Analysis of Food for Contamination - Shimadzu...the possibility of matrix effects can and will affect instrumentation. It is vital that any XRF spectrometer have built in spectrographic

RaynyEDX-700/800 Application Data

Analysis of Food for Contamination

Application Number: AsCdKAsEDX-700/80051 Description In order to provide a benefit to public health concern, Arsenic has been tested in a variety of contaminated food products. As part of an ongoing Japanese mandate, to accurately test foods, the EDX provides a solution for testing if a food product contains as low as 0.5 ppm (and below) of Arsenic. Using a number of x-ray beam filters, the EDX 700/800 is able to increase the signal to noise ratio of the As signal.

Application Data The following four (4) figures show various spectrums of Arsenic in differing concentrations. In addition the benefit of using a primary beam filter is shown in Figure 4. Notice how the spectrum is greatly enhanced through the use of a Ni beam filter.

Figure 1. 0.39% Arsenic in Oolong Tea. Figure2. 0.35% Arsenic in Orange Juice

Figure 3. 0.39% of Arsenic in Curry Figure 4. 10 ppm As, viewed with and

without a Ni filter. Notice the Signal to Noise Enhancement.

Result Summary Quantitative Accuracy: Samples were made with 0.39% As. Semi-quantitative results, without the use of standards showed the following results.

Element Oolong Tea Juice Curry As H2O

0.39% 99.61%

0.35% 99.65%

0.33% 99.67%

Minimum Detection Limits: The minimum detection limit of Arsenic with and without filters is shown in Table 1.

Measurement Times

With Ni Filter Without Filter

40 Seconds 0.9 ppm 2.0 ppm 100 Seconds 0.6 ppm 1.3 ppm 1000 Seconds 0.19 ppm 0.4 ppm

Measuring Conditions :

Instrument : EDX-700 X-ray Tube : Rh Filter : Ni or Without Atmosphere : Air

Power: 50 kV at 15 µA Dead Time 25% Measurement Diameter 10 mm Measurement Time 40 Seconds

RaynyEDX-700/800Application Data

Analysis of Low-Alloy Steel

Application Number: Steel-MX-700-1

DescriptionSteel analysis is a particularly good application for XRF. The bulk, of the material, ratherthan the surface is measured, sample preparation is often easy, or non-existent. The rangeof elements reported by EDXRF is also very useful for the XRF analyst. With any sample,the possibility of matrix effects can and will affect instrumentation. It is vital that anyXRF spectrometer have built in spectrographic corrections, such as those used by theEDX-700/800, to account for these matrix affects. These exist when a spectral line isclose to another spectral line, or absorption edge. Often times this causes one spectral lineto enhance the production of another line, limit the production, or even overlap theexisting line. This application note will demonstrate the EDX 700/800 and its ability tocorrect for these matrix effects and produce accurate data. In addition samples areanalyzed in a “Standardless configuration”, and the accuracy of the results are shownbelow.

Application DataA spectrum from a stainless steel standard: ST01-1ST-10-110, is shown below, alongwith the corresponding semi-quantitative analysis.

Fig. 1. Spectrum of Sc - Tu

Fig. 2. Spectrum of Na – Sc Fig. 3. Spectrum Zoom of Cr, V, Mn, and Fe. Notice thesevere overlapping. The EDX-700, can resolve thesepeaks, and correctly determine quantitative information.

Fig.1 Qualitative Analysis of ST07-1

Table 1 Quantitative Value of Certified Standard ST07-1 by FP MethodFe Ni Cr Mn Mo Ti Si Cu

Measured Value(%) 94.47 1.78 1.15 1.02 0.46 0.25 0.25 0.19Certified Value(%) -- 2.02 0.98 1.01 0.59 0.17 0.38 0.20

S Ta V Pb P Zr NbMeasured Value(%) 0.12 0.12 0.094 0.048 0.033 0.016 0.008Certified Value(%) 0.025 0.068 0.10 0.010 0.033 0.010 0.008

Matrix CorrectionIn any inter-elemental mixture, the emission of x rays from each element are inter-related.For instance, in Steel, the x rays from Fe, will excite the Chromium atoms to fluoresce,more than they would in the absence of Fe. This enhancement, or secondary effect is anexample of the need for a Matrix correction. Other inter-elemental effects includeabsorption, and most notably in EDXRF, overlapping. The test of a good EDXRFquantitative data processor, is its ability to correct for these matrix effects. The EDX-800,with built in matrix corrections, quickly and easily corrects for overlapping, enhancementand absorption effects. A number of calibration lines are shown below. The followinglegend applies to these graphs.

-- Before Matrix Correction-- After Matrix Correction

.

. 05

. 1

. 15

0 0. 05 0 . 1 0 . 15

Concent r a t i on( wt %)

Intensity(cps/uA)

0

5

10

0 1 2 3

Concent r at i on( wt %)

Intensity(cps/uA)

Fig. 4. Calibration Line of Sulfur. Fig. 5. Calibration Line of Manganese

.

. 05

. 1

0 0. 4 0 . 8


Intensity(cps/uA)

0

2

4

6

0 2 4


Intensity(cps/uA)

Fig. 6. Calibration Line of Silicon Fig. 7. Calibration Line of Nickel

- 0 . 1

0 . 1

0 . 3

0 . 5

0 . 7

0 . 9

1 . 1

1 . 3

1 . 5

0 0 . 4 0 . 8

Co n c e n t r a t i o n ( wt % )

0

0 . 5

1

1 . 5

0 0 . 0 4 0 . 0 8 0 . 1 2

Con c e n t r a t i o n ( wt % )

Fig. 8. Calibration Line of Copper Fig. 9. Calibration Line of Niobium

Table 2. Summary of Inter-elemental effects in SteelAnalyte Mn S Cu NiInterferingElement

Cr Mo Mo, Ni Cr

Type ofInterference

Overlap Overlap Absorption andEnhancement

Absorption andEnhancement

Discussion of ResultsAs shown in Figures 4 through 9, matrix effects can significantly effect the linearity of acalibration curve. The EDX-700/800 software, easily removes all matrix effects presentin a steel matrix. There are generally 4 recognized choices of matrix corrections in thespectroscopy community. The choice an analyst makes, would be based on the type ofinterference, and the range of calibration. It is important that quantitative softwareincorporates all types of corrections, many analytical laboratories use more than one typeof correction. The EDX-700/800 software included as a standard feature, contains thefour (4) most widely recognized algorithms for automatic matrix correction. In addition,each element can have multiple calibration curves, depending upon which concentrationrange is being addressed. In this way, hi and low concentration ranges can be addressed.It is important that the analyst have these powerful tools available to completely addressall types of inter-elemental effects that may be present in even routine analysis. Measuring Conditions :

Instrument : EDX-700X-ray Tube : RhFilter : NoneAtmosphere : Air

Power: 15 - 50 kV at 15 - 200 µADead Time 25%Measurement Diameter 10 mmMeasurement Time 300 Seconds


EDXRF Analysis of Orchard Leaves

Application Number: Orchid-EDX700-11199

DescriptionOrchid leaves are used to determine the accuracy of XRF instruments in evaluating traceelements. The orchard leaf, is particularly useful, in extracting a range of elements in theppm level from the surrounding soil. The orchard leaves used here come from NISTCertified Reference Materials (NIST-SRM Program), and are verified by variousmethods, including wet chemistry.

Application DataA number of XRF spectrums are obtained from NIST-SRM-1751, certified OrchardLeaves from the National Institute of Science and Technology. The results are shownbelow. In addition, using “Peak Fitting” methods, the sample is analyzed for elementalconcentrations along with Fundamental Parameters. The result, an accurate quantitativeanalysis of all inorganic elements present in the leaves.

Fig. 1. Spectrum of Orchid Leaves (Mn Kα to Rh Kβ : 5 keV to 24 keV)

Fig. 2. Spectrum of Orchid Leaves (Mg Kα to Ca Kβ : 0.50 keV to 5 keV). Notice theability of the peak fitting software to resolve the K Kβ line and the Ca Kα line.

Table 1 Quantitative Value of NIST 1571 Orchard Leaves by FP Method

Ca K Mg P S Si Fe MnMeasured Value (%) 2.149 1.648 0.769 0.213 0.205 0.167 0.032 0.010Certified Value (%) 2.090 1.470 0.620 0.210 0.190 -- 0.030 0.009

Accuracy (%) 0.059 0.178 0.149 0.003 0.005 -- 0.002 0.001Pb Cu Sr Zn Rb N C6H10O5

Measured Value (%) 0.009 0.004 0.004 0.004 0.002 -- 94.785Certified Value (%) 0.005 0.001 0.004 0.003 0.001 2.76 --

Accuracy (%) 0.004 0.003 0.000 0.001 0.001 -- --


Instrument : EDX-700X-ray Tube : RhFilter : NoneAtmosphere : Vacuum



Analysis of Ceramics

Application Number: AsCdKAsEDX-700/80051

DescriptionIn this application note, Ceramic powder is analyzed for a wide elemental range.Elements present in a Ceramic are often present in the form of oxides. Various oxides inceramics are measured in two ways. The first, a standardless approach, uses fundamentalparameters to provide elemental content. The second approach, purely empirical, createsa calibration line based on the intensity emitted from each element for a number ofstandards. These two methods are compared. It is very clear from the results, that in manycases fundamental parameters can be a very accurate method of analyzing an unknownsamples. The ceramic powder, is created from a pre-existing ceramic bulk by means of asample grinder available from either Kratos or Spex Certiprep.

Semi-Quantitative AnalysisThe following are spectrum from a certified ceramic standard, R-603, available fromShimadzu, Japan.

Fig. 1. Spectrum of Oxides in Ceramic Powder Fig. 2. Al2O3, and SiO2, spectrum in CeramicPowder

The results in Table 1, shows the ability of Shimadzu’s Fundamental Parameter softwareto quantitatively analyze, an unknown sample, without the use of standards.

SiO2 Al2O3 CaO Fe2O3 K2O Na2O MgO TiO2

Measured Value(%) 46.6 37.2 1.69 0.60 0.42 0.34 0.31 0.09Certified Value(%) 46.1 37.0 1.66 0.65 0.40 0.84 0.29 0.08

SO3 MnO CuO Ga2O3 PbO ZnO Rb2O Ignition LossMeasured Value(%) 0.05 0.03 0.01 0.005 0.005 0.003 0.002 12.60Certified Value(%) ----- ------ ------ ------ ------ ------ ------ ------

Table1. Comparison of Semi-Quantitative results to Certified Elemental Concentration.

Quantitative AnalysisAlthough, the Fundamental Parameter method is very accurate in determining elementalconcentration, it is often beneficial to use an empirical method. There can be manyreasons for using an empirical approach. Most notably, is accuracy. An empirical methodalmost always provides the user with a higher accuracy. This is often due to physicaldifferences between sample lots, such as particle size.

Many times, analysis, is required to conform to an ISO-900x regulation. In this case,Quality Control (QC) procedures are required to be documented. Due to the complexnature of the FP method, this is not always possible, and if it is, often it is notstraightforward. An empirical method, as used on the EDX-700/800 reports, to the user, acomplete set of parameters associated with each Quantitative method. These results areclearly understood by the user and can be used for ISO-900x documentation.

The figures below show examples of empirically created calibration lines that are usedfor oxides measured in ceramic analysis.

2

6

10

14

18

40 60 80 100Concent r a t i on( wt %)

Intensity(cps/uA)

0 . 0

0 . 2

0 . 4

0 . 6

0 . 8

1 . 0

1 . 2

1 . 4

0 0 . 2 0 . 4 0 . 6 0 . 8


Intensity(cps/uA)

Fig. 3. Calibration Line for SiO2 Fig. 4. Calibration Line for TiO2

0

0. 5

1

1 . 5

2

2 . 5

3

3 . 5

4

4 . 5

0 4 8 12


Intensity(cps/uA)

0

0 . 1

0. 2

0. 3

0. 4

0. 5

0. 6

0. 7

0. 8

0. 9

0 0. 6 1. 2 1. 8

Concent r at i on( wt %)

Intensity(cps/uA)

Fig. 5. Calibration Line for K2O Fig. 6. Calibration Line for CaO

Repeatability of ProcedureThe samples were measured a number of times, n = 10, to determine the precision of theanalysis tool. There are two values associated with a precision measurement. The first, isstandard deviation, and is the absolute precision of the instrument. The second value, thecoefficient of variation, is the relative precision of the instrument. The results, for R-603(certified ceramic standard), are shown below in Table 2.

Table 2 Result of Repeatability Test for R-603Compound SiO2 Al2O3 Fe2O3 TiO2 CaO MgO Na2O K2OAverage(%) 47.10 36.89 0.67 0.099 1.62 0.22 0.67 0.41

StandardDeviation(%)

0.061 0.150 0.004 0.004 0.010 0.015 0.091 0.010

Coefficient ofVariation(%)

0.13 0.41 0.61 4.0 0.60 7.7 13.7 2.5



Power: 15-50 kV at 30 - 250 µADead Time 25%Measurement Diameter 10 mmMeasurement Time 40 Seconds


Analysis of Food Products for ContaminationApplication Number: CdAsKcn-80051-700-2

Description:In order to provide a benefit to public health concern, Toxic elements and compoundshave been tested in a variety of contaminated food products. As part of an ongoingJapanese mandate, to accurately test foods, the EDX provides a solution for testing if afood product contains as low as 0.5 ppm (and below) of Arsenic. Using a number of x-ray beam filters, the EDX 700/800 is able to increase the signal to noise ratio of specificelements.

Application DataThe following five (5) figures show various spectrums of elements in differingconcentrations. In addition the benefit of using a primary beam filters are shown. All ofthese spectrum are acquired with the use of a primary beam filter. Notice how thespectrums are greatly enhanced through the use of a beam filter.

Fig.1 Qualitative and Quantitative nalysisof Oolong Tea Mixed KCN. This spectrumis obtained using an Aluminum Filter.

Fig. 2 Qualitative Analysis of pure OolongTea. This spectrum is obtained using anAluminum Filter

Fig.3 Qualitative and QuantitativeAnalysis of Oolong Tea Mixed KCN withNo Filter

Fig.4 Qualitative and QuantitativeAnalysis of Oolong Tea Mixed Cd.

Fig.5 Qualitative and Quantitative analysisof Oolong Tea with and without anAluminum Filter

Result Summary

Detection Limits

Element MeasurementTime

Al Filter Al Filter inVacuum

No Filter

K 40 Seconds 88 ppm 49 ppm 120 ppmK 100 Seconds 56 ppm 31 ppm 76 ppmK 1000 Seconds 18 ppm 10 ppm 24 ppm


Instrument : EDX-700X-ray Tube : RhFilter : Ni, Al, and ZrAtmosphere : Air or Vacuum

Power: 50 kV at 15 – 400 µADead Time 25%Measurement Diameter 10 mmMeasurement Time 40 Seconds


Analysis of Pharmaceutical Products

Application Number: CM-2299-K

DescriptionIn this application note, the EDX-700/800 is applied towards analysis of a cold tablet. Inthis report, the range of elements that can be identified and quantified is shown. Inaddition, the repeatability of this procedure is shown by measuring a tablet a number oftimes.

Sample PreparationWith the EDX-700/800, there is no need for sample preparation. The tablet is simplyplaced on commercially available sample holders. This is shown below in Figure. 1.

Fig. 1. Analysis of a Pharmaceutical Product OftenRequires no Sample Preparation

Application DataThe following are two spectrum acquired by the EDX 800.

Fig. 2. Spectrum of Na through Ca Fig. 3. Spectrum of Br.

Quantitative Results

The data in Table1, shows the quantitative results of the Cold Tablet, by standardlessanalysis.

Table 1 Quantitative Value of Pharmaceuticals by FP MethodSi Cl Na Br S Mg P Ca C8H9NO2

Measured Value(%)

0.98 0.46 0.12 0.10 0.079 0.035 0.026 0.011 98.19

Precision ResultsThe elements in the tablet were measured for repeatability. This provides the analyst withthe precision they will expect to obtain once using the EDX 700/800 in their analyticallaboratory.

Table 2 Repeatability of Quantitative Value(%)Cl Br

Average(%)Standard Deviation(%)

Coefficient of Variation(%)

0.464 0.0070 1.5

0.103 0.00063 0.61




Fields:Pharmaceuticals, Agriculture, Food Product

EDXRF Analysis of Brewer’s Yeast PreparationEDXRF Analysis of Brewer’s Yeast PreparationEDXRF Analysis of Brewer’s Yeast PreparationEDXRF Analysis of Brewer’s Yeast Preparation

Various minerals are included in brewer’s yeast preparation, and it is thus used as a nutritional supplement as well. With EDX the qualitative and quantitative analysis of the constituent minerals in these tablets can be achieved simply and conveniently. We have given an example of such analysis below. ■■■■SampleSampleSampleSample

A brewer’s yeast preparation(tablet) commonly available on the market was analyzed. ■■■■Sample PreparationSample PreparationSample PreparationSample Preparation The tablet was affixed to adhesive tape without any prior preparation of the sample. A photograph showing the condition in which the sample is analyzed in shown in Fig.1 ■■■■Result of Qualitative AnalysisResult of Qualitative AnalysisResult of Qualitative AnalysisResult of Qualitative Analysis The result of the qualitative analysis of the brewer’s yeast preparation is shown in Fig.2.

Fig.1 Sample Loading

Fig.2 Qualitative Analysis of Brewer’s Yeast Preparation

RaynyRaynyRaynyRayny EDXEDXEDXEDX----700/800700/800700/800700/800 Application Data No.7Application Data No.7Application Data No.7Application Data No.7

Sample Pressure Sensitive-Tape

Sample Holder Analytical Surface

■■■■Effect of the Effect of the Effect of the Effect of the Zr FilterZr FilterZr FilterZr Filter By using the filter effectively, the scattering of the primary X-rays from the X-ray tube can be reduced to achieve an analysis with a good S/N ratio. In the instance Cl and Sr was detected using the filter. The result of this qualitative analysis is shown inFig.3.

Element detected Cl Al Filter Sr Ni Filter (In addition to this the EDX-700/800 comes equipped with Zr, Ti and polymer filters as standard)

Fig.3 Qualitative Analysis of Brewer’s Yeast Preparation using Filters

■■■■Result of Quantitative AnalysisResult of Quantitative AnalysisResult of Quantitative AnalysisResult of Quantitative Analysis The quantitative analysis result arrived at by the FP method from the qualitative analysis results shown in table 1. Note that in the quantitative

calculations the major was assume to be protein(amino acid) and used as the balance(residue).

Table 2 Quantitative Value of Medicun by FP Method

K P Ca Si S Mg Na Cl Cu Quantitative Value(%) 2.70 1.46 0.98 0.68 0.23 0.23 0.21 0.11 0.002

Reference Value(%) 1.900 1.600 0.260 -- -- 0.250 0.162 -- 0.0003

Fe Zn Sr C2H5NO2 Quantitative Value(%) 0.009 0.006 0.001 93.38

Reference Value(%) 0.0066 0.0048 -- Protein etc.

■■■■Analytical Conditions Instrument : EDX-800 X-ray Tube : Rh target Filter : not used, Al, Ni Voltage - Current : 50kV-17～31μA(Auto) 15kV-240～565μA(Auto) Atmosphere : Vacuum Measurement Diameter : 10mmφ Measuring Time : 300sec Dead Time : 25～26%

RhLα

RhLβ1

Rayny Rayny Rayny Rayny ApplicationApplicationApplicationApplication DataDataDataData No. 7 No. 7 No. 7 No. 7

Fields: Environment, Chemical Industry

EDXRF Analysis of Vehicle Exhaust ParticulatesEDXRF Analysis of Vehicle Exhaust ParticulatesEDXRF Analysis of Vehicle Exhaust ParticulatesEDXRF Analysis of Vehicle Exhaust Particulates

As environmental awareness grows steadily, research into exhaust emissions from sources such as factories and vehicles which cause air and environmental pollution has gained in importance. Particles separated and collected from exhaust gases, or collected on filter paper, can be simply and conveniently analyzed with EDX. Shown below is an example of a qualitative and quantitative analysis of vehicle exhaust particlates. ■■■■SampleSampleSampleSample

The standard environmental sampleThe standard environmental sampleThe standard environmental sampleThe standard environmental sample NIES(National Institute for Environmental Studies) No.8 “Vehicle Exhaust ParticulatesVehicle Exhaust ParticulatesVehicle Exhaust ParticulatesVehicle Exhaust Particulates” was analyzed. ■■■■Sample PreparationSample PreparationSample PreparationSample Preparation Using a vinyl chloride ring, the sample was

pressed into shape under a total pressure of 10t applied for 10 seconds. ■■■■Result of qualitative AnalysisResult of qualitative AnalysisResult of qualitative AnalysisResult of qualitative Analysis

The result of the qualitative analysis of the vehicle exhaust particlates is shown in Fig.1. By using an Al filter the presence of Cl has been detected(Bottom left graph).

Fig.1 Qualitative Analysis of Vehicle Exhaust Particulates

RaynyRaynyRaynyRayny EDXEDXEDXEDX----700/800700/800700/800700/800

Application Data No.8Application Data No.8Application Data No.8Application Data No.8

With Al Filter

■■■■Result of Quantitative AnalysisResult of Quantitative AnalysisResult of Quantitative AnalysisResult of Quantitative Analysis

The result of the quantitative analysis derived by the FP method from the qualitative analysis result on the previous page is indicated in Table 1 together

with the standard values. Note that in the quantitative calculations the major was assumed to be carbon(C) and used as the balance(residue).

Table 1 Quantitative Value of Vehicle Exhaust Particulates by FP Method

Element QuantitativeValue(%)

Standard Value(%)

Deviation(%)

11 Na 12 Mg 13 Al 14 Si 15 P 16 S 17 Cl 19 K 20 Ca 22 Ti 23 V 24 Cr 25Mn 26 Fe 28 Ni 29 Cu 30 Zn 35 Br 38 Sr 82 Pb

0.171 0.022 0.163 0.793 0.052 1.837

0.042 0.080 0.456 0.028 0.006 0.004 0.006 0.302 0.003 0.006 0.069 0.004 0.005 0.015

0.192 0.101 0.330 0.051 0.085 0.115 0.530 0.027 0.002 0.003 0.008 0.490 0.002 0.007 0.104 0.006 0.009 0.022

-0.021 -0.079 -0.167 0.001 -0.043 -0.035 -0.074 0.001 0.004 0.001 -0.002 -0.188 0.001 -0.001 -0.035 -0.002 -0.004 -0.007

■■■■Analytical Conditions Instrument : EDX-700 X-ray Tube : Rh target Filter : not used Voltage - Current : 50kV-17μA(Auto) 15kV-175μA(Auto) Atmosphere : Vacuum Measurement Diameter : 10mmφ Measuring Time : 600sec Dead Time : 25～26% ■■■■ReferenceReferenceReferenceReference Standard Environmental Sample NIES No.8 “Vehicle Exhaust Particulates” – The Preparation, Analysis, and Guaranteed Quality of the Vehicle Exhaust Particulate Standard Sample – National institute for Environmental Studies Measurement Technology, Mr.Kensaku Okamoto. Article extracted from the Environmental Studies Quarterly 1987 No.66. Published September 1987. Environmental Research Center(incorporated foundation) Issue.

Rayny Rayny Rayny Rayny Application Data No. 8Application Data No. 8Application Data No. 8Application Data No. 8

Fields: Chemical Industry, Electric/Magnetic Materials

EDXRF Analysis of Polymer Film:EDXRF Analysis of Polymer Film:EDXRF Analysis of Polymer Film:EDXRF Analysis of Polymer Film: Determination of Thickness, Determination of Both Thickness and Concentration Determination of Thickness, Determination of Both Thickness and Concentration Determination of Thickness, Determination of Both Thickness and Concentration Determination of Thickness, Determination of Both Thickness and Concentration

Shimadzu’s original “Background FP Method” (hereafter referrd to as te “BG-FP method”) is efective for

determining the thickness of polymer films such as polyethylene and polyester. This method incorporates X-ray scattering theory calculation into the FP method. By applying the principle that the intensity of the Comptom scattering lines made by a polymer film is proportional to its thickness, the thickness of the film can be determined in air at the same time as content of its constituent elements. Show below are tow examples of this. ■■■■Sample Polyester film 6μm、12μm、25μm Polyethylene film including inorganic elements

200μm

■■■■Sample Preparation The sample is submitted for testing without prior

preparation.


■■■■Qualitative Analysis of Polyester Films In the BG-FP method of polymer film thickness determination, the Compton scattering lines of the “characteristic” X-rays of the X-ray tube target(Rh) is measured. The RhKa Compton scattering profiles of the 3 polymer films of differing thickness is shown superimposed on the same graph in Fig.2. From this it can be seen that the intensity of the RhKa Compton scattering lines becomes greater as the thickness of the film increases.

Fig.2 RhKaCompton Profile of Polyester Films

■■■■Determining the Thickness of Polyester Films

The results of the thickness determination analysis by BG-FP method are shown in Table 1. In order to calculate the film’s thickness the density of the film is required. In this case the 1.39g/cm3 density of polyester is used. In addition it was assumed that the composition of the film was C10H8O4.

Table 1 Thickness Determination of Polyester Films by Background FP Method Sample Chemical Formula Film Density Determined Value Reference Value by Micrometer

Polyester

Films

(C8H10O4)n

1.39g/cm3

7.2μm 14.5μm 29.7μm

6μm 12μm 25μm

7～14μm 14 μm 26～30μm

RaynyRaynyRaynyRayny EDXEDXEDXEDX----700/800700/800700/800700/800 ApplicationApplicationApplicationApplication DataDataDataData No.9No.9No.9No.9

■■■■Determination of Both the Thickness and the Concentration

The thickness of polyethylene that includes the elements Cr, Mn, Fe, Co, Ni, Cu and Zn was determined at the same time as the content of the elements within the polyethylene.

The quantitative profiles are shown in Fig.3, while in Table 2 the values calculated from the

quantitative profiles by the BG-FP method is shown together with their equivalent area density(30mmφ)conversion values and standard values. Note that the major was assumed to be polyethylene (CH2)n and used as the balance(residue balance), while the density of the film was assumed to be that of polyethylene(0.92g/cm3).

Fig.3 Profiles of Polyethylene Film for Quantitative Analysis

Table 2 Determined Thickness and Concentration of/in Polyethylene Film by Background FP Method Sample Film

Density Determined

Value Standard

Value

Polyethylene Film including Inorganic Compounds

0.92 g/cm3

((CH2)n)

Cr 91μg/30mmφ( 645ppm) Mn 297 ( 2096 ) Fe 219 ( 1546 ) Co 21 ( 149 ) Ni 87 ( 612 ) Cu 85 ( 598 ) Zn 88 ( 620 ) Thickness 218μm

100μg/30mmφ( 769ppm) 300 ( 2307 ) 200 ( 1538 ) 20 ( 154 ) 100 ( 769 ) 100 ( 769 ) 100 ( 769 ) 200μm

■■■■Analytical Conditions Instrument : EDX-700 X-ray Tube : Rh target Filter : not used Voltage - Current : 50kV- 77μA(Auto) 50kV- 446μA(Auto) Atmosphere : Air Measurement Diameter : 10mmφ Measuring Time : 100sec Dead Time : 24%

■■■■References Shimadzu Application News X-ray Analysis

No.175,176 ”The Application of Background FP Method”(1),(2).

Shimadzu Application News X-ray Analysis No.190 ”The Measurement of the Thickness of a Polymer Coat on a Steel Plate Using the Theoretical Intensity of the Compton Scattering X-rays”.

RaynyRaynyRaynyRayny ApplicationApplicationApplicationApplication DataDataDataData No.9No.9No.9No.9

Fields:Ceramics, Electronic/Magnetic Materials, Industrial Waste

EDXRFEDXRFEDXRFEDXRF AnalysisAnalysisAnalysisAnalysis ofofofof GlassGlassGlassGlass

Since EDX can analyze a sample regardless of its size or shape, irregular objects such as glass bottles or their broken pieces and laser disc plates can be easily analyzed. In addition, trace elements in glass can be detected using a Zr filter. Shown below are examples of qualitative and quantitative analysis of borosilicate glass and qualitative analysis of trace elements within special glass. ■■■■SampleSampleSampleSample ・ NBS standard sample 93a Borosilicate glass. ・ Special glass A, B

■■■■SampleSampleSampleSample PreparationPreparationPreparationPreparation The sample was placed directly on the sample stage. ■■■■ResultResultResultResult ofofofof thethethethe QualitativeQualitativeQualitativeQualitative andandandand QuantitativeQuantitativeQuantitativeQuantitative AnalysisAnalysisAnalysisAnalysis ofofofof BorosilicateBorosilicateBorosilicateBorosilicate GlassGlassGlassGlass

The result of the qualitative analysis is shown in Fig.1. The graph on the bottom right superimposes the results with and without the Al filter, through which the presence of Cl was detected.

The quantitative analysis results by the FP method is shown in Table 1. The quantitative calculations were made by employing the standard value as the fixed value because Boron cannot be detected.

Fig.1 Qualitative Analysis of Borosilicate Glass NBS93a

Table 1 Quantitative Value of Borosilicate Glass NBS93a by FP Method

Compound SiO2 Na2O Al2O3 Cl ZrO2 Fe2O3 K2O CaO TiO2 B2O3 Quantitative Value(%) 80.80 3.43 2.93 0.086 0.054 0.040 0.039 0.036 0.027 (12.56)

Standard Value(%) 80.8 3.98 2.28 0.060 0.042 0.044 0.014 0.01 0.014 12.56 ( )known value


■■■■ QualitativeQualitativeQualitativeQualitative AnalysiAnalysiAnalysiAnalysissss ofofofof TraceTraceTraceTrace ElementsElementsElementsElements inininin SpecialSpecialSpecialSpecial GlassGlassGlassGlass usingusingusingusing thethethethe ZrZrZrZr FilterFilterFilterFilter

By using the filter effectively, the scattering of the primaryprimaryprimaryprimary XXXX----raysraysraysrays from the X-ray tube can be reduced, and a good S/N ratio can be achieved during measurement. In Fig.2 the qualitative analysis

results of trace elements for the two types of special glass are shown, with the results obtained using Zr filter superimposed on the results obtained without the filter.

Fig.2 Qualitative Analysis of Traces in Glasses using Zr Filter (a)Glass A (b)Glass B ■■■■AnalyticalAnalyticalAnalyticalAnalytical ConditionsConditionsConditionsConditions Instrument : EDX-700 X-ray Tube : Rh target Filter : not used, Al, Zr Voltage - Current : 50kV-9～202μA(Auto) 15kV-182～1000μA(Auto)

Atmosphere : Vacuum

Measurement Diameter : 10mmφ Measuring Time : 300sec

Dead Time : 24～27% ■■■■ ReferenceReferenceReferenceReference Shimadzu Application News X-ray Analysis No.188””””TheTheTheThe XXXX----rayrayrayray FluorescenceFluorescenceFluorescenceFluorescence AnalysisAnalysisAnalysisAnalysis ofofofof GlassGlassGlassGlass””””


Filds:Medical Treatment, Food Products

EDXRF Analysis of Cd, Hg, and Pb in BloodEDXRF Analysis of Cd, Hg, and Pb in BloodEDXRF Analysis of Cd, Hg, and Pb in BloodEDXRF Analysis of Cd, Hg, and Pb in Blood

There is a need nowadays for the rapid estimation of the various type of poisons in medicine that have combined with metals in order to be able to give emergency treatment through the administering of an antidote. EDX-700/800 can identify various types of metals after a simple preparation of the sample.

Furthermore the testing is non-destructive so the sample can be analyzed with a different analyzer after testing. Shown below are examples of qualitative analysis with the sample in liquid form and with the sample dried on filter paper. ■■■■SampleSampleSampleSample ・A sample of blood to which the anticoagulant Heparin has been added. ・ A sample where aqueous solutions for atomic absorption spectrometry with 1000ppm of Cd, Hg, and Pb

has been dropped and mixed into the blood and prepared so that the concentrations of Cd, Hg, and Pb are 10 ppm.

■■■■Sample PreparationSample PreparationSample PreparationSample Preparation （１）Liquid Cell Method Approximately 10ml of the sample was poured into the liquid sample receptacle sealed with 5μm polypropylene film.

―― Liquid State ――

Sample loading

（２）Filter Method After dropping 100μl of the sample onto filter paper, the paper was dried for 5 minutes at 80℃.

―― Dried on Filter ――

Sample loading


Snap-on ring

5μm polypropylene film

Cell made of polyethylene

～10ml

Adopter for liquid

Dry for 5 minute, at 80 ℃ 100μl

Micro pipette

Filter Paper Paraffin ring

Blood

⇒ ⇒

■■■■Result of the Result of the Result of the Result of the Qualitative Analysis of BloodQualitative Analysis of BloodQualitative Analysis of BloodQualitative Analysis of Blood

The sample of blood and the sample with 10ppm of Cd, Hg, and Pb were qualitatively analyzed with the liquid cell method and the filter method. The comparative results are shown on Fig.1 In addition the difference in profile between the blood of Fig.1(b) and that of the sample with the added Cd, Hg, and Pb is compared in Fig.2.

―― Liquid State ―― ―― Dried on Filter ――

“Only Blood” Profile has offset (Backgrounds are same between “Only Blood” and “Blood added Cd, Hg, Pb “)

Fig.1 Qualitative Analysis of Cd, Hg, Pb 10ppm in Blood ■■■■Lower Limit of Detection(L.L.D)Lower Limit of Detection(L.L.D)Lower Limit of Detection(L.L.D)Lower Limit of Detection(L.L.D) The lower limit of detection of Cd, Hg, and Pb in blood calculated from the results of the qualitative analysis is shown in Table 1.

Table 1 L.L.D of Cd, Hg, Pb in Blood Element Liquid State Dried on Filter

Cd 9.9 ppm 8.0 ppm Hg 3.4 ppm 1.9 ppm Pb 2.2 ppm 1.6 ppm

■■■■Analytical Conditions

Instrument : EDX-700 X-ray Tube : Rh target Filter : Ni, Zr Voltage - Current : 50kV-24～500μA(Auto) Atmosphere : Air Measurement Diameter : 10mmφ Measuring Time : 1000sec Dead Time : 6～26%

Fig.2 Difference of Two Profiles in Fig.1(b)


Fields:Medical Treatment, Food Products

EDXRFEDXRFEDXRFEDXRF AnalysisAnalysisAnalysisAnalysis ofofofof P,P,P,P, Cl,Cl,Cl,Cl, KKKK andandandand CaCaCaCa inininin BloodBloodBloodBlood

EDX is effective for quick screening analysis of tests for electrolytes (such as P, Cl, K, Ca) in blood. Carrying out the analysis in air with these light elements results in the X-ray fluorescence from the sample being absorbed by the air, consequently lowering the sensitivity. The analysis therefore needs to be carried out either in helium or a vacuum. Though it is impossible to directly analyze a liquid such as blood in a vacuum, the liquid can be dropped onto filter paper, dried, and then analyzed in a vacuum. Shown below is an example of such a qualitative analysis. ■■■■SampleSampleSampleSample

Blood to which the anticoagulant Heparin has been added (Heparin is unnecessary if the sample is prepared as shown below).

■■■■SampleSampleSampleSample PreparationPreparationPreparationPreparation After 100μl of the sample has dropped onto the filter paper, the paper is dried for 5 minutes at 80℃(If

heparin is not added the paper is dried at normal temperature). This is described in the diagrams below.

Sample Loading Measurement

Dry (for 5 minute at 80 ℃ ）


（Heparin）

Micro pipette

100μl

Blood

STARTSTARTSTARTSTART

■■■■TheTheTheThe ResultResultResultResult ofofofof thethethethe QualitativeQualitativeQualitativeQualitative AnalysisAnalysisAnalysisAnalysis ofofofof ElectrolytesElectrolytesElectrolytesElectrolytes inininin BloodBloodBloodBlood The Results of the qualitative analysis of electrolytes such as P, Cl, K, and Ca present in the blood is shown

in Fig.. P-Ca have been detected (S has been detected as well, but it is assumed that this is from the Heparin). The reference values of these constituent elements for an adult male are shown in Table 1.

Fig.1 Qualitative Analysis of Electrolytes in Blood

Table 1 Reference of Electrolyte in Blood1)

P(Inorganic) Cl K Ca 2.6～4.4mg/dl

(26～44ppm) 97.8～102.6mEq/l

(0.35～0.36%) 3.5～4.8mEq/l

(137～187ppm) 8.6～10.4mg/dl

(86～104ppm) ■■■■ComparisonComparisonComparisonComparison ofofofof thethethethe AtmosphereAtmosphereAtmosphereAtmosphere inininin whichwhichwhichwhich AnalysisAnalysisAnalysisAnalysis waswaswaswas CarriedCarriedCarriedCarried OutOutOutOut

The various sensitivities and methods are compared and summarized in Table 2 for the liquid and filter methods in air, vacuum, and helium.

Table 2 Comparison of Atmospheres Air Vacuum He Atmosphere

Filter Paper ◎ Simple, fast, drying not necessary

○ Drying necessary ○Drying not necessary

Liquid ◎ Simple, fast, feasible × Not possible ○ Possible Sensitivity ○ Reduces with elements

lighter than Ti ◎ Good ◎ Good

■■■■AnalyticalAnalyticalAnalyticalAnalytical ConditionsConditionsConditionsConditions Instrument : EDX-700 X-ray Tube : Rh target Filter : Al Voltage - Current : 15kV-1000μA(Auto)

Measurement Diameter : 10mmφ Atmosphere : Vacuum Measuring Time : 500sec Dead Time : 21%

■■■■Reference 1)Extensive Blood/Urine Chemistry Tests, Immunological Tests – How to Interpret the Values – (First Volume) Nihon Rin-rin Special Autumn Issue 1985, Nihon Rin-rin sha



ApplicationApplicationApplicationApplication DataDataDataData No.13No.13No.13No.13 Fields:Machinery, Food Products

EDXRF Analysis of OilEDXRF Analysis of OilEDXRF Analysis of OilEDXRF Analysis of Oil

When analyzing metallic elements within oil or gel-form substances the method of dropping and drying the sample onto filter is effective but difficult to handle and prepare. EDX is therefore the best and easiest method of analysis as it does not require the sample to be prepared beforehand.

As liquids cannot be analyzed in a vacuum, the analysis is carried out in either air or helium. Whereas the X-ray fluorescence from a sample is only slightly absorbed in air in the case of heavy elements, with light elements this absorption greatens, so helium is used as it absorbs only a small amount.

Shown below is an example of qualitative analysis of a standard oil from Conostan Co.Conostan Co.Conostan Co.Conostan Co. ■■■■SampleSampleSampleSample Conostan S-21 Blended Standard Hydrocarbon oil which includes 100ppm of each element listed below. ■■■■ElementsElementsElementsElements Si, P , Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Mo, Ag, Cd, Sn, Pb

■■■■Sample PreparationSample PreparationSample PreparationSample Preparation

5μm polypropylene was stuck onto the base of liquid sample receptacle into which approximately 5ml of the sample was poured without any preparation.

■■■■Lower Limit of Detection by QualitativeLower Limit of Detection by QualitativeLower Limit of Detection by QualitativeLower Limit of Detection by Qualitative

AnalysisAnalysisAnalysisAnalysis＊＊＊＊

Table 1 Lower Limit of Detection Element Spectra L.L.D. Filter

14Si 15P

20Ca 22Ti 23V

24Cr 25Mn 26Fe 28Ni 29Cu 30Zn 42Mo 47Ag 48Cd 50Sn 82Pb

Kα Kα Kα Kα Kα Kα Kα Kα Kα Kα Kα Kα Kα1 Kα1 Kα1 Lα

77ppm 59 15 12 11 9.6 6.4 4.7 3.2 2.1 1.9 6.9 14 13 17 5.3

Al Al Al Al Ti Ti Zr Zr Zr Ni Zr Zr Zr Ni

Taking this sample to be the standard sample, the lower limit of detection for each element was calculated from the results of the qualitative analysis, and this is shown in Table 1. From these results it can be seen that the ppm levels of heavy elements in the air can be detected.

In addition, a logarithmic graph of the X-ray fluorescence energy of this lower limit of detection is shown in Fig.1.

Fig.1 Lower Limit of Detection of Metal Elements in Standard Oil, S-21

■■■■Qualitative Qualitative Qualitative Qualitative ProfileProfileProfileProfile The result of the qualitative analysis is shown in Fig.2.

Fig.2 Qualitative Analysis of Standard Oil, S-21

■■■■Analytical Conditions ―――――――――――――――――――――――――――――――――――――― Instrument : EDX-700 X-ray Tube : Rh target Filter : Al, Ti, Ni, Zr or without Voltage - Current : 15kV-301μA(Auto), -352μA(Auto), 50kV-24μA(Auto), -39μA(Auto), -286μA(Auto） Atmosphere : Air, He Measurement Diameter : 10mmφ Measurement Time : 1000sec Dead Time : 24～25% ―――――――――――――――――――――――――――――――――――――― *The equation for the Lower Limit of Detection(L.L.D.)


C ： Standard Value(wt%)

Inet ： Net Intensity(Counts)

Iback ： Background Intensity(Counts) √ Inet Iback Ｃ L.L.D.=３× ――― ×


Fields:Iron and Steel, Non-ferrous Metals, Machinery

TheTheTheThe ContentContentContentContent MatchingMatchingMatchingMatching FunctionFunctionFunctionFunction --- Applications for the Differentiation and Identification of Steel Types ---

When using devices such as X-ray fluorescence spectrometers for process and quality management, the aim is to ascertain whether the analyzed values are within the parameters set by standards (such as JIS). A new matching function that identifies the steel type has been added to the EDX-700/800 separate to the function which determines whether standards are being met. This function selects a type of steel with a high degree of similarity (for example SUS304) from a stored library. It incorporates two methods, the conventional method of spectral matching by comparison of the X-ray intensity, and the content matching method, which works by comparing quantitative values. Shimadzu has been the first to install the latter method in an X-ray fluorescence spectrometer, and enables it to be used not just with finished products but with acceptance materials and waste materials. Examples of use particularly suited to this content matching function, stainless steel, and aluminum alloys are introduced below. ■■■■ContentContentContentContent MatchingMatchingMatchingMatching Since conventional spectral matching involves the comparison of X-ray intensity it is necessary at first to get measurements of samples to be registered, such as that of standard samples. With content matching however this is not necessary as all that is required is to input the standard values. Thus even if there is no sample to compare with, differentiation and comparisons can be made. ■MatchingMatchingMatchingMatching LibraryLibraryLibraryLibrary

A library is created in advance in which the details of the types of material and the elements contained in each type of material is stored. In this instance the 49 types of the JIS G 4303 has been registered for stainless steel, and the 38 types of the JIS H 4000 for aluminum alloys. ■SampleSampleSampleSample (1) The Iron and Steel Institute of Japan

Standard Sample Stainless Steel Series SUS-430、-309S、-304、-310S、-316 (2)Standard Sample Aluminum Alloy

Type 1050, 3004, 5052, 6061 ■MethodMethodMethodMethod ofofofof QuantitativeQuantitativeQuantitativeQuantitative AnalysisAnalysisAnalysisAnalysis

1. By qualitative – quantitative (FP), 2. By quantitative FP, 3. By calibration curves. In this instance the second method by quantitative FP was employed.

■■■■ResultResultResultResult ofofofof MatchingMatchingMatchingMatching,,,, andandandand itsitsitsits DetailDetailDetailDetailssss The results of the matching and quantitative

analysis for SUS430 is shown in Fig.2.

Fig.1 Matching Library

Fig.2 Result of Quantitative Analysis & Matching

The quantitative values for each element

(expressed as the degree of discrepancy) which is the most similar (i.e. the degree of discrepancy is the smallest) to the comparative values of the contents of the samples registered in the library will be displayed. By processing the data the details of the matching results can be seen. As indicated in Fig.3, the degree of discrepancy for the top 10 types is displayed, including that for the second type onwards which could not be differentiated. In addition the deviation for each element can be displayed (diagram is omitted). (1)Stainless steel The results of the other 4 samples are shown in Fig.4 Each of the 4 samples of SUS430, 316 309S, & 310S have been identified as themselves.

The SUS304 has been identified as SUS304LN, and is itself ranked at number 3. This is because the C and N which are difficult to differentiate by EDX have been excluded from the comparison. It would be best in the case of the SUS304 type to group the SUS304, 304L and 304LN together when registering them in the library.

Fig.3 Detail of Matching for SUS430

Fig.4 Result of Matching for Stainless

(2) Aluminum Alloy

The results of 4 samples are shown in Fig.5. Out of the 38 types of aluminum alloys a match with the smallest degree of discrepancy has been found for each sample ■NoteNoteNoteNote Where the difference in the degree of discrepancy between the first match and the second match onwards is great, as in the case of SUS309S and SUS310S, the results can be considered highly reliable. Fig.5 Result of Matching for Aluminum Alloys On the other hand, in instances where the difference is not so big, as in the case of Al1050 and Al3004, the possibility arises that any of the top few results could be the correct match ■ AnalyAnalyAnalyAnalyticalticalticaltical ConditionsConditionsConditionsConditions ―――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――― Instrument : EDX-700 X-ray Tube : Rh target Filter : without Voltage - Current : 15kV/50kV-(Auto),

Atmosphere : Vacuum Measurement Diameter : 10mmφ Measurement Time : 100sec Dead Time : 25%

--------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------



Fields: Food Products, Pharmaceuticals, Chemistry

Analysis of Foreign Matter Using CCDAnalysis of Foreign Matter Using CCDAnalysis of Foreign Matter Using CCDAnalysis of Foreign Matter Using CCD The type of foreign matter adhered or mixed into food products, pharmaceuticals, and products can be easily determined in a short period of time using the EDX. If the observation capability of the CCD (optional) is utilized, foreign matter of less than 1mm can be easily measured. In addition, by using an X-ray irradiation collimator, the neighboring foreign matter can be easily separated and analyzed. 5 varieties of foreign matter (metal fragments) of about 0.3mm to 1mm were adhered or buried in a chocolate bar and used as the sample. The result of qualitative and quantitative analysis for each substance is shown below. ----SSSSample:ample:ample:ample: Unknown foreign matter A Unknown foreign matter B Unknown foreign matter C Known foreign matter D (a scrap of chocolate wrapping) Unknown foreign matter E (Refer to Fig.1) ----Sample Preparation:Sample Preparation:Sample Preparation:Sample Preparation: Place the sample on the sample stage (see Fig.2) and start the CCD image viewing software in Windows. An image like that shown in Fig.1 will be displayed on the CRT. Fix the position by moving the sample so that the object of measurement is under the point where the crosshairs meet (Fig.1 shows B as the object being measured).

Fig.1 Picture of Foreign Matters by CCD

The concentric circles from the center indicate the diameter of the X-ray irradiation collimator (optional), and hence indicates the measurement range. ----Results of Qualitative AnalysisResults of Qualitative AnalysisResults of Qualitative AnalysisResults of Qualitative Analysis:::: Qualitative analysis was carried out in air (vacuum for D only) for each foreign matter A, B, C, D & E using a 1 mmφ collimator. The overlaid qualitative analysis results are shown in Fig.3. The elements detected are shown in Table 1.

Table 1 Detected Elements Chocolate K、Ca、Fe

Ａ K、Ca、Cr、Mn、Fe、Ni、Mo B K、Ca、Cu C K、Ca、Fe、Cu、Pb、Sn D Al、K、Ca、Fe E K、Ca、Fe、Zn


Fig.3 Qualitative Analysis of Foreign Matters

Fig.4 Quantitative Result of Foreign Matter A by FP Method

---- Results of Quantitative A Results of Quantitative A Results of Quantitative A Results of Quantitative Analysisnalysisnalysisnalysis:::: As an example of the result of a quantitative analysis, the result of quantifying foreign matter A by the FP method is shown in Fig.4. K and Ca are included in chocolate and were thus omitted from the quantitative calculations. ----Investigation:Investigation:Investigation:Investigation: It is inferred that the identity of each foreign matter is as follows. A: Stainless steel B: Copper wire C: Lead bronze E: Zinc plated steel wire

----Analytical Conditions:Analytical Conditions:Analytical Conditions:Analytical Conditions: ―――――――――――――――――――――― Instrument : EDX-700 X-ray Tube : Rh target Filter : without Voltage - Current : 50kV-(Auto） Atmosphere : Air,Vacuum Measurement Diameter : 1mmφ Measurement Time : 30sec Dead Time : 25%



Field: Environment, Chemistry

AnalysisAnalysisAnalysisAnalysis ofofofof TraceTraceTraceTrace ElementsElementsElementsElements inininin WaterWaterWaterWater usingusingusingusing UltraUltraUltraUltra ThinThinThinThin FilmFilmFilmFilm (1)(1)(1)(1)

When analyzing water solution using the EDX, the detectable and quantifiable concentration range was in the ppm or higher level for the conventional solution measuring method and the spotting filter paper method, where the sample was spotted and dried on filter paper. By replacing the filter paper with ultra thin polymer film, however, quantum improvements have been made to the S/N ratio, enabling detection and quantification to the ppb level. The following introduces the pretreatment and the qualitative results and lower detection limits for trace elements in a sample. ■Ultra Thin Polymer Film

A 0.15µm polyimide film is stretched in midair across sample holders. A 2 mm diameter section in the center of the film is specially prepared to gather the precipitate after the sample has been dried (see Figs. 1 and 2). ■Sample Preparation

Fifty µL of sample solution was dropped using a micro pipette, and was dried at 70°C for 40 minutes in a drier (see Fig. 2). Fig. 3 shows the image of the dried sample observed using the optional CCD camera. ■Sample

NIST 1643d Trace Elements in Water Table 1 shows the standard values. ■Qualitative Analysis

Fig. 4 shows the qualitative analysis results for NIST 1643d. The upper graph shows the result obtained without the filter, while the lower graphs show the results obtained using a Ti filter and a Ni filter, respectively.

Fig.3 Picture of sample after dry

0.15μm Polyimide

2mm

Plastics holder Fig.1 Ultra thin polymer film and sample holder

Drops side

Residue

50μl

Dry

Fig.2 Sample preparation(Drop & Dry)

Fig. 4 Qualitative Analysis of NIST1643d

Table 1 Certified or reference Mass Concentrations for 1643dμg/L(ppb) and L.L.D

Element Certified L.L.D Na Mg Al Si K Ca V Cr Mn Fe Co Ni Cu Zn As Sr Mo Ba Pb

22.07 * 7.989* 127.6 2.7* 2.365* 31.04* 35.1 18.53 37.66 91.2 25.00 58.1 20.5 72.48 56.02 294.8 112.9 506.5 18.15

1911ppb 406 -- 44 121 -- -- -- 12 10 18 15 -- 15 15 18 22 65 --

*marked :mg/L(ppm), --Not calculated

■Lower Limits of Detection(L.L.D) Table 1 shows the lower limits of detection

calculated from the intensities of the detected elements. The calculation formula is as follows:

L.L.D = 3 x (BG/T)1/2 x C/NET where BG: background, NET: net intensity (cps),

T: measurement time (sec), C: reference value (ppm/ppb).

■Analytical Conditions

Instrument : X-ray Tube :

Filter : Voltage - Current :

Atmosphere :

Measurement Diameter : Measurement Time :

Dead Time :

EDX-700 Rh target without,Ti,Ni 50kV-(Auto）15kV-(Auto) Vacuum 3mmφ 1000sec 0～12%


upper:without filter lower left:Ti filter lower right: Ni filter


Field: Environment, Chemistry

AnalysisAnalysisAnalysisAnalysis ofofofof TraceTraceTraceTrace ElementsElementsElementsElements inininin WaterWaterWaterWater usingusingusingusing UltraUltraUltraUltra ThinThinThinThin FilmFilmFilmFilm (2)(2)(2)(2) This Application Data introduces an example of comparison between qualitative/quantitative analysis

using the FP method, and qualitative analysis using the calibration curve method. The NRC (National Research Council Canada) river water standard sample was analyzed after the same pretreatment that was introduced in Application Data No.16.

In the spotting filter paper method and the thin film method in the EDX-700/800 standard software, the quantitative values are shown in the concentration in water solution, and the amount of deposition on the thin film, respectively. ■Sample , Elements (1) Quantitative sample

NRC SLRS-4 River Water Reference Material for Trace Metals

Table 1 shows the standard values. (2) Standard samples for calibration curve method

Na: 0.5 to 5ppm K: 0.5 to 20ppm Fe: 100 to 500ppb

A standard liquid for atomic absorption was used with dilution. ■Sample Preparation

Fifty µL sample was dropped and dried for 40 minutes at 70°C. ■Qualitative and Quantitative Analysis

Fig. 1 shows qualitative analysis results for SLRS-4 and Table 1 shows the quantitative values obtained by the FP method, in comparison to the

reference values.

Table 1 Certified Mass Concentrations for SLRS-4 μg/L(ppb) and Quantitative Value

Element Certified Value

Qualitative Value

Na Mg Si S K Ca Mn Fe Br Rb Sr

2.4* 1.6* - - 0.68* 6.2* 3.37 103 - - 26.3

2.6* 1.4* 1.3* 697 0.61* 5.6* 7.1 98 11 7.1 39

*marked :mg/L(ppm) NIST 1643d Trace Elements in Water was used

as the reference for the FP method.

Fig.1 Qualitative Result of SLRS-4

■Quantitative Analysis by Empirical Correction Method

Fig. 2 shows the calibration curves for Na, K and Fe. These were used for SLRS-4 quantitative analysis and repeatability tests (n = 10). Table 2 shows the results.

Na K Fe

Fig.2 Calibration Curve of Na, K and Fe

Table 2 Quantitative Value and Repeatability (n=10) Elements Na K Fe Average

Standard Deviation Coefficient of Variation

0.339ppm 0.083ppm

24%

0.558ppm 0.027ppm

4.8%

159ppb 13.7ppb

8.6% Accuracy of Calibration Curve 0.068ppm 0.008ppm 12.1ppb

■Conclusion

Quantitative results showed that the FP method provided values closer to the reference values than the calibration curve method. This is considered to be due to the difference in matrix effects (absorption and excitation effects due to coexisting elements) between the reference and the measured sample. Therefore, the calibration curve method is effective for measurements of samples of the same type, while the FP method is effective for measurements of different types of samples. ■ References

EDX-700/800 Application Data No. 11, 12 and 16

■Analytical Conditions Instrument : X-ray Tube :


Atmosphere :

Measurement Diameter : Measurement Time :

Dead Time :

EDX-700,800 Rh target without,Ti 50kV-(Auto） 15kV-(Auto) Vacuum 3mmφ 1000sec 0～12%



ApplicationApplicationApplicationApplication DataDataDataData No.1No.1No.1No.18888

Field: Chemistry, Automobiles

EDXRF Analysis of EDXRF Analysis of EDXRF Analysis of EDXRF Analysis of Sulfur in Sulfur in Sulfur in Sulfur in OilOilOilOil The EDX is the optimum tool for straightforward no-pretreatment analysis of sulfur in heavy and light oils.

The lower limits of detection and repeatability were investigated in air/He atmospheres. The EDX is also effective for measurements of high-concentration samples (% order), because it assures

sufficient sensitivity even in the air atmosphere. This Application Data also introduces an example of quantitative analysis and repeatability tests using the FP method and the calibration curve method. <Measurement of lower limits of detection and repeatability for low<Measurement of lower limits of detection and repeatability for low<Measurement of lower limits of detection and repeatability for low<Measurement of lower limits of detection and repeatability for low----concentration standard samples>concentration standard samples>concentration standard samples>concentration standard samples>

■■■■Sample

Commercially available standard samples Sulfur content: 0, 10, 25, 50, 100, 200, 300µg/g ■■■■Sample Preparation

Approximately 6mL of samples were put into a liquid-sample container coated with 5µm thick polypropylene on the bottom. ■■■■Lower Limit of Detection, Calibration Curve

Fig. 1 shows the calibration curves and Table 1 shows the lower limits of detection calculated from the calibration curves. Table １ Lower Limit of Detection

In Air 34μg/g In He 9.6μg/g

■■■■Repeatability Test

The 200µg/g sample was analyzed repeatedly 10 times.

Table 2 Repeatability of S Air He

Average Standard Deviation

Coefficient of Variation

199μg/g 8.1μg/g

4.1%

202μg/g 5.8μg/g

2.9%

Fig.1 Calibration Curve of S in Light Mineral Oil ■Analytical Conditions



Atmosphere : Measurement Diameter :

Measurement Time : Dead Time :

EDX-700 Rh target without 15kV-(Auto) Air,He 10mmφ 300sec 25%

(When analyzing gasoline)

Gasoline can be analyzed using the same pretreatment method and under the same measurement conditions as described above. However, it is recommended to use gasoline-durable mylar film to coat the bottom of the container when measurement takes a long time. (The thickness of the mylar film should be less than 3µm to obtain the same lower limits of detection, as mylar shows smaller transmissibity for sulfur than polypropylene.)

As the EDX is not explosion-proof, take the most care for ventilation.

<Quantitative analysis and repeatability test for high<Quantitative analysis and repeatability test for high<Quantitative analysis and repeatability test for high<Quantitative analysis and repeatability test for high----concentraconcentraconcentraconcentration standard samples>tion standard samples>tion standard samples>tion standard samples> ■■■■Sample

JPI heavy oil standard sample: Sulfur content 4.26%, 1.07%

Mixture of standard samples : 2.73% ■■■■Sample Preparation

Approximately 6mL of samples were put into a liquid-sample container coated with 5µm-thick polypropylene on the bottom. ■■■■Quantitative Analysis , Repeatability Test (1) FP Method (Fundamental Parameter Method)

Element sensitivity coefficient was determined from the measurement points of the three samples.(Fig.2(a))

(2) Calibration Curve Method (Empirical Correction Method)

A calibration curve (Fig. 2 (b)) was created for the three measurement points and the origin. (3) Results of quantitative analysis and repeatability test

Quantitative analyses were repeated ten times for the mixed sample (2.73% sulfur) for both the FP and calibration curve methods. Table 3 shows the results.

In the quantitative calculation for the FP method, the heavy oil’s main component is assumed to be CH2 and balanced accordingly.

Fig.2 (a)Sensitive Coefficient (b)Calibration Curve

Table 3 Repeatability FP EC



2.75% 0.028% 1.0%

2.75% 0.029% 1.0%

Accuracy of Calibration Curve -- 0.059% ■■■■Conclusion

The quantitative accuracy and repeatability are almost the same for the FP method and calibration curve method.

With the calibration curve method, multiple reference samples are required depending on the measurement concentration range, as the curve tends to flatten in the higher-concentration region. With the FP method, a reference sample of high concentration allows quantification across a wide

range of concentrations, as the element sensitivity coefficient creates a straight line. ■Analytical Conditions





EDX-700 Rh target without 15kV-(Auto) Air 10mmφ 75sec 25%

RaynyRaynyRaynyRayny ApplicApplicApplicApplicationationationation DataDataDataData No.1No.1No.1No.18888


ApplicationApplicationApplicationApplication DataDataDataData No.1No.1No.1No.19999

Field: Electronic materials, Chemistry, Steel, Non-ferrous

EDXRF Analysis of EDXRF Analysis of EDXRF Analysis of EDXRF Analysis of Thin FilmThin FilmThin FilmThin Film The X-ray fluorescence analysis allows film thickness and composition analyses in the order of several nm

to several µm for light elements such as Al and Si, and sub-nm (several Å) to several tens of µm for heavy elements such as Ni. Here, the thickness of Au films deposited on glass plates were measured and the repeatability was tested using the FP method and the calibration curve method. The lower limits of detection were also calculated. ■■■■Sample

Au films of different thickness (10nm, 20nm, 30nm, 40nm and 50nm) deposited on boro-silicate glass plates. ■■■■Sample Preparation

The samples were measured without any pretreatment. ■■■■Quantitative Analysis and Repeatability Test with FP Method

The five samples (each with differing film thickness) were quantitatively analyzed using the FP method. Table 1 shows the results.

Table 1 Quantitative Result with FP Sample Quantitative

Value Deviation

10nm 20nm 30nm 40nm 50nm

10.3nm 19.8 29.7 40.1 50.1

0.3nm －0.2 －0.3 0.1 0.1

Standard Deviation 0.24nm Table 2 shows the result of the repeatability test. The 30 nm sample was analyzed 10 times with the FP method.

Table 2 Repeatability of 30nm with FP Average

Standard Deviation Coefficient of Variation

29.3nm 0.55nm

1.9% An Au thin film was used as the reference, because the commonly used bulk samples are not suitable for the measurement of ultra thin films due to density difference and effects of the base plate. ■■■■Spectra for Quantitative Analysis Fig. 1 shows the Au spectrum for quantitative analysis.

Fig.1 Spectra of Au for Quantitative Analysis

A strong Zn spectrum is observed because several percent of ZnO is contained in the boro-silicate glass base plate. Therefore, the AuLβ1 beam was used to avoid the overlapping of the commonly used AuLα beam with the ZnKβ beam. In measurements using the EDX, spectrums may become superimposed if the sample contains multiple elements. As shown in this example, using a different analysis beam enables quantitative analysis of such samples. In this example, an Ni filter was used to reduce the background (The background tends to be increased as the base plate is mainly composed of SiO2, a light element). The use of an Ni filter improves the P/B ratio, enabling highly accurate quantitative analysis of thin films.

The analyses and measurements performed in this example are all possible with the EDX-700/800 standard configuration.

■■■■Calibration Curve, Lower Limit of Detection,

Repeatability with Empirical Correction Metho Fig. 2 shows the calibration curve created by the five samples.

Fig.2 Calibration Curve of Au Thickness

The lower limit of detection calculated from the calibration curve is 0.49nm (= 4.9 Å).

Table 3 shows the result of the repeatability test.

The 30nm sample was analyzed 10 times using the calibration curve method.

Table 3 Repeatability of 30nm with EC



29.5nm 0.37nm

1.3% ■Analytical Conditions





EDX-700 Rh target Ni 50kV-(Auto) Air 10mmφ 300sec 25%

■■■■Some Examples of Other Kind of Films

Sample Film(Layer) structure Quantitative Results Coated steel sheet

Amount of film deposition: ?mg/m2 Film composition: Cr 100% Amount of film deposition: ?g/m2

Film composition: Zn 100%

Base Plate: Fe 100%

Cr layer: 75.4mg/m2 Zn layer: 31.6g/m2

Film on silicon wafer

Film thickness: ?nm Film composition: Fe ?% Ni ?%

Base plate: Si 100%

Film thickness: 111nm Fe: 18.8% Ni: 81.2% （C.V 0.2%，0.05%）

Anti-static film and anti-peeling coating on polymer film

Amount of film deposition: ?μg/cm2

Film composition: Si compound＊

Polymer film composition: C10H8O4（PET） 100%

Si compound: 5.5μg/cm2 （C.V 0.8%）＊The actual chemical formula should be set depending on the case.

Paper

Film weight: 10.5ｍg/cm2 Components: ？, Composition？

SiO2 : 1.16%, MgO: 0.54%Others C6H10O5:97.65%（balance）

C.V:Repeatability coefficient of Variation In X-ray fluorescence analysis, thin films are measured in amounts (the amount of deposition or film

weight) and expressed in the units such as mg/m2. Film thickness is calculated by dividing the amount by the


Accuracy = 0.16nm

density of the film or the layer (g/m3).

RaynyRaynyRaynyRayny EDXEDXEDXEDX----700/800700/800700/800700/800/900/900/900/900 ApplicationApplicationApplicationApplication DataDataDataData No.No.No.No.20202020 Fields: Environment, Re-use

EDXRF and WDXRF Analysis of Cd

It have been a must to analyzing the heavy elements in the products, the industrial waste and the material for re-use as the interest for the environment has been build up in the recent. Then we report the lower limits of detection (Minimum Detection Limits) of Cd in many materials with different measurement conditions.

■■■■Sample & Preparation

Cd is 0, 100, 250, 500ppm in the glassbeads. These glassbeads are Lithium tetra-boron oxide added Cd which are got cool and solidified after melted. Then they are measured without treatment. ■■■■Qualitative Result, Calibration Curve

(a) Qualitative Result (b) Calibration Curve Fig. 1 Cd 0,100,250,500ppm (10mmφ)

■■■■LLD(M.D.L)LLD(M.D.L)LLD(M.D.L)LLD(M.D.L)

Lower Limits of Detection(L.L.D) L.L.D 5.9ppm

■■■■RepeatabilityRepeatabilityRepeatabilityRepeatability

Average 107ppm

Repeatability 1.2ppm Coefficient of Variation 1.1%

■■■■Analytical Conditions

Instrument : EDX-700

X-ray Tube : Voltage :

Current : Filter :

Atmosphere : Measurement :

Diameter : Measurement Time :

Dead Time :

Rh target 50kV Auto Zr Air 10mmφ,5mmφ, 3mmφ,1mmφ 600sec 0~25%

■■■■Relationship of Analytical Conditions and Lower Limits of Detection(L.L.D)

L.L.D(M.D.L) of different measurement conditions are shown in Table 1. The difference is aperture and measurement condition. EDX-700/800/900 has the optional 4 normal apertures, which are 10mmφ, 5mmφ, 3mmφ, 1mmφ, and optional special aperture, which is 0.3mmφ.

Table 1 L.L.D of Each Measurement Time & Diameter (ppm) Diameter/Time 30Sec 100Sec 300Sec 600Sec 1000Sec

10mmφ 26 14 8.3 5.95.95.95.9 4.6 5mmφ 27 15 8.6 6.16.16.16.1 4.7 3mmφ 36 20 11 8.18.18.18.1 6.3 1mmφ 103 56 33 23232323 18

0.3mmφ 309 169 98 69 53 Thick are actually measured values, others are calculated values.

■■■■Relationship of Material and Lower Limits of Detection(L.L.D)

The L.L.D(M.D.L) are calculated theoretically for some materials such as cellose, resin and soil. And they are shown in Table 2.

Table 2 L.L.D of Each Sample Material Main Composite L.L.D(ppm) Density Glassbead Li2B4O7 5.9 1.3 Poly Vinyl Chrolide C2H3Cl 11 1.16~1.7 Cellose C6H10O5 5.9 -- Water H2O 6.3 1 ABS resin C15H17N 5.3 0.98~1.12 Soil SiO2 8.6 2.65 Ash CaO 18 3.3~3.4

RaynRaynRaynRaynyyyy ApplicationApplicationApplicationApplication DataDataDataData No.No.No.No.20202020

RaynyRaynyRaynyRayny EDXEDXEDXEDX----700/800700/800700/800700/800/900/900/900/900 ApplicationApplicationApplicationApplication DataDataDataData No.No.No.No.21212121 Field : Environment, Recycling

EDXRF Analysis of Incinerated AshEDXRF Analysis of Incinerated AshEDXRF Analysis of Incinerated AshEDXRF Analysis of Incinerated Ash

The use of XRF measurement is expanding in the environmental and recycling fields more and more. One is content control of Calcium oxide, silica and alumina which are main constituents of the incinerated ash, and then this ash is used recycling such as cement material, building materials. Tow is check of Chlorine. Three is exist or not of harmful heavy elements such as lead. This report describes the Qual-Quan analysis of incinerated ash and empirical correction method which is useful for precious quantification of trace elements.

<Qualitative<Qualitative<Qualitative<Qualitative----Quantitative Analysis of Incinerated Ash>Quantitative Analysis of Incinerated Ash>Quantitative Analysis of Incinerated Ash>Quantitative Analysis of Incinerated Ash> ■■■■Sample Preparation

5um polypropylene was stuck onto the base of powder sample receptacle into which approximately 3g of the sample was put without any preparation.

■■■■Result of Qualitative and Quantitative Analysis

Fig.1 shows qualitative analysis results and quantitative values obtained by the FP method for incinerated ash. Chlorine and heavy elements of small contents are detected and quantified easily. These constituents were assumed as oxide.

(a) Ti-U Qualitative Result

(b) Na-Sc Qualitative Result

(c) Quantitative Result

Fig.1 Qualitative and Quantitative Analysis of Ash

<Calibration Curve of Trace Elements><Calibration Curve of Trace Elements><Calibration Curve of Trace Elements><Calibration Curve of Trace Elements> ■■■■Sample

The compounds are what standard solutions of AA were dropped on the reagent SiO2 powder. These were dried and mixed homogeneously. ■■■■Sample Preparation

5um polypropylene was stuck onto the base of powder sample receptacle into which approximately 3g of the sample was put without any preparation.

■■■■Calibration Curve

The calibration curves of Pb, Zn and Cu are shown in Fig.2. Then Lower Limits of Detection(L.L.D) and accuracy calculated from them are shown in Table 2.

Pb Zn Cu Fig.2 Calibration Curves

Table 1 Calibration Curve

Element Pb Zn Cu Range 0～1000 0～4000 0～5000

Accuracy 7.0 22 60 Lower Limit of Detection 31 25 22

■ Analytical Conditions <Qualitative Analysis>


Voltage - Current ::



EDX-700 Rh target 50kV-(Auto) 15kV-(Auto) Vaccum 10mmφ 100sec 25%

<Empirical Correction Analysis> Instrument : X-ray Tube :

Voltage - Current : Filter :



EDX-700 Rh target 50kV-(Auto) Ni,Ti Vaccum 10mmφ 100sec 25%

RaynyRaynyRaynyRayny ApplicationApplicationApplicationApplication DataDataDataData No.No.No.No.21212121

Rayny EDX-700/800/900 Application Data No.22

EDXRF Analysis of Cd and Pb Fields : Electrical and electronic equipment, Environmental, Recycling

SInce the concerns regarding harmful heavy metals increase in numerous fields, improvement in the detection sensitivity of XRF analysis and the quantitative accuracy in non-standard-size samples is required. Shimadzu has approached these improvements in two ways. First, the detection sensitivity has been increased by a factor of 2 to 3 compared to conventional machines, thanks to changing the primary filter. Second, the improvement of the quantitative accuracy, regardless of the thickness, form, and size of the sample, using the BG (background) internal standard correction method1)2) has been examined. The results of this research show the utility and strength of XRF analysis as maximizing high throughput & non-destructive analysis. This system is very effective for use in various regulational compliance checks, such as the WEEE & RoHS directives (regulation values are unpublished at the present, Dec 3rd, 2002) and the ELV directive in the EU. <Increased Sensitivity to Cd and Pb>

The detection limits of Cd and Pb in polymer resins have been improved. The new lower limit of detection (LLD) is now down to about 1/2 the previous LLD attained with conventional methods for Cd and 1/3 of that for Pb. This is achieved with two changes. One is the improvement in S/N ratio by changing the primary filter to Mo (for Cd, Tc-Ba) and Ni (for Pb, Ga-Mo, Hg-U). The other is doubling the power of the X-ray tube. ■ Samples Cd:PVC (polyvinyl chloride) 0, 24, 48, 94, 190, and 300 ppm Pb:PVC (polyvinyl chloride) 0, 24, 67, 230, and 500 ppm ■ Qualitative result and Lower Limits of Detection (1) Cd 24ppm

(2) Pb 24ppm

Table 2 L.L.D. of Pb in

PVC Nickel filter

4 ppm (300 sec)3.7 ppm in

polyethylene

Table 1 L.L.D. of Cd in

PVC Mo filter

3. 7 ppm (300 sec) 1.9 ppm in

polyethylene

8.

For actual samples, since additive agents such as pigments and stabilizers may be present, the LLD may differ.

<Improvement in the quantitative accuracy by the BG internal standard correction> ■ Sample Standard sample :P E (polyethylene) standard sample, molded BCR-680, 681, and PVC Evaluation sample: Each form of BCR-680 (Refer to photographs below)

Molds Multiple Pellets One pellet Films Curved Parts

Rayny Application Data No.22

■ Quantitative Results (1) Form, quantity, thickness, position, etc. were investigated. The results are shown in Table 3.

Table 3 Comparison with and without using the BG internal standard correction. Cd Pb

with correction without with correction without Sample

BCR-680 (a) (b) (a) (b) (a) (b) (a) (b)

Molding, STD 140.8 1.00 140.8 1.00 107.6 1.00 107.6 1.00 Multiple Pellets 137.2 0.97 85.5 0.61 105.0 0.98 74.1 0.69

One piece on center 151.9 1.08 15.5 0.11 111.9 1.04 17.3 0.16 One on the side 174.5 1.24 26.6 0.19 109.9 1.02 (-8.5) --

One on back side 194.4 1.38 6.8 0.05 65.0 0.60 (-8.3) --

Pellet

One on right side 224.7 1.60 6.7 0.05 90.6 0.84 (-8.2) -- One sheet 143.4 1.02 57.5 0.41 104.7 0.97 57.9 0.54

Two sheets 135.1 0.96 99.1 0.70 103.3 0.96 90.6 0.84 Three sheets 140.7 1.00 132.5 0.94 101.1 0.94 109.5 1.02

Film

Four sheets 134.5 0.96 138.6 0.98 104.8 0.97 114.5 1.06 Curved Surface 146.8 1.04 11.4 0.08 97.0 0.90 15.4 0.14

(a) Quantitative value, (b) Ratio against standard value (2) The quantitative test of the PE samples was carried out to investigate the effect of different resins using the PVC calibration. The results are shown in Table 4.

Table 4 Comparison with and without using the BG internal standard correction. Cd Pb

with correction without with correction without Sample BCR-

(a) (b) (a) (b) (a) (b) (a) (b) 680(STD) 124.9(140.8) 0.89 171.4(140.8) 1.22 76.7(107.6) 0.71 320.3(107.6) 2.98 681(STD) 16.3(21.7) 0.75 25.3(21.7) 1.17 9.4(21.7) 0.68 84.9(21.7) 6.15

■ Conclusion

When the BG internal standard correction is performed, the errors caused by variation in form and thickness are within ±10%, which is fairly effective compared with the ~90% when not correcting for this. However, since this exceeds 10% for one pellet when the measurement position is not in the center, it is necessary to use a CCD camera option for precise positioning. Moreover, even in different types of resins, this correction is quite effective for Pb, although not quite as accurate for Cd. ■ The BG-Internal standard correction method

The internal standard correction is a method of taking the fluorescent X-ray intensity and the scattered ray (BG), RhKa(primary X-ray target material), or the Compton scattered X-rays, in order to remove changes in absolute intensity due to variations in the density, form, or size of a sample. In addtion, X-rays from a matrix element or another component element may be used as an internal standard as a complement to the scattered rays.

References

1) Kimiko Seno, Hideo Ishizuka, Yoichi Motoyoshi and Kazuyuki Shiraishi, (2002): Quantitative chemical analyses of rocks with X-ray fluorescence analyzer: (3) Rare

earth elements, Antarctic Record , Vol.46, No.1, 15-33

2) Hirotomo Ochi, Shinji Watanabe (2002): X-ray fluorescence analysis of minor heavy elements in soil and rock using theoretical intensity of X-ray scattering, Summaries

of the 38th X-ray National annual discussion of the discussion group X-ray, 20

Rayny EDX-700/800/900

Application Data No.23

Field: Precious metals, recycling

EDXRF Analysis of Precious Metal

EDX is used for simple judgment of ornaments containing precious metals like composition analysis, analysis of additions and ranking by the result, ascertainment of the truth. Elements like Platinum (Pt), Gold (Au), Silver (Ag), Cupper (Cu) are well known, but in case additions like Palladium (Pd), Ruthenium (Ru), and plating of Rhodium (Rh), that are not prevailing, are contained, judgement made by weight or observation may not be sufficient. EDX can provide solution for this issue with non-destructive and short time analysis. The following is the example of such case.

<High speed analysis of the composition> ■ Sample Ornament Ａ, Ｂ, Ｃ, Ｄ, Ｅ ■ Qualitative Result Fig.1 shows graph of qualitative analysis result of 5 kinds of ornament. Contained elements and its quantity are clearly observed. Zr filter is used for X-ray primary filter and this helps simultaneous detection of Rh and Ru, which normally are difficult elements to detect, this analysis achieves high throughput like 10sec/1sample).

Fig.1 Qualitative result of five kind of ornament including precious materials

Table 1 Detected elements 試料 Co Cu Ru Rh Pd Ag Pt Au A ● ● ● ● B ● ● C ● ● ● ● D ● ● ● E ● ● ●

■ Analytical Conditions


Voltage - Current : Primery Filter :


Measurement Time :

EDX-700 Rh target 50kV-(Auto) Zr Air 10mmφ 10sec

<Qualitative-Quantitative analysis of minute area with collimator> ■ Sample

Pure gold Ｆ, Golden alloy G, H, Platinum Alloy Ｉ, Ｊ ■ Qualitative Result With collimator (1mm dia.), composition of small area can be analyzed. Fig.2, Table2 and Fig.3 and table 3 show

qualitative – quantitative analysis result of the samples. About 1% difference of Au, Ag and Cu can be observed.

Fig. 2 Qualitative result of golden alloy s with 1mmφ collimator

Fig. 3 Qualitative result of platinum alloy s with 1mmφ collimator

Table 2 Quantitative result of golden alloys

with 1mmφ collimator Au Ag Cu Ｆ 100 ― ― Ｇ 76.9(0.23) 11.7(0.15) 11.4(0.06) Ｈ 76.0(0.23) 12.1(0.16) 11.8(0.07)

（）Std.Dev. Table 3 Quantitative result of platinum alloys

with 1mmφ collimator Cu Pt Pd Ｉ 7.3(0.04) 85.3(0.25) 7.3(0.13) Ｊ 5.1(0.04) 89.5(0.25) 5.4(0.12)

（）Std.Dev.

■ Analytical Conditions Instrument : X-ray Tube :

Voltage - Current : Primery Filter :


Measurement Time :

EDX-700 Rh target 50kV-(Auto) without, Zr Air 1mmφ 100sec


Rayny EDX-720


Field：Electrical and electronic equipment, Environmental, Recycling

EDXRF Analysis of Chromium, Mercury, Bromine, Lead and Cadmium in Plastic Materials

Restriction of Hazardous Substance (RoHS) will be implement in European Union (EU) as environmental efforts. In this

situation, it is getting more important to measure the hazardous elements in electrical and electronic equipments. EDXRF is

getting used for screening method generally because EDXRF can measure various sample states (solid, powder, liquid and so

on) as nondestructive and rapid analysis technique. In this report, the sensitivity and repeatability of each hazardous element are

performed by EDX-720 using polyvinyl chloride (PVC) resin plastic material, which used as electrical cable covering or chassis.

<Features of EDX-720>

The sensitivity of hazardous elements such as chromium, Mercury, Bromine, Lead and Cadmium improves more than 2

times higher adopting new type of filters and high counting rate systems.

■Sample

PVC (PolyVinyl Chloride) samples included Cr, Hg, Pb, Br and Cd

made by Sumika Chemical Analysis Service, Ltd.

Concentration (ppm)

Cr Hg Pb Br Cd

No.1 0 0 0 0 0

No.2 50 50 50 1200 25

No.3 100 100 100 600 50

No.4 300 1200 300 300 75

No.5 600 600 600 100 100

No.6 1200 300 1200 50 300 Above concentration value is calibrated by ICP/MS.

■Result - Lower Limits of Detection - Element Cr (Ka) Hg (La) Pb (La) Pb (Lb1) Br (Ka) Cd (Ka)

Voltage (kV) 30 50 50 50 50 50

Current (uA) 190 446 446 446 446 1000

Measurement time (sec.)

300 300 300 300 300 300

L.L.D. (ppm) 10.9 4.2 2.9 3.7 1.4 2.5 ・ The measurement conditions of each element are optimized.

・ The calculation of Lower Limits of Detection (L.L.D.) is used below formula.

*The formula of L.L.D. k ： Calibration curve constant

Iback ： Background intensity

T ： Measurement time

TIkDLL back××= 3...

・ The analysis of Br-Ka is used overlap correction because Br-Ka overlaps with Hg-Lb1.


■Result - Calibration Curve - The calibration curves of each element are shown in Fig.1 to Fig.6.

Fig.1 Calibration curve for Cr-Ka Fig.2 Calibration curve for Hg-La Fig.3 Calibration curve for Pb-La

Accuracy : 9.1ppm Accuracy : 30ppm Accuracy : 23ppm

Fig.5 Calibration curve for Br-KaFig.4 Calibration curve for Pb-Lb1 Fig.6 Calibration curve for Cd-Ka

Accuracy : 26ppm Accuracy : 13ppm Accuracy : 3.3ppm

■ Result - Repeatability Test - Using the PVC sample measures the 10 times repeatability test.

Element Cr (Ka) Hg (La) Pb (La) Pb (Lb1) Br (Ka) Cd (Ka)

Standard value (ppm) 97 120 110 98 54

Quantitative value (ppm) as average

110.9 104.3 102.4 108.4 111.8 52.5

Standard Deviation (ppm)

1.8 2.3 1.3 1.2 0.7 1.5

Practical CV(%) 1.6 2.2 1.2 1.1 0.6 2.9 Theoretical

CV(%) 1.5 1.5 1.2 1.1 0.7 1.3 *Standard value is calibrated by WDX using calibration curve method.


―――――――――――――――――――――――――――――――――――――――――――――――――― Instrument : EDX-720 X-ray Tube : Rh target Filter : Al (for Cr), New Filter #1 (for Hg, Pb, and Br), New Filter #2 (for Cd) Voltage - Current : 50kV - (Auto)μA except for Cr Cr : 30kV – (Auto) μA Atmosphere : Air Measurement Diameter : 10mmφ Measurement Time : 300sec Dead Time : 40% ――――――――――――――――――――――――――――――――――――――――――――――――――

Rayny EDX-720



EDXRF Analysis of Chromium, Lead and Cadmium in Metals

(Brass) Restriction of Hazardous Substance (RoHS) will be implement in European Union (EU) as environmental efforts. In this




performed by EDX-720 using brass, which used as screw or spacer.




■Sample

Brass samples included Cr, Pb, Cd

made by Sumitomo Metal Technology Inc.

Concentration (ppm)

Cr Pb Cd

GBR1 <10 <10 <10

GBR2 960 1000 60

GBR3 450 200 20

GBR4 1120 100 40

GBR5 70 1200 170

GBR6 160 510 140 Above concentration value is calibrated by ICP/MS.

■Result - Lower Limits of Detection - Element Cr (Ka) Pb (La) Pb (Lb1) Cd (Ka)

Voltage (kV) 30 50 50 50

Current (uA) 20 121 121 1000


300 300 300 300

L.L.D. (ppm) 33.9 69.3 35.5 8.2 ・ The measurement conditions of each element are optimized.








Fig.1 Calibration curve for Cr-Ka Fig.2 Calibration curve for Pb-La Fig.3 Calibration curve for Pb-Lb1

Accuracy : 23ppm Accuracy : 15ppm Accuracy : 27ppm

Fig.4 Calibration curve for Cd-Ka

Accuracy : 4.3ppm

■ Result - Repeatability Test -

Using the brass sample (BCR6) measures the 10 times repeatability test.

Element Cr (Ka) Pb (La) Pb (Lb1) Cd (Ka)

Standard value (ppm) 160 510 140


138.4 513.5 495.2 138.5


9.2 38.2 29.1 4.2

Practical CV(%) 6.7 7.4 5.9 3.0 Theoretical

CV(%) 2.7 3.6 3.0 2.1 *Standard value is calibrated by ICP/MS.


―――――――――――――――――――――――――――――――――――――――――――――――――― Instrument : EDX-720 X-ray Tube : Rh target Filter : Without (for Cr), New Filter #1 (for Pb), New Filter #2 (for Cd) Voltage - Current : 50kV - (Auto)μA except for Cr Cr : 30kV – (Auto) μA Atmosphere : Air Measurement Diameter : 10mmφ Measurement Time : 300sec Dead Time : 40% ――――――――――――――――――――――――――――――――――――――――――――――――――

Rayny EDX-720



EDXRF Analysis of Lead in Lead-Free Solder Materials





performed by EDX-720 using lead-free solder, which used for high mounting circuit boad.




■Sample

Lead-free solder samples included Pb

made by MBH ANALYTICAL LTD.

Concentration(ppm)

Pb

74X-E 262

74X-HN 820

74X-TC 1830

74X-AM 1740

74X-HA 250

74X-HB 590 Above concentration value is calibrated by ICP/MS.

■Result - Lower Limits of Detection - Element Pb (Lb1)

Voltage (kV) 30

Current (uA) 1000


300

L.L.D. (ppm) 24.8 ・ The measurement conditions of each element are optimized.







■Result - Calibration Curve - The calibration curves of Pb-Lb1 is shown in Fig.1.

Fig.1 Calibration curve for Pb-Lb1

Accuracy : 48ppm


Using the lead-free solder sample (74X-E) measures the 10 times repeatability test.

Element Pb (Lb1)

Standard value (ppm) 262


259.3


7.4

Practical CV(%) 2.9 Theoretical

CV(%) 2.5 *Standard value is calibrated by ICP/MS.


―――――――――――――――――――――――――――――――――――――――――――――――――― Instrument : EDX-720

X-ray Tube : Rh target Filter : New Filter #1 (for Pb) Voltage - Current : 30kV - (Auto)μA Atmosphere : Air

Measurement Diameter : 10mmφ Measurement Time : 300sec

Dead Time : 40% ――――――――――――――――――――――――――――――――――――――――――――――――――

Rayny EDX-720



EDXRF Analysis of Lead and Cadmium in Aluminum Alloy





performed by EDX-720 using brass, which used as plate in aviation or vehicle industry.




■Sample

Aluminum alloy sample included Pb and Cd

made by Sumitomo Metal Technology Inc.

Concentration (ppm)

Pb Cd

GAL1 70 10

GAL2 900 90

GAL3 200 20

GAL4 100 40

GAL5 1160 180

GAL6 540 140

Above concentration value is calibrated by ICP/MS.

■Result - Lower Limits of Detection - Element Pb (La) Pb (Lb1) Cd (Ka)

Voltage (kV) 50 50 50

Current (uA) 440 440 1000


300 300 300

L.L.D. (ppm) 3.7 3.3 2.2 ・ The measurement conditions of each element are optimized.








Fig.1 Calibration curve for Pb-La Fig.2 Calibration curve for Pb-Lb1 Fig.3 Calibration curve for Cd-Ka

Accuracy : 5.8ppm Accuracy : 10ppm Accuracy : 1.5ppm


Using the Aluminum alloy sample (GAL4) measures the 10 times repeatability test.

Element Pb (La) Pb (Lb1) Cd (Ka)

Standard value (ppm) 100 40


106.1 106.1 42.7


2.5 0.9 0.7

Practical CV(%) 2.4 0.9 1.7 Theoretical

CV(%) 1.3 1.1 1.2 *Standard value is calibrated by ICP/MS.


―――――――――――――――――――――――――――――――――――――――――――――――――― Instrument : EDX-720

X-ray Tube : Rh target Filter : New Filter #1 (for Pb), New Filter #2 (for Cd) Voltage - Current : 50kV - (Auto)μA Atmosphere : Air Measurement Diameter : 10mmφ Measurement Time : 300sec Dead Time : 40% ――――――――――――――――――――――――――――――――――――――――――――――――――

Documents

Analysis of Food for Contamination - Shimadzu...the possibility of matrix effects can and will affect instrumentation. It is vital that any XRF spectrometer have built in spectrographic