10/7/2010

5.2 API 578 Positive Material

Identification (PMI)
• Objectives and methodologies (e.g. X-Ray
Fluorescence and Optical Emission Spectroscopy)
– ASTM- E1916
– Pipe Fabricator Institute PFI-ES42
– API 578
– MSS SP-137-2007
– Material Test Reports

Positive Material Identification

(PMI) Testing
• Any physical evaluation or test of a material to
confirm that the material which has been or will be
placed into service is consistent with the selected or
specified alloy material designated by the owner/user.
• These evaluations or tests may provide qualitative or
quantitative information that is sufficient to verify the
nominal alloy composition.
composition

N. Al-Khirdaji, AZTech Sr. Consultant 1

 10/7/2010

Positive Material Identification (PMI)

• It is critically important for workers in inspection,
safety and maintenance departments in refineries,
safety, refineries
petrochemical, process, power and other industrial
plants to prevent the accidents that can occur as a
result of the installation of incorrect or out-of-
specification metal alloy parts.
• With Positive Material Identification (PMI) the alloy
composition and so, the identity of materials can be
determined/verified.

Positive Material Identification (PMI)

• As a result of a series of accidents resulting
from material mix
mix-ups,
ups many companies have
instituted stringent Positive Material
Identification (PMI) programs.
• Industry organization has also worked to
develop guidelines to assure that the nominal
compositions of all alloy components in a
process system are consistent with design
specification.

N. Al-Khirdaji, AZTech Sr. Consultant 2

 10/7/2010

OSHA Regulations and PMI 1/2

• Inspection Scheduling by OSHA: All Refineries –
Section E-10
E 10
– It should be noted that both PMI and proper OPERATOR
TRAINING programs are QUESTIONS that the
Compliance Safety and Health Officer (CSHO) will
address to the Owner/Operator as to compliance with their
Process Safety Management (PSM) program.
– Does
D the
h employer
l ensure that
h replacement
l piping
i i isi
suitable for its process application?
Yes, No, N/A

OSHA Regulations and PMI 2/2

• If no, possible violations include:
– The employer
p y did not ffollow Recognized
g z And Generallyy
Accepted Good Engineering Practice (RAGAGEP) when
it failed to conduct Positive Material Identification (PMI)
testing to ensure that construction materials of
replacement/repaired piping were adequate for process
conditions. Examples RAGAGEP for PMI testing for
existing piping systems include but is not limited to,
• API RP 578, Material Verification Program for New
and Existing Alloy Piping Systems, Section 4.3, and
• CSB, Safety Bulletin – Positive Material Verification:
Prevent Errors During Alloy Steel Systems
Maintenance, BP Texas City, TX Refinery Fire;

N. Al-Khirdaji, AZTech Sr. Consultant 3

 10/7/2010

Recognized And Generally Accepted

Good Engineering Practice (RAGAGEP)
• “Recognized And Generally Accepted Good
Engineering Practice”
Practice (RAGAGEP) - are
engineering, operation, or maintenance activities
based on established codes, standards, published
technical reports or recommended practices (RP) or a
similar document.
• RAGAGEPs detail generally approved ways to
perform specific engineering,
engineering inspection or
mechanical integrity activities, such as fabricating a
vessel, inspecting a storage tank, or servicing a relief
valve

Regulatory Compliance
Positive Material Identification (PMI)
• Does the employer ensure that replacement piping
is suitable for its p
process application?
pp
– Yes, No, N/A
• If no, possible violations include:
– The employer did not follow RAGAGEP when it failed to
conduct Positive material identification (PMI) testing to
ensure that construction materials of replacement/repaired
piping were adequate for process conditions (An example
RAGAGEP for PMI testing for existing piping systems
includes but is not limited to, API RP 578, Material
Verification Program for New and Existing Alloy Piping
Systems, Section 4.3), and CSB, Safety Bulletin – Positive
Material Verification: Prevent Errors During Alloy Steel
Systems Maintenance, BP Texas City, TX Refinery Fire);

N. Al-Khirdaji, AZTech Sr. Consultant 4

 10/7/2010

Approximate Hardness of Steel

By the File Test

File Reaction Brinell Hardness Type of Steel

File bites easily into metal 100 BHN Mild Steel
File bites into metal with 200 BHN Medium carbon steel
pressure
File does not bite into metal 300 BHN High carbon steel
except with extreme pressure High alloy steel
Metal can only be filed with 400 BHN Unhardened tool steel
difficulty
File will mark metal but 500 BHN Hardened tool steel
metal is almost as hard as the
file and filing is impractical
Metal is harder than file 600+ BHN

Metal Identification – Spark Test

N. Al-Khirdaji, AZTech Sr. Consultant 5

 10/7/2010

PMI Standards
• ASTM E1916
Standard Guide for Identification and/or Segregation of Mixed Lots of
Metals
American Society of Testing Material /1997 , reaffirmed 2004

• MSS SP-137-2007 - Quality Standard for Positive Material

Identification of Metal Valves, Flanges, Fittings, and Other Piping
Components
Edition: 1st
Manufacturers Standardization Society / 01-May-2007
This Standard Practice provides methods and acceptance standards for
Positive Material Identification (PMI) of metal flanges, fittings, valves, and
pressure boundary parts of valves and other piping components.

• PFI ES42 - Standard for Positive Material Identification of Piping

Components Using Portable X-Ray Emission Type Test Equipment
Pipe Fabrication Institute / 01-Oct-1996

PMI Standards
• API R P 578
Material Verification Program for New and
Existing Alloy Piping Systems
American Petroleum Institute / May 1999

N. Al-Khirdaji, AZTech Sr. Consultant 6

 10/7/2010

PMI Standards – API RP 578

SCOPE
• This recommended practice provides the guidelines for
material control and material verification programs on ferrous
and nonferrous alloys during the construction, installation,
maintenance, and inspection of new and existing process
piping systems covered by the ASME B31.3 and API 570
piping codes.
• This practice applies to metallic alloy materials purchased for
use either directly by the owner/user or indirectly through
vendors, fabricators, or contractors and includes the supply,
fabrication, and erection of these materials.
• Carbon steel components specified in new or existing piping
systems are not specifically covered under the scope of this
document.

PMI Standards – API RP 578

ROLES AND RESPONSIBILITIES
• A material verification program for piping systems may
involve participation of several groups within the operating
plant or the shop of a contractor, vendor, or fabricator.
• When establishing a material verification program,
consideration should be given to the roles and responsibilities
that each group has within the specific organization.
• These roles and responsibilities should be clearly defined and
d
documented. d Within
Wi hi theh operating
i plant,
l this
hi can include
i l d those
h
groups responsible for purchasing, engineering,
warehousing/receiving, operations, reliability, maintenance,
and inspection

N. Al-Khirdaji, AZTech Sr. Consultant 7

 10/7/2010

PMI Standards – API RP 578

• Carbon Steel Substitutions in Low Alloy Steel
Systems
– In determining the likelihood of material nonconformances,
it is worth noting that historically the greatest number of
material nonconformances with serious consequences have
involved carbon steel components in low alloy steel
– (e.g., 1 ¼ Cr– ½ Mo, 2 ¼ Cr–1 Mo, 5 Cr– ½ Mo, 9 Cr–1
M ) piping
Mo) i i systems. There
Th have h been
b relatively
l i l fewer
f
nonconformances in stainless steel and nonferrous (e.g.
Monel, Inconel) systems because of appearance and
weldability issues.

PMI Standards – API RP 578

• Alloy Substitutions In Carbon Steel Systems
– Wh
When determining
d t i i the
th needd to
t perform
f material
t i l verification
ifi ti
on carbon steel systems, the owner/user should evaluate the
effect that the process stream could have on substituted
alloy materials.
– In some cases, the substitution of hardenable alloy
materials in carbon steel piping systems resulted in failure
and loss of containment.
containment Examples of such systems include
wet hydrogen sulfide (H2S), hydrofluoric acid (HF), and
sulfuric acid (H2S04) services

N. Al-Khirdaji, AZTech Sr. Consultant 8

 10/7/2010

PMI Standards – API RP 578

• Some Highlights
– PMI Testingg of W Welding gCConsumables - W When weldingg is
conducted, one electrode or wire sample from each lot or
package of alloy weld rod should be positively identified.
The remainder of the lot should be compared to the sample
to verify that the markings of the wires/electrodes are
correct
– Maintenance Repairs of Piping Systems - It is important
that repair procedures include consideration of PMI testing
as part of obtaining satisfactory alloy materials to be used
for the repair
– Material Certifications - Material certifications, mill test
reports, or Certificates of Compliance should not be
considered a substitute for PMI testing, but may be an
important part of an overall quality assurance program

Positive Material Identification (PMI)

• Positive Material Identification (PMI) is one
off the
th more specialized
i li d non-destructive
d t ti
testing (NDT) methods.
• There are two methods for PMI:
1. The XRF-principle (x-ray fluorescence)
2 Optical emission systems (OES),
2. (OES) also called
arc/spark

N. Al-Khirdaji, AZTech Sr. Consultant 9

 10/7/2010

PMI Methods - XRF

1. The X-Ray Fluorescence Technique XRF
• XRF iinstruments
t t workk by
b exposing
i a sample
l to
t
a beam of X-rays.
– The atoms of the sample absorb energy from the X-
rays, become temporarily excited and then emit
secondary X-rays.
– Each chemical element emits X-rays y at a unique
q
energy. By measuring intensity and characteristic
energy of the emitted X-rays, an XRF analyzer can
provide qualitative and quantitative analysis regarding
the composition of the material being tested.

PMI Methods - OES

2. The Optical Emission Spectroscopy Technique OES
• In the OES technique
technique, atoms also are excited; however,
however
the excitation energy comes from a spark formed between
sample and electrode.
– The energy of the spark causes the electrons in the sample to
emit light, which is converted into a spectral pattern.
– By measuring the intensity of the peaks in this spectrum, the
OES analyzer can produce qualitative and quantitative analysis
off th
the material
t i l composition.
iti
• Although OES is considered a non-destructive testing
method, the spark does leave a small burn on the sample
surface

N. Al-Khirdaji, AZTech Sr. Consultant 10

 10/7/2010

PMI Methods - OES

Optical Emission Spectrography – A spark is released
that vaporizes a very small portion of the sample (without
impairing its functionality).

The analyzer optically

measures the atoms in the
vapor and
d determines
d t i the
th
components of the material.

“Spectro” metal analyzer

XRF Excitation Model

X-ray fluorescence (XRF) spectrometry is an elemental analysis technique
with broad application in science and industry. XRF is based on the principle
that individual atoms, when excited by an external energy source, emit X-ray
photons of a characteristic energy or wavelength.

The identification of elements by

X-ray methods is possible due to
the characteristic radiation emitted
from the inner electronic shells of
the atoms under certain conditions.
The
h emitted
i d quanta off radiation
di i are
X-ray photons whose specific
energies permit the identification of
their source atoms.

By counting the number of photons of each energy emitted from a sample, the
elements present may be identified and quantified.

N. Al-Khirdaji, AZTech Sr. Consultant 11

 10/7/2010

Optical Emission Analyzer

Optical Emission analyzer designed to identify all the key elements in metals -
especially
p y where highest
g accuracy
y and/or the analysis
y of light
g elements like C,,
Al, S, P, Mg, Si is needed and when sorting low alloys and aluminums. Ideal,
for example, for separation of 316 H (>0.04% C) and 316 L (<0.03% C).

ARC-MET 8000 Optical Emission Analyzer.

Case Study 1 – Chlorine Transfer Hose

Failure
– On August 14, 2002, a 1-inch transfer line
ruptured during a railcar offloading operation at
DPC Enterprises in Festus, Missouri and released
48,000 pounds of Chlorine into neighboring area.
– Safety Bulletin from U.S. Chemical Safety and
Hazard Investigation Board (CSB)-Chlorine
Transfer Hose Failure due to improper material
braid construction (i.e.,316L and not the
recommended braid of Hastelloy C-276).

N. Al-Khirdaji, AZTech Sr. Consultant 12

 10/7/2010

PMI Testing
The elements of the basic alloy materials to be verified should be
in accordance with Table below:

Basic Alloy Elements to be Verified

Carbon-Molybdenum, Manganese
Molybdenum, and Chromium
Molybdenum steels
Nickel steels
Regular carbon grade stainless steels
Low carbon stainless steels
Low-carbon
Stabilized stainless steels
Nickel-based alloys
Copper-based alloys
Chromium and Molybdenum
Nickel
Chromium, Nickel, and Molybdenum
Chromium Nickel,
Chromium, Nickel Molybdenum
Molybdenum, and Carbon
Chromium, Nickel, Molybdenum, Titanium and
Niobium
Nickel, Iron, Copper, Chromium, and
Molybdenum
Copper, Zinc, and other elements specified in
purchase order or SAMS catalog description

X-Ray Fluorescence (XRF) Analyzer

When an electron beam of high energy strikes a material, one of the
results of the interaction is the emission of photons which have a
broad continuum of energies. This radiation, called bremsstrahlung.

N. Al-Khirdaji, AZTech Sr. Consultant 13

 10/7/2010

Component Identification
• The ASME B31.3 Code requires random
examination
i ti off materials
t i l andd components t to
t
ensure conformance to listed specifications
and standards.
• B31.3 also requires these materials to be free
from defects.
• Component standards and specifications have
various marking requirements.

Material Verification And

Traceability
• During repairs or alterations alloy material piping
systems WHERE THE ALLOY MATERIAL IS
systems,
REQUIRED TO MAINTAIN PRESSURE
CONTAINMENT, the inspector shall verify that the
installation of new materials is consistent with the
selected or specified construction materials.
• This material verification program should be
consistent with API RP 578,
578 Material Verification
Program for New and Existing Alloy Piping Systems.

N. Al-Khirdaji, AZTech Sr. Consultant 14

 10/7/2010

Case Study 1: Failure of A Slurry Recycle

Line in a Delayed Coker – Canada 1984
• Failure of a slurry recycle line in a delayed coker unit
in Canada in 1984.
The line was specified to be NPS 6, schedule 40
ASTM A 335 grade P5 (UNS K41545) seamless pipe
having a nominal composition of 5% chromium and
½% molybdenum.
• The line contained oil with sulfur compounds and
coke particles at a temperature of 705 °F (374 °C)
and a pressure of 240 psig (1(1.66
66 MPa)
MPa).
• The line split longitudinally, showering the unit with
hot oil and causing a fire to spread through the unit
resulting in a half dozen additional pipe failures

Case Study 1: Failure of A Slurry Recycle

Line in a Delayed Coker – Canada 1984
The fire was traced to
the rupture of a 16-in.
(406-mm) long section
of carbon steel, shown
in Figure, that had
been welded into the
line approximately
fi years previously.
five i l

The carbon steel section had a thickness of only 0.090 to 0.125 in.
(2.3 to 3.2 mm) prior to the failure while the adjacent pipe was
between 0.250 and 0.260 in. (6.4 to 6.6 mm) thick.

N. Al-Khirdaji, AZTech Sr. Consultant 15

 10/7/2010

Case Study 1: Failure of A Slurry Recycle

Line in a Delayed Coker – Canada 1984
Figure below is a longitudinal metallographic section of one of the
girth welds at the end of the carbon steel section illustrating the
abrupt change in wall thickness between the carbon steel section
and the adjacent 5% chromium steel pipe and weld.

Safety Bulletin - U.S. Chemical Safety

and Hazard Investigation Board (CSB)
Positive Material Verification: Prevent Errors During
Alloy Steel Systems Maintenance
• The U.S. Chemical Safety and Hazard Investigation Board
(CSB) issues this Safety Bulletin to focus attention on
process equipment configuration control and positive
material verification of critical alloy steel piping
components.
• The CSB recommends
e e d th
thatt the refining,
efi i petrochemical,
et he i l andd
chemical industries review material verification programs
to ensure that maintenance procedures include sufficient
controls and positive material identification (PMI) testing
to prevent improper material substitutions in hazardous
process systems.

N. Al-Khirdaji, AZTech Sr. Consultant 16

 10/7/2010

Case Study 2: Material Verification Error

• On July 28, 2005, the BP Texas City refinery
experienced
i d a major
j fire
fi in
i the
th Resid
R id
Hydrotreater Unit (RHU) that caused a
reported $30 million in property damage.
• One employee sustained a minor injury during
the emergency unit shutdown and there were
no fatalities.

Case Study 2: Material Verification Error

The RHU incident investigation determined that an 8-inch diameter
carbon steel elbow inadvertently installed in a high-pressure, high-
temperature hydrogen line ruptured after operating for only 3 months.
months
The escaping hydrogen gas from the ruptured elbow quickly ignited.

Carbon steel RHU heat exchanger outlet pipe (arrow) ruptured after operating only
3 months in high-temperature hydrogen service.

N. Al-Khirdaji, AZTech Sr. Consultant 17

 10/7/2010

Case Study 2: Material Verification Error

• This incident occurred after a maintenance contractor
accidentally switched a carbon steel elbow with an
alloy steel elbow during a scheduled heat exchanger
overhaul in February 2005.
• The alloy steel elbow was resistant to high
temperature hydrogen attack (HTHA) but the carbon
steel elbow was not.
not Metallurgical analyses of the
failed elbow concluded that HTHA severely
weakened the carbon steel elbow.

Case Study 2: Material Verification Error

Dimensionally identical piping elbows on RHU heat exchangers A and B.

N. Al-Khirdaji, AZTech Sr. Consultant 18

 10/7/2010

Case Study 2: Material Verification Error

Ruptured 8-inch carbon steel pipe elbow pieces recovered after the fire

Case Study: Material

Verification Error

RHU hydrogen heat exchanger

piping material requirements.

N. Al-Khirdaji, AZTech Sr. Consultant 19

 10/7/2010

API RP 578: Material Verification Program for

New and Existing Alloy Piping Systems
• Provides guidelines for a material quality assurance system to
verify the consistency between the nominal composition of alloy
components t within
ithi the
th pressure envelop
l off a process piping
i i
system with the selected or specified construction materials to
minimize the potential for catastrophic release of toxic or
hazardous liquids or vapors.
• Presents material control and verification programs on ferrous
and nonferrous alloys during construction, installation,
maintenance, and inspection of new and existing process piping
systems covered under the ASME B31.3 and API 570 codes.
• Applies to metallic alloy materials purchased for use by the
owner/user or indirectly through vendors, fabricators, or
contractors, and includes the supply, fabrication and erection of
these materials.
• Carbon steel components specified in new or existing piping
systems are not covered under the scope of this document.

Positive Material Identification (PMI)

• The ASME B31.3 Code requires random
examination
i ti off materials
t i l andd components t to
t
ensure conformance to listed specifications
and standards.
• B31.3 also requires these materials to be free
from defects.
• Component standards and specifications have
various marking requirements.

N. Al-Khirdaji, AZTech Sr. Consultant 20

 10/7/2010

Markings – Pipe
Standard Title and Marking Requirements
Pipe, Steel, Black and Hot-Dipped, Zinc Coated, Welded and
Seamless
ASTM A53 1. Name of Brand of Manufacturer
2. Kind of Pipe (e.g. ERW B, XS)
3. Specification Number
4. Length
Seamless Carbon Steel Pipe for High-Temperature Service
1. Marking requirements of A530/A530M
2. Heat Number
3. Hydro/NDE
y Marking
g
ASTM A106 4. “S” for supplementary requirements as specified (stress-relieved
annealed tubes, air underwater pressure test, and stabilizing
heat treatment)
5. Length
6. Schedule Number
7. Weight on NPS 4 and larger

Markings – Flanges & Flanged Fittings

Standard Title and Marking Requirements

ASME B16.5 Pipe Flanges and Flanged Fittings

1. Manufacturer’s Name or Trademark
2. ASTM Specification and Grade
3. Rating Class
4. “B16”
5. Size
ASME B16.36 Orifice Flanges Classes 300, 400, 600, 1500 and 2500
1 Fl
1. Flanges shall
h ll b
be marked
k d as required
i dbby ASME B16
B16.55
2. For welding neck flanges only, the bore diameter shall be
marked.

N. Al-Khirdaji, AZTech Sr. Consultant 21

 10/7/2010

Markings – Fittings
Standard Title and Marking Requirements
Factory Made Wrought Steel Buttwelding Fittings
Factory-Made
1. Manufacturer’s Name or Trademark
2. Material and Product Identification (ASTM or ASME grade
ASME B16.9 symbol).
3. “WP” in grade symbol.
4. Schedule number or nominal wall thickness.
5. NPS

Forged Fittings, Socket-Welding and Threaded

1. Manufacturer’s Name or Trademark.
2 M
2. Material
t i l id
identification
tifi ti iin accordance
d with
ith th
the appropriate
i t ASTM
ASTM.
ASME B16.11 3. Product conformance symbol, either “WP” or “B16”.
4. Class designation - 2000, 3000, 6000, or 9000. Where size and
shape do not permit all of the above markings, they may be
omitted in the reverse order given above

Markings - Fasteners
Standard Title and Marking Requirements
Specification for Alloy-Steel and Stainless Steel Bolting Materials for High-
Temperature Service
ASTM 193 1.Grade or manufacturer’s identification symbols shall be applied to one end of studs
3/8” in diameter and larger and to the heads of bolts ¼ ” in diameter and larger.

Specification for Carbon and Alloy Steel Nuts for Bolts for High-Pressure and
High-Temperature Service
ASTM 194 1.Manufacturer’s identification mark.
2.Grade and process of manufacture (e.g. 8F indicates nuts that are hot-forged or
cold-forged)
Specification for Carbon Steel Bolts and Studs
ASTM 307 1.Manufacturer’s identification mark.
2.All bolt heads, one end of studs 3/8” and larger, and whenever feasible studs less
than 3/8”, shall be marked with a grade material.
Specification for Carbon and Alloy Steel Nuts
1.Grades O, A, and B are not required to be marked unless identified as such by the
purchaser.
ASTM 563 2.Grade D, DH, DH3 shall be marked with the symbol HX3 on one face. Heavy hex
nuts made to the requirements of DH3 are marked with HX3 on one face.
3.Grades C, C3, D, DH, and DH3 and hex nuts made to the requirements of DH3,
are marked with the manufacturers symbol.

N. Al-Khirdaji, AZTech Sr. Consultant 22

 10/7/2010

Metal Analyzers
Positive Material Identification (PMI) refers to the identification and
analysis of various metal alloys based on their chemical composition
in non-destructive testing (NDT). Measurement results are shown in
the form of elemental concentration in percentage or by specific
alloy name such as SS316L or Inconel 625. PMI is a field-testing
method made possible by the portability of most PMI analyzers.

The two main technologies used for alloy

identification in PMI are:
X-ray Fluorescence (XRF), and
Optical Emission Spectroscopy (OES)

Innov-X Portable XRF Metal Analyzer

Spark Emission Spectrometer –

PMI-MASTER SORT (Oxford)
The PMI-MASTER is a portable universal spectrometer for alloy sorting. The
instrument provides a quick and precise analytical overview of all common
materials with a Fe, Al, Cu, Ni, Ti and CO base.
The instrument source works with a high-frequency spark in argon or a direct
current arc in air. The respective excitation mode can be selected according to
application and can be changed easily.

Depending upon the

requirements, the instrument
offers three different operation
modes;
• sorting;
• Grade ID; and
• complete analysis of metals.

N. Al-Khirdaji, AZTech Sr. Consultant 23

 10/7/2010

CSB Bulletin – Failure Due to

Improper Material
August 14, 2002, a 1-inch transfer line
ruptured during a railcar offloading operation
at DPC Enterprises in Festus, Missouri and
released 48,000 pounds of Chlorine into
neighboring area.
Safety Bulletin from U.S. Chemical Safety and
Hazard Investigation Board (CSB)-Chlorine
Transfer Hose Failure due to improper
material braid construction (i.e., 316L and
not the recommended braid of Hastelloy
C-276 as specified by DPC).
The CSB also recommended that the hose
fabricator implement a materials’ verification
procedure to improve quality and ensure that
Hastelloy chlorine hoses are readily identifiable

Example: PMI on Type 304 SS Sample

Using NITON XRF Analyzer
Sample: SS 304
Cert 5 Sec +/- 20 Sec +/-
Grade ID 304 304
Cr 18.31 18.36 0.32 18.39 0.14
Ni 9.52 9.57 0.45 9.55 0.21
Mn 1.73 1.81 0.30 1.80 0.14
Mo 0.38 0.40 0.03 0.40 0.01
W 0.13 0.14 0.10 0.13 0.05

NITON XRF instruments report a two-sigma precision along with the result for
each element. This represents an error band of two standard deviations on either
side of the result. The two sigma precision represents a 95 % confidence interval
for the data. Note the precision, or +/- error band, is not an indication of accuracy,
but a measurement of repeatability around a most probable value. Accuracy must
be assessed by comparing the measured result and precision to known values
from a reference standard.

N. Al-Khirdaji, AZTech Sr. Consultant 24