R. Härdtl, G.

Bolte, Heidelberg Cement Technology Center

A suitable measuring process for assessing the potential for brown

discoloration?
Magotteaux test for cement analysis
Yellowish to brownish discolorations restrict the quality of concrete products. These undesirable
discolorations are caused by small quantities of soluble iron ions brought to the concrete surface
through the pore system. There they can be bonded into the lime efflorescences that begins to form,
where already traces of them will cause yellowish to brownish discolorations of the crystal.
Discolorations of this kind that can be visually detected are triggered by a complex interaction of
numerous constitutive and process parameters. This begins with the choice of suitable constituent
materials of the concrete: cement, additions, admixtures and aggregate. Type, content and
granulometric distribution of the components play here a decisive role. The dense pore structure
required for the finished products can only be obtained with the proper mix and with appropriately
adjusted compaction. Temperature and air humidity, in particular during curing in the hours following
production and subsequent storage, significantly influence the type of discoloration as well as the time
at which they may occur.

Significance of the Magotteaux tests

Cement, as a possible source of water-soluble, divalent iron (FeO), is an essential constituent of
concrete. The Magotteaux Test [1] is recommended as a rapid and easy to perform analysis method
for semi-quantitative determination of the FeO content [2]. For the test, droplets of two defined
chemical solutions are applied to a cement or ground clinker specimen. The FeO content in the
specimen is then determined based on the resulting pink coloration of the solution (Table). The test
procedure is described in detail in [2]. In order to verify the precision of this test method for
determining the FeO content, various clinkers and cements were investigated. For this purpose,
clinkers were obtained from different cement plants as well as different types of cement. This provided
a representative cross-section of specimen materials. In parallel to the Magotteaux test, the exact FeO
contents in the specimens were ascertained by wet processing, using the typical titration of potassium
manganate solution.

Table 1. Assessment of the FeO content based on theMagotteaux test

Figure 1: Color reaction in the Magotteaux test

A comparison of the test results from the two methods of analysis shows that no or only very small
quantities of FeO are contained in a sample when no color reaction occurs. On the other hand,
however, no reliable conclusion on the magnitude of the FeO content can be derived based on the
coloration. In an extreme case, for example, virtually no FeO was detected by the wet process, despite
a very strong color reaction (FeO content implicating > 0.16 M.-%). Looking at the results of the tests
in which slight color reactions occurred in the Magotteaux test, for example, a substantial number of
specimens were found to be within the relevant range of 0.04 to 0.08 M.-% FeO. On the other hand,
however, there was also a relatively great number of specimens where the actual FeO content was
found to be less or even clearly above (Figure).

Assessment of results
What are the possible causes for the poor conformity of the results? For the Magotteaux test, a
subjective classification of color reaction is required for conducting a simple test. Here, errors are
possible. But this alone can be no plausible explanation for the discrepancies determined. The
Magotteaux test was initially designed for obtaining oriented conclusions on the conditions prevailing
in the burning zone of a cement kiln. Its application therefore focused on the investigation of clinkers or
pure portland cements. During reaction with the test solutions not only divalent iron can be fused, but
other ferriferous constituents as well. Modern cements, such as composite cements as (CEM II) and
Blastfurnace slag cements (CEM III) contain in addition to clinker further constituents of cement. In
particular in cements containing granulated blast-furnace slag, strong color reactions are almost
invariably observed with the Magotteaux test, although the measured FeO contents are much lower.
Here, quite obviously, the Magotteaux test reacts strongly to the ferriferous constituents. A
dependence of the amount of granulated blast furnace slag contained in the cement could not be
established. Even the prescribed removal of the ferriferous constituents by magnets prior to the
analysis, did not change the results.

Summary
The conclusion that a strong reaction of the Magotteaux test in cements indicates an increased
potential for brown discoloration, is clearly not in line with verified practical experience. It is for
example a well known fact that in particular the use of cements containing granulated blast-furnace
slag is an effective measure for reducing the risk of brown discoloration. More recent findings show
moreover that the FeO content of a cement is a rather unsuitable parameter for assessing the
potential for brown discoloration in a cement [3]. The amount of FeO that is as a rule required for
causing brown discoloration is very low and virtually always present in concrete. Of much greater
significance is how the iron ions are dissolved and are transported to the surface of the concrete.
Against this background, the Magotteaux test, from our point of view, appears to be an unsuitable
measuring process for assessing the potential for brown discoloration in cement, both for reason of the
imprecise measuring results and the lack of lack of significance of the parameters determined.

Literature
[1] American Magotteaux Corporation: A rapid test for detecting reducing conditions in the kiln. Test
discription. Brentwood 1992 [2] Manns, W.: Zur Braunverfärbung von Betonwaren – Möglichkeit der
frühzeitigen Erkennung. Betonwerk + Fertigteil- Technik 68 (2002) Heft 11, S. 32–47
[3] Härdtl, R.; Bolte, G.; Tax, M.; Dienemann, W.: Das Braunverfärbungpotenzial von Zementen.
Cement International, Heft 4/2003 (erscheint in Kürze)