You are on page 1of 12

Saudi Aramco

Inspection Department

Positive Material Identification

The training materials contained in this module are the property of the Saudi Arabian Oil Company (Saudi Aramco) and are intended for the exclusive use of Saudi Aramco employees enrolled in advanced inspection training courses. Any material contained in this manual which is not already in the public domain, may not be copied, reproduced, sold, given or disclosed to third parties or otherwise used, in whole or in part, for purposes other than for use in Saudi Aramcos Professional Engineering Development Unit courses without the prior written permission of the Chief Engineer of Saudi Aramco

Positive Material Identification


Positive material identification (PMI) is a powerful methodology for assuring that manufacturing companies operate with greater profit, more efficiency, and the highest possible levels of safety. The requirement for PMI of alloy materials in refinery systems and petrochemical plant operations has grown dramatically from the late 1970s when it was a rarity, to nearly 100% PMI in todays risk-based QC environment The consequences of using the wrong material in a process plant can range from costly to disastrous, and may involve loss of plant property, loss of production capacity, and loss of life. Compared to 1990 vintage PMI tools, the latest hand-held, battery-operated, field portable X-ray fluorescence (FP-XRF) analyzers (Fig. 1) are about five times smaller, five times faster, and half the price, and are equivalent to lab-based XRF in terms of performance. A recently introduced model has all but eliminated routine maintenance costs as well.

Figure 1 Modern PMI tools

The Need for PMI


As an example of the critical need for PMI the inadvertent substitution of a carbon steel elbow in a 5Cr- 1/2Mo alloy steel piping system resulted in a premature rupture due to hot sulfide corrosion, which led to a major fire at a Louisiana refinery in 1993 . These types of incidents are more prevalent than generally assumed and have led to the adoption of FP-XRF for PMI of incoming plant replacement parts such as pipes, valves, fittings, pressure vessels, and welding materials. In high-risk services, 100% inspection of materials is generally required. Until recently, replacement parts could only be tested at ambient or room temperature. Now, however, the capability to test materials at elevated temperatures tip to 1000F (543 C) is possible. With this new capability, parts in service can be tested during plant operation. This form of testing is referred to as retrospective positive mate rials identification or RPMI. The key advantage of RPMl is that incorrect parts can be detected and the correct parts ordered for replacement during the next plant shutdown. This provides savings to facility operation by reducing the time required for turn arounds, and has the potential for saving many months of operation under potential As a result, most every petrochemical process plant in developed countries has established a mandate to perform PMI. The PMI cycle extends to such diverse requirements as analysis of supplier materials of construction (at the suppliers facility), incoming materials, in-stock materials, in-process materials at the operating plant itself, and, finally, to the salvage of used material for recycling (Fig. 2)

Figure 2 The PMI cycle

Field portable XRF


Field portable X-ray fluorescence (FP-XRF) is a technique for quickly determining, often in-situ, that the correct alloy has been used for the intended application. Over the past decade, PMI testing tools have been miniaturized, field hardened, and improved in performance to the point where they are now comparable, for PMI purposes, to taking the laboratory to the field. These tools can be effectively used to accurately evaluate alloy grades based on their elemental composition. The technology will assist in determining whether a given component or part is in accordance with drawings and specifications, or whether it should be flagged as out of spec. Today. FP-XRF is widely used to identify incorrect materials during PM! of incoming fabricated components, as well as in-service and in-stock materials. Positive material identification may be performed in the plant or in the field under a wide range of operating environments, including ambient temperatures ranging from 20 to 120 F (-7 to 49C), rain, dust, magnetic fields, acoustical noise, surface vibration, and extreme sample surface temperatures, up to 1000F (543C) Fig. 3.

Figure 3 High temperature accessory

How FP-XRF Works

When the FP-XRF tool is placed on an alloy component and a measurement initiated, the process of analyzing the alloy composition and determining the alloy grade is accomplished as follows: The trigger is activated, moving aside an internal radiation shield allowing a lowenergy beam of X rays to illuminate the alloy sample surface. Electrons of elements in the alloys are exposed to the X-ray beam and are temporarily raised to an excited state. In the process of nearly instantaneous de-excitation, these atoms emit characteristic fluorescent X rays Fig. 4A. Each of the X rays emitted by the alloy samples atoms possess a well-defined energy a characteristic X-ray energy that is unique for each element present. The corresponding intensity of these characteristic X rays is proportional to the concentration of a given element in the sample Fig. 4B. Therefore, by measuring both the energy and intensity of the characteristic X-rays from a sample, both the element and its percentage concentration can he determined.

Figure 4A X-Ray production Atomic level (A)

Figure 4B Macro level (B)

XRF Is Both Qualitative and Quantitative


A FP-XRF Instrument can provide both quantitive (what elements are present) and quantitative (percent composition of these elements) analysis. In the past, FP-XRF analyzers traditionally employed up to three radioisotopes contained in small capsules; these isotopes were used as primary radiation sources for excitation of a sample.

X-ray Excitation Source Options


Today, the newest FP-XRF analyzers come with two different source excitation options. The first uses a single isotope for X-ray excitation and the other uses an electronic tube. The configuration with only one isotope uses a specially packaged 241Am to excite the full range of elements that previously required three isotopes. This single-isotope version simplifies the design, improves reliability, reduces the measurements required from three to one, eliminates periodic source replacements due to short half-life considerations (241Am has a 433 year half-life), and eliminates source decay as an operational consideration since measurements never slow down in compensation for weakening source output Mother added advantage is that the source never needs replacement, which eliminates routine maintenance costs.

The second configuration of FP-XRF analyzers uses a tube-excited X-ray source. This configuration shares the advantage of the isotope-excited X-ray source in that only a single measurement is required. It is also usually subject to fewer regulatory considerations than isotope-based instruments. The only disadvantage of the tubeexcitation approach is the cost of eventual replacement of the tube, which has a finite lifetime of service

The Detector
A semiconductor detector receives the fluoresced X rays and converts them to electronic signals. This information is then passed to the electronics and microprocessor, which analyzes and displays the alloy composition and grade identification data to the operator Fig. 5.

Figure 5 Diagram of Si PIN detector

Alloy Analysis by XRF


Alloys of primary use in refinery and petrochemical operations are chromiummolybdenum steels, stainless steels, and some nickel-based alloys such as the HastelloysTM and lnconelsTM. Carbon steels are less resistant to corrosion, but are less costly and have good utility in low-corrosion operating environments. Carbon steels are applicable to portable XRF by generic category only, e.g., 1010, 1020, 1030, etc.; all carbon steel grades will be classified generically as C-Steel. Often, only 2025 alloy grades comprise the entire need in a typical refinery or related-type process plant. Note that FP-XRF is not universally applicable to all alloys and all alloying elements. Figure 6 is an example of alloys used in a typical petrochemical operation. Of the 22 alloys shown in Fig. 7, 20 are possible to positively identify with the FP-XRF analyzer. Note that the 304 vs. 304L and 316 vs. 316L differ only in carbon content. These Lgrade alloys cannot be separated with any portable XRF analyzer, and so will be identified simply as either 304 or 316.

Figure 6

Compensation for Detector, Electronic, and Other Sources of Drift


All XRF analyzers offer software for the analysis of the X-ray spectrum obtained by the instruments detector. Some instruments require an empirical calibration or frequent standardization due to detector instabilities, electronic drift, or isotope decay. Others with more robust programming eliminate these (often-neglected) chores by automatically compensating for any source of drift.

Compensation for Alloy Sizes, Shapes, and Access


Additional software features include the ability to analyze small, irregular objects such as small-diameter pipes and tubes, welding rods, small bolts, flanges, and complex shaped valves. Some analyzers provide optional attachments for analysis of hot surfaces. Some have a geometry that lends them to testing in tight spaces (including corner or fillet welds) Fig. 7.

Figure 7 Example of access to a fillet weld

Testing Time
Typical testing times may run from a few seconds to 20 seconds, depending on several factors including the particular analyzer iii use, the excitation source, the alloy sample itself (both composition and! size), and the standard operating procedure (SOP) in use by the instrument operator. Some providers of PMI tools provide a generic SOP for PMI at petrochemical operations. These procedures can be easily adapted to each operation with generally only minor changes.

10

The Testing Process


To initiate a test, the operator places the instrument (or instrument probe) on the surface to be analyzed and either pulls a trigger or pushes a button to open a safety shutter. This process also activates the electronics and the system begins acquiring spectral data. Results are displayed on an LCD screen, and generally include both the chemical composition and the common trade name of the identified alloy grade. This information is stored for subsequent download to a PC, and includes any additional identifying criteria input by the operator including: sample name, operator name, lot number, vendor name, etc. The time and date of each test are also contained in the downloaded information. Some analyzers can also display and download the full X-ray energy spectra for documentation purposes Fig. 8.

Figure 8 Test results A- X-ray energy spectra B display readout

XRF Is Nondestructive
X-ray fluorescence analysis is completely nondestructive to the component being tested, with little or no sample preparation required. Analyzers come equipped with a preprogrammed alloy library of the few hundred most commonly used alloy grades for identification, which may then be modified or supplemented by the end user.

11

Modes of Operation
The most advanced instruments provide at least three different analysis modes. The alloy mode performs an analysis for a variable period of time dependent upon the user depressing the instrument trigger (the longer the test, the greater the precision). As the instrument receives X rays from the sample, it performs the necessary calculations, and displays both the percent concentrations of alloying elements and the grade ID of the alloy. A second available mode of operation is the spectral match mode, sometimes referred to as fingerprint mode. In this mode, the operator first builds a library of alloys in the instrument memory by collecting (measuring) X-ray spectra of known standards. and storing each spectral fingerprint into the instrument along with its grade name. The instrument can then be used to test the unknown samples against the library of stored fingerprints for rapid match determinations. In this mode, an unknown alloy can be identified in as little as in two to three seconds, allowing a large number of parts to be rapidly sorted in a short period of time. A third mode is a type standardization mode, or as one popu lar provider terms it, a SuperChem mode. In this mode, the unknown alloy is first identified then compared to a stored set of data for the specific grade. Based on the stored intensity data, the exact chemistry can be determined, including compensation for light-element content not directly detectable with the FP-XRF. This mode provides the most accurate and comprehensive results when particularly rigorous testing is required

PMI Reduces Cost


Even routine plant operating costs can be reduced by performing in-service inspection. This gives needed alloy composition information necessary to prioritize and schedule replacement prior to temporary plant shutdown, and allows any required replacement components to be prefabricated. Turnaround surprises are subsequently reduced. Field portable XRF is also used to verify material on new construction sites. As a result, petrochemical companies have developed rigorous PMI programs, and FPXRF analyzers have become the PMI tools of choice. If a potential failure or reduction in performance can be predicted early enough, there are direct savings in plant and equipment costs as well as avoidance of harm to personnel. In addition, there is potentially a much greater savings through reducing production losses due to piping and component failures.

12