 Reagents
Solutions — Prepare appropriate combinations according
A4.4.1 Purity of Reagents — Reagent grade chemi- to anion concentration to be determined. If NO2− and PO43−
cals shall be used in all tests. Unless otherwise indicated, are not included, the combined working standard is stable
it is intended that all reagents shall conform to the specifi- for one month.
cations of the Committee on Analytical Reagents of the
American Chemical Society, where such specifications are A4.5 Decomposition Procedure
available. Other grades may be used, provided it is first A4.5.1 Preparation of Bomb and Sample — Cut a
ascertained that the reagent has sufficiently high purity piece of firing wire approximately 100 mm in length. Coil
to permit its use without lessening the accuracy of the the middle section (about 20 mm) and attach the free ends
determination. to the terminals. Arrange the coil so that it will be above
and to one side of the sample cup. Place 5 mL of Na2CO3/
A4.4.2 Deionized or Distilled Water, free from inter- NaHCO3 solution in the bomb, place the cover on the bomb,
ferences at the minimum detection limit of each constituent and vigorously shake for 15 s to distribute the solution over
and filtered through a 0.2-␮m membrane filter to avoid the inside of the bomb. Open the bomb, place the sample-
plugging columns. filled sample cup in the terminal holder, and insert a short
A4.4.3 Eluant Solution, sodium bicarbonate-sodium length of thread between the firing wire and the sample.
carbonate, 0.003M NaHCO3− 0.0024M Na2CO3: dissolve The sample weight used should not exceed 1 g. If the
1.008 g NaHCO3 and 1.0176 g Na2CO3 in water and dilute sample is a solid, add a few drops of white oil at this time
to 4 L. to ensure ignition of the sample.
464
--`,,```,,,,````-`-`,,`,,`,`,,`---

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

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

may cause corrosion of the bomb. To avoid this it is recommended that
for samples containing over 2% chlorine, the sample weight be based on
the following:
Chlorine Sample
Content, Weight, White Oil
% g Weight, g separation achieved in Fig. A4.1 (2 to 3 mL/min). Adjust
2 to 5 0.4 0.4
detector to desired setting (usually 10 ␮mho) and let system
5 to 10 0.2 0.6 come to equilibrium (15 to 20 min). A stable base line
10 to 20 0.1 0.7 indicates equilibrium conditions. Adjust detector offset to
20 to 50 0.05 0.7 zero-out eluant conductivity; with the fiber suppressor
CAUTION: Do not use more than 1 g total of sample and white oil
adjust the regeneration flow rate to maintain stability, usu-
or other fluorine-free combustible material.
ally 2.5 to 3 mL/min.
A4.5.2 Addition of Oxygen — Place the sample cup
A4.6.1.1 Set up the ion chromatograph in accor-
in position and arrange the nylon thread, or wisp of cotton
dance with the manufacturer’s instructions.
so that the end dips into the sample. Assemble the bomb
and tighten the cover securely. Admit oxygen (Caution, A4.6.2 Calibration — Inject standards containing a
Note A4.4) slowly (to avoid blowing the sample from the single anion or a mixture and determine approximate reten-
cup) until a pressure is reached as indicated in Table A4.1. tion times. Observed times vary with conditions but if
standard eluant and anion separator column are used, reten-
NOTE A4.4: Caution — Do not add oxygen or ignite the sample if the
bomb has been jarred, dropped, or tilted. tion always in the order F−, Cl−, NO2−, PO43−, Br−, NO3−,
and SO42−. Inject at least three different concentrations for
A4.5.3 Combustion — Immerse the bomb in a cold-
each anion to be measured and construct a calibration curve
water bath. Connect the terminals to the open electrical
by plotting peak height or area against concentration on
circuit. Close the circuit to ignite the sample. Remove the
linear graph paper. Recalibrate whenever the detector set-
bomb from the bath after immersion for at least 10 min.
ting is changed. With a system requiring suppressor regen-
Release the pressure at a slow, uniform rate such that the
eration, NO2− interaction with the suppressor may lead to
operation requires not less than 1 min. Open the bomb and
examine the contents. If traces of unburned oil or sooty erroneous NO2− results; make this determination only when
deposits are found, discard the determination, and thor- the suppressor is at the same stage of exhaustion as during
oughly clean the bomb before again putting it in use. standardization or recalibrate frequently. In this type of
system the water dip (see Note A4.4) may shift slightly
A4.5.4 Collection of Solution — Remove the sample
during suppressor exhaustion and with a fast run column
cup with clean forceps and rinse with deionized water and
this may lead to slight interference for F− or Cl−. To elimi-
filter the washings into a 100-mL volumetric flask. Rinse
nate this interference, analyze standards that bracket the
the walls of the bomb shell with a fine stream of deionized
expected result or eliminate the water dip by diluting the
water from a wash bottle, and add the washings through
sample with eluant or by adding concentrated eluant to the
the filter paper to the flask. Next, rinse the bomb cover
sample to give the same HCO3−/CO32− concentration as in
and terminals and add the washings through the filter into
the eluant. If sample adjustments are made, adjust standards
the volumetric flask. Finally, add deionized water to bring
and blanks identically.
the contents of the flask to the line. Use aliquots of this
solution for the ion chromatography (IC) analysis. NOTE A4.5: Water dip occurs because water conductivity in sample is
A4.6 Procedure less than eluant conductivity (eluant is diluted by water).
A4.6.1 System Equilibration — Turn on ion chroma- A4.6.2.1 If linearity is established for a given
tograph and adjust eluant flow rate to approximate the detector setting, it is acceptable to calibrate with a single
465 --`,,```,,,,````-`-`,,`,,`,`,,`---

standard. Record the peak height or area and retention time TABLE A4.2
to permit calculation of the calibration factor, F. PRECISION AND ACCURACY OBSERVED FOR ANIONS
AT VARIOUS CONCENTRATION LEVELS IN REAGENT
A4.6.3 Sample Analysis — Remove sample particu- WATER
lates, if necessary, by filtering through a prewashed 0.2-
␮m-porediam membrane filter. Using a prewashed syringe Single-
Amount Amount Overall Operator Significant
of 1 to 10 mL capacity equipped with a male luer fitting Added, Found, Precision, Precision, Bias 95%
inject sample or standard. Inject enough sample to flush Anion mg/L mg/L mg/L mg/L Level
sample loop several times: for 0.1 mL sample loop inject
at least 1 mL. Switch ion chromatograph from load to F− 0.48 0.49 0.05 0.03 No
F− 4.84 4.64 0.52 0.46 No
inject mode and record peak heights and retention times Cl 0.76 0.86 0.38 0.11 No
on strip chart recorder. After the last peak (SO42−) has Cl− 17 17.2 0.82 0.43 No
appeared and the conductivity signal has returned to base Cl 455 471 46 13 No
line, another sample can be injected. NO2 0.45 0.09 0.09 0.04 Yes, neg
NO2 21.8 19.4 1.9 1.3 Yes, neg
A4.6.4 Regeneration — For systems without fiber Br− 0.25 0.25 0.04 0.02 No
suppressor regenerate with 1 N H2SO4 in accordance with Br− 13.7 12.9 1.0 0.6 No
the manufacturer’s instructions when the conductivity base PO43− 0.18 0.10 0.06 0.03 Yes, neg
PO43− 0.49 0.34 0.15 0.17 Yes, neg
line exceeds 300 ␮mho when the suppressor column is NO3− 0.50 0.33 0.16 0.03 No
on line. NO3− 15.1 14.8 1.15 0.9 No
SO42− 0.51 0.52 0.07 0.03 No
A4.7 Calculation SO42− 43.7 43.5 2.5 2.2 No
A4.7.1 Calculate concentration of each anion, in mg/
L, by referring to the appropriate calibration curve. Alterna-
tively, when the response is shown to be linear, use the F p response factor − concentration of standard/
following equation: height (or area) of standard, and
D p dilution factor for those samples requiring
CpHⴛFⴛD dilution.
A4.8 Precision and Bias
where:
A4.8.1 Samples of reagent water to which were
C p mg anion/L, added the common anions were analyzed in 15 laboratories
H p peak height or area, with the results shown in Table A4.2.
--`,,```,,,,````-`-`,,`,,`,`,,`---
466

Se 165

Uploaded by

Copyright:

Available Formats

Se 165

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Se 165

Uploaded by

Copyright:

Available Formats

ARTICLE 24, SE-165 2007 SECTION V

STANDARD TEST METHOD FOR

(Identical with ASTM Specification E 165-02)

1. Scope the responsibility of the user of this standard to establish

Copyright ASME International

E 1316 Terminology for Nondestructive Examinations TABLE 1

7.2 Penetrants: 7.4 Solvent Removers function by dissolving the pene-

Copyright ASME International

FIG. 3 SOLVENT-REMOVABLE PENETRANT EXAMINATION GENERAL PROCEDURE FLOWSHEET

Dwell TimesA (minutes)

NOTE 14: Caution — Avoid overwashing. Excessive washing can cause

Copyright ASME International

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

Copyright ASME International

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

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

Copyright ASME International

A2.7.6 Precision and Accuracy: A3.4 Apparatus

Copyright ASME International

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

Copyright ASME International

Copyright ASME International

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

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

Copyright ASME International

You might also like