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Approaching a universal sample preparation

method for XRF analysis of powder materials

Article January 2001

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APPROACHING A UNIVERSAL SAMPLE PREPARATION METHOD

FOR XRF ANALYSIS OF POWDER MATERIALS

John Anzelmo, Alexander Seyfarth, Larry Arias

Bruker AXS, Inc. Madison, Wisconsin

Abstract

It is well known that the preparation of metals and liquids for XRF analysis is fast, easy, and
usually requires little strategy. The preparation of powder samples such as silicates, carbonates,
slags, cements, ferro-alloys and other powdered materials however requires careful planning in
the way of additives, lubricants, binders, dilution, backing and holders. The ratio of binder to
sample must include forethought regarding the homogeneity of the briquette, the stability of the
briquette, the cleaning and cleanliness of the grinding vessel, and the performance requirements
of the analysis. The ideal situation would be to have one set of preparation materials, with only
one sample to additive ratio suffice for all powder preparations. Various preparation materials
and strategies are examined, and their usefulness toward achieving a universal preparation
method considered.

Introduction

The word approaching was chosen very carefully when deciding on the title of this paper,
because there is no universal preparation method for pressed powders. However, it is possible to
greatly reduce the number of different methods in many laboratories. Many laboratories use
widely varying techniques in their selection of preparation methods, when it may have been
possible for that laboratory to use only one method.

The use of a grinding aid or lubricant is the one material that is not made use of in many
laboratories. This material has many properties which make the consideration of other
parameters in the preparation method unnecessary. The grinding aid Vertrel XFTM (1) was
reported in a previous paper(2) to have these properties in the preparation of cement, clinker and
related raw materials. This lubricant, which replaces previously used Freon TF, is a clear
colorless liquid, which is not retained in the pressed pellet as shown by scans for fluorine in
finished sample briquettes. Vertrel XF is the trade name for 2,3 Dihydroperfluoropentane, and the
material Safety Data Sheet(1) (MSDS) for this product should be consulted for properties and
characteristics of this material. It is not intended for this method to be selected as a universal
method. But, rather, it is hoped that the concepts presented here will be applied, and more
thought given to reducing the number of variables considered when preparing various materials.

Discussion

There are many variables (Table 1) to consider when designing a method for preparation of a
material for XRF analysis. Many times, the container material chosen is W/C because of the
need to eliminate iron contamination when using steel grinding media. A grinding aid acts as a
lubricant, and minimizes if not eliminates, the iron contamination, so that a hardened steel
container can be used. The binder to sample dilution is another area where multiple methods can

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be reduced. Typical binders stick to the grinding vessel and components unless the proper ratio
is determined, making many trial and error experiments necessary. The use of Vertrel XF along
with a Whatman CF11 fibrous cellulose(3) minimizes the need to vary dilution ratios. The low
ash content (typically ~ 50 ppm) of this binder, used in a dilution ratio of 20% insures that the
most contamination possible from the binder is 10 ppm total. No expanding of briquettes has
been observed when using the the formula listed in Table 2, even after years.

After grinding, the mixture exists as a slurry. A gentle draft for ~15 seconds will vaporize the
liquid. The remaining powder can be brushed from the container and components very easily,
almost dust free. The container and components need only a gentle wiping with clean,
disposable, paper towels to remove contamination for the next grind.

Table 1. Sample Preparation Variables

1. Grinder Type (manual, mixer, ring and puck disk mill)
- Particle size distribution desired
- Grinding time allowed or desired
2. Container Material (Fe/Cr, W/C, ZrO, Si/N, Al2O3)
- Weight, brittleness, expense
3. Grinder cleanliness and container condition (rust outside inserts)
4. Workbench contamination
5. Sample volume
6. Container/Ring/Puck/Lid condition
7. Component dimensions and pitting
8. Binder type and dilution
9. Grinding Aid Lubricant
10. Dust
11. Sample contamination
12. Ease of cleaning

Table 2. Proposed General Method for Sample Preparation

Disc Mill (ring and puck type)
Hardened steel container and components
10.00x grams of sample
2.50x grams Whatman CF11 cellulose as binder
7 ml Dupont Vertral XF
90 second grinding time
15 second press at 40, 000 lbs. in 40mm die mold
Tapered Aluminum pellet cup

The elimination of contamination for subsequent sample preparations is of paramount

importance. Typical binders leave material stuck to the components that is difficult to remove,
even after thorough wiping (Figure 1). Washing with water is then necessary, causing loss of
time.
In some cases, such as when using Boric acid as a binder (Fig. 2), this effect is quite noticeable.
The sample preparation method shown in Table 2 makes cleaning the grinding vessel and
components easy, dustless, and contamination free, while making a homogenous, stable, sturdy

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pellet. After the liquid has been removed from the freshly ground slurry, most materials appear
evenly and smoothly distributed over the grinding media (Fig. 3). After the material is brushed
out, and the vessel and components are wiped clean with a paper towel, the vessel appears
spotless as shown in Figure 4. In many critical applications where tight precision and accuracy
specifications must be met, the smallest amount of contamination from the vessel or previous
samples will not allow the method to pass. Table 3 shows the accuracy and precision
requirements of such a method, ASTM C-114 Qualification(2).

Table 3. ASTM C-114 Qualification Specifications

Max Max
Difference Difference of
between the Average
Duplicates of Duplicates
on alternate from SRM
Component days Certificate
SiO 2 0.16 0.2
Al2O3 0.20 0.2
Fe 2O3 0.10 0.10
CaO 0.20 0.3
MgO 0.16 0.2
SO 3 0.10 0.1
Na2O 0.03 0.05
K 2O 0.03 0.05
TiO2 0.02 0.03
P 2O5 0.03 0.03
ZnO 0.03 0.03
Mn2O3 0.03 0.03

The instrumentation used to generate data for this study was the S4 Explorer (Figure 5).

Many other materials (Table 4) were evaluated for preparation using the General Method
proposed, and all had excellent results except gypsum, which is well know for its preparation
problems unless pressed as is.

Table 4. Various materials types prepared successfully with proposed General Method

Titanium, Iron, Copper Ores,

Corrundum, Mullite, Kyanite, Etc.
Coke
FeMo, FeSi
Kaolin and lower quality clays
Cement, Limestone
Salts
Quartz, Silicates
Slags

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Figure 1. Components after brushing typical binder

Figure 2. Components after brushing boric acid binder

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Figure 3. Material after grinding with lubricant

Figure 4. Components after brushing lubricant used with binder

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Figure 5. S4 Explorer XRF Spectrometer

Conclusion

The use of a grinding aid or lubricant, together with the proper binder and dilution, can eliminate
most of the variations in sample preparation for widely varying materials. A lubricant utilized
during the grinding process can eliminate wear and contamination, reduce dust, contribute to
stable, homogenous briquettes, and reduce operator fatigue. The authors have no affiliation with
the vendors mentioned in this article, and only mention specific names because these materials
are known to produce the desired results.

References:

1. MSDS VERTREL XF, Dupont Chemicals, Engineering and Product Safety, P.O. Box
80709, Chestnut Run, Wilmington, DE 19880-0709, December 29, 1998

2. Anzelmo, Seyfarth, Arias, XRF Analysis of Cement ASTM C-114 Qualification,

Presented at the Denver X-ray Conference, Steamboat Springs, CO, August 4, 1999

3. Whatman CF11 fibrous, cellulose powder, Whatman International Ltd., Springfield Mill,
James Whatman Way, Maidstone, Kent, ME142LE England

4. Uhlig, Mauser, Granacher, XRF Spectrometers For Multi-Element Analysis, World

Cement, June, 1999

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