A Discussion Regarding a Novel Method:The Use of

X-Ray Fluorescence

for

Quantitative Analysis of Elements in Carpet

Deborah Lema, Racine Industries May 26, 2010

SUMMARY

Ranking carpet cleaning events is deemed important by the carpet industry so that it may answer thequestion, “what is the most effective way to clean my carpet?” Being able to answer this question withreasonable certainty would be good customer service and could potentially reduce the amount of warrantyclaims.With this in mind, Professional Testing Laboratory (PTL) worked with a manufacturer of x-rayspectrometry (XRF) equipment to develop a novel testing method for use by the carpet industry’s tradeassociation: Carpet and Rug Institute. The intention was to quantify soil levels in carpet in order to testand rank carpet cleaning events, and the “…hope (is) that this test will be adopted as a standard for cleaning performance.”

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Carpet and Rug Institute (CRI) has put PTL’s new way of using XRF into commercial application viatheir Seal of Approval program. The use of products that have “passed” testing at PTL has been made arequirement not only in some carpet warranties, but also in some third-party environmental certificationsand legislation. Therefore, carpet owners, professional cleaners and cleaning product manufacturers aremore inclined to have a heightened interest in the Seal of Approval.However, considering the potential health implications and fiscal ramifications of relying on this testmethod for decision making, the author suggests that more work needs to be completed. The testingmethod has not yet been validated, demonstrated relevant to its intended purpose, and no precision,accuracy or bias statements may be made

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. An independent peer review has not beenaccomplished. Those affected by this testing would feel more confident if it was externally validated, andif the laboratory-generated results were demonstrated via an independent third party to be relevant to thequestion of how to best clean a “real world” carpet. For instance, do extractors used in the field performthe same as they do in the lab when they are facing actual trafficked carpet with real soils containingsoluble and oily components?This paper briefly discusses some of the technical considerations involved in the novel PTL testingmethod, and looks at some potential areas for more work to be done if the Carpet and Rug Institute Sealof Approval program hopes to be a robust program with practical impact in which consumers and theindustry can have confidence.

The author would like to give special thanks to the numerous XRF experts and/or reviewers who gavetheir time and input on this topic, and in some cases even lent their staff and equipment for experimentation. Note: In an effort to remain faithful to some of the original sources used in this document, I have purposefully maintained at times an inconsistency between standard International System (SI) units and non-SI units.

A Discussion Regarding a Novel Method

BACKGROUND AND INTRODUCTION

Previous methods used in attempts to measure and rank carpet cleaning events have been shown to beunreliable and not wholly useful. Gravimetric methods, weighing samples before and after cleaning, arenot reproducible and can’t control for variables that would affect the results (such as cleaning residues or fiber loss). Spectrophotometry, measuring the light intensity change of the surface of the carpet beforeand after cleaning, only gives a clue to the color change on the tops of the fibers and not what may be below. Hence, the desire for a way to measure soil in a carpet.X-ray fluorescence is an element detection method with various technological iterations that have been inuse for many years and in many fields of study. The particular instrument used in the PTL testing is the portable TRACeR II: a small, energy-dispersive XRF model. Simply stated, the XRF instrument sendsout energy and software displays spectra reflecting the detected photons counts coming in. These spectrashow intensities versus energies, i.e., how many photons are counted from each detected element.The testing incorporates the use of XRF to try to determine which vacuums, extractors and cleaningsystems remove a higher percentage of elements than others*. After a soiling process and brushing, andin some cases vacuuming, three carpet samples are scanned in order to calculate concentrations of soil. If the three concentrations are found to be within 20% of each other, the samples are consideredsuccessfully prepared and testing may continue. Each sample is then cleaned, left overnight or so to dry,and is scanned for 180 seconds

†

(3 minutes) from a small distance, with the portable XRF device mountedin a stand over a moving conveyor with a jig, scanning 120 square inches or so of the 400 square inchmoving sample at 1.3 meters per minute

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.In order to assign a comparable “score” to a cleaning event, the calculated level of soil after cleaning iscompared to the calculated level of soil before cleaning. Results are given as percentages rather thanquantities, since the PTL method cannot determine accurate amounts of the compounds and because of “possible variations i(n) starting concentrations”

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. While the method does not discern exactly how muchsoil is in any given sample, the method developers state that the

percentages

between cleaned anduncleaned samples are accurate

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and therefore are useful to compare and rank cleaning events. Productseither fail, or receive a bronze, silver, gold or platinum rating depending on their assigned removal percentages.The testing treats a cleaning event as one independent variable that changes nothing about the sampleexcept for the amount of soil. However, a cleaned carpet through the eyes of XRF has experienced morechanges than just the amount of soil, and these changes affect the ability of XRF to create comparable andrankable data.The changes from a cleaning event that may affect XRF data include:

•

Distribution and location of remaining soils

•

Concentration of remaining soils and inter-element interference

•

Moisture content

See an overview of the process online athttp://www.carpet-rug.org/media/SOA_XRF/SOA_XRF.wmv. Note thatthe NASA-enhanced model shown in the beginning of this video is not the actual model used for cleaning eventtesting.

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In addition to this scan time, it has also been stated

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that five scans lasting 36 seconds each (rather than onelonger scan) may be performed. While this adds up to the same amount of time (180 seconds), this would probablychange the data acquired, as well as the precision calculations.

A Discussion Regarding a Novel Method

•

Yarn arrangement, distance and densityThe cleaning process is actually a number of variables. Each of these variables would be different for every kind of cleaning event, and each of these variables adds a different level of uncertainty, variation, or error to the data. If the variables between cleaning events are consistent, they could perhaps be“subtracted out”. If, however, they are

not

consistent, then there are simply too many uncontrollable andunpredictable variables for this testing method to be quantitatively useful. Therefore, a closer look at thedifferent variables would be worthwhile.

DISCUSSION

In order for XRF to be useful as a quantitative tool, certain prerequisites must be met. These prerequisitesinclude proper equipment and method calibration and proper sample preparation

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Further, any newtesting method should be compared—validated—against an already established one.

CALIBRATION

In practical application, XRF is a comparative method. In other words, an XRF device has to be shownsomething (a reference, or standard) with an already-known quantity so that it has something to comparefuture samples to. This process is calibration, and is in essence a series of programming steps. Adjustingone’s watch, for instance, is calibrating it to a more reliable reference; without that reference, one cannotreliably tell the time. The more thorough the calibration, the more useful and trustworthy themeasurements are. It is calibration that turns an XRF spectrometer from a radiation measuring deviceinto an analytical tool.A reliable calibration model uses references that are representative of the sample and soil concentrationranges

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and it is vital that all references and unknowns be presented to the spectrometer in a reproducibleand identical manner

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. A reference used for calibration must represent the sample to be analyzed; itmust have the same morphology (structure and form) characteristics as the sample would. Thesecharacteristics include particle size, distribution, surface condition, density, and homogeneity (i.e. even blending throughout). A reliable calibration model also includes controlling the measurement geometry

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, because when the distance and geometry change, so does the data. (See also SAMPLE DISTANCEAND GEOMETRY, below.)Since there is no certified calibration reference available for carpet, a calibration reference for this testing purpose was created. This was done by first reading compound-coated nylon pellets and normalizing thesignal

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. The pellets are then used to soil a carpet sample, and then are picked out and scanned again

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. The difference between the starting fluorescence intensity from the pellets and the intensity from the picked-out pellets after carpet soiling is assumed to be the concentration of each compound transferred tothe carpet sample. Using the assumed concentrations from the pellet scans, carpet samples soiled with asingle compound each are then scanned to complete the calibration.It may be argued that this calibration procedure does not meet the prerequisites for a reliable calibrationmodel, as the pellets are not representative of carpet, nor is XRF used the same way in the pelletcalibration procedures as is it on the carpet samples. For instance, the pellets used are a different shapeand density than carpet yarns, and have different chemical and surface characteristics. Further, thecompound distribution is different and the distance away from the XRF gun is different. The pellets arealso scanned for a different amount of time than the carpet samples, the number of averaged scans is

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The signal is normalized for Compton backscattering, which helps reduce variation

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