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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

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-ofspecification 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

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 is i 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 f follow Recognized g z And Generally y 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

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 process application? pp is suitable for its p
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

10/7/2010

Approximate Hardness of Steel By the File Test


File Reaction
File bites easily into metal File bites into metal with pressure File does not bite into metal except with extreme pressure Metal can only be filed with difficulty File will mark metal but metal is almost as hard as the file and filing is impractical Metal is harder than file

Brinell Hardness
100 BHN 200 BHN 300 BHN 400 BHN 500 BHN

Type of Steel
Mild Steel Medium carbon steel High carbon steel High alloy steel Unhardened tool steel Hardened tool steel

600+ BHN

Metal Identification Spark Test

N. Al-Khirdaji, AZTech Sr. Consultant

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

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 the h 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

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 Cr Mo, 2 Cr1 Mo, 5 Cr Mo, 9 Cr1 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 need d 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

10/7/2010

PMI Standards API RP 578


Some Highlights
PMI Testing g of W Welding gC Consumables - W When welding g 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 of f 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

10/7/2010

PMI Methods - XRF


1. The X-Ray Fluorescence Technique XRF XRF i instruments t t work k by b exposing i a sample l to t a beam of X-rays.
The atoms of the sample absorb energy from the Xrays, 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 of f 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

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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 of f 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.

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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

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PMI Testing
The elements of the basic alloy materials to be verified should be in accordance with Table below:
Basic Alloy 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 Elements to be Verified 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.

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Component Identification
The ASME B31.3 Code requires random examination i ti of f materials t i l and d 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.

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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 % 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

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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 that t the refining, efi i petrochemical, et he i l and d 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.

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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, hightemperature 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

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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

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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

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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 of f 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 of f materials t i l and d 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

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Markings Pipe
Standard Title and Marking Requirements Pipe, Steel, Black and Hot-Dipped, Zinc Coated, Welded and Seamless 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 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 ASTM A53

ASTM A106

Markings Flanges & Flanged Fittings


Standard ASME B16.5 Title and Marking Requirements Pipe Flanges and Flanged Fittings 1. Manufacturers Name or Trademark 2. ASTM Specification and Grade 3. Rating Class 4. B16 5. Size Orifice Flanges Classes 300, 400, 600, 1500 and 2500 1 Fl 1. Flanges shall h ll b be marked k d as required i db by ASME B16 B16.5 5 2. For welding neck flanges only, the bore diameter shall be marked.

ASME B16.36

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Markings Fittings
Standard Title and Marking Requirements Factory Made Wrought Steel Buttwelding Fittings Factory-Made 1. Manufacturers Name or Trademark 2. Material and Product Identification (ASTM or ASME grade symbol). 3. WP in grade symbol. 4. Schedule number or nominal wall thickness. 5. NPS Forged Fittings, Socket-Welding and Threaded 1. Manufacturers Name or Trademark. 2 M 2. Material t i l id identification tifi ti i in accordance d with ith th the appropriate i t ASTM ASTM. 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

ASME B16.9

ASME B16.11

Markings - Fasteners
Standard Title and Marking Requirements Specification for Alloy-Steel and Stainless Steel Bolting Materials for HighTemperature Service 1.Grade or manufacturers identification symbols shall be applied to one end of studs 3/8 in diameter and larger and to the heads of bolts in diameter and larger. Specification for Carbon and Alloy Steel Nuts for Bolts for High-Pressure and High-Temperature Service 1.Manufacturers 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 1.Manufacturers 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. 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. ASTM 193

ASTM 194

ASTM 307

ASTM 563

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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

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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 Grade ID Cr Ni Mn Mo W 18.31 9.52 1.73 0.38 0.13 5 Sec 304 18.36 9.57 1.81 0.40 0.14 0.32 0.45 0.30 0.03 0.10 +/20 Sec 304 18.39 9.55 1.80 0.40 0.13 0.14 0.21 0.14 0.01 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

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