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Measuring T

he coating industry understands


that salt contamination under-
neath a coating can cause seri-
ous problems in future years.
This is because of the hygroscopic nature

NaCl, Salt, of salt. This tendency to attract water,


in combination with the permeability of
a coating, creates an accumulation of
water molecules between the substrate
and coating. The presence of these water

and Soluble molecules, together with the entrapment


and migration of oxidation agents, is
ideal for creating an electrochemical
shift that causes corrosion in conjunction

Contaminants with the ions from salt present.


Blasting or mechanical cleaning will
not remove these salt molecules com-
pletely and often causes chloride inclu-
sion into the substrate, making the situ-

with Bresle ation even worse. Washing the surface


with deionized water is the most-used
solution. A substrate with a controlled
amount of soluble salts is critical in to-

Patches—Part 1 day’s protective coating work and is an


Q[[]M QV MIKP XIQV\ [XMKQÅKI\QWV _PQKP
nowadays can include limits for soluble
salts. Some regulations set the maximum
N. FRANKHUIZEN, TQC, Zevenhuizen, The Netherlands concentration of soluble salts, measured
as sodium chloride (NaCl), on a surface
to 20 mg/m2.

The presence of salts on a substrate can have serious The Principle of a


Bresle Test
effects on coating performance. This two-part article When performing the soluble salt test,
water is injected in a patch that is placed
on the surface. The injected water dis-
discusses understandings and misunderstandings solves the salt present at the surface. The
salt solubility in water depends on the
about salt contamination, describes the Bresle test type of salt. Common salt, NaCl, can be
dissolved in cold water to a concentra-
and the complexities involved in obtaining accurate tion of 357 g/L. Not only does solubility
differ among salts, but conductivity also
data, and explains the importance of correct data differs. Thus, when taking a measure-
ment, common salt and all other salts
interpretation. Part 2 will be published in the present on the surface are dissolved. This
mixture of salts is eventually measured

December 2009 issue of MP.


with a conductivity meter or by other
means.
36 MATERIALS PERFORMANCE November 2009
C O AT I N G S & L I N I N G S

FIGURE 1

Misunderstanding of Solubility
What is Actually The nominal volume in the test cham-
Measured ber of the original Bresle patch is 2.5 cm3.
Because it is impossible to predict Considering the volume and solubility of
which salts are present at the surface, an salt, it is possible to dissolve 892.5 mg of
assumption is made in the Bresle method. common salt in the patch. This correlates
The term “measured as sodium chloride” to 7.29 × 105 mg/m2 NaCl. Comparing
indicates that this mixture of salts is inter- this to the IMO regulation of 20 mg/m2,
preted as being only NaCl. Clearly indi- there is a factor of ~36,000 between these
cating how the conductivity is interpreted concentrations. Thus, the solubility of salt
is essential when creating a report. At is not an issue when conducting the test.
present, there are several interpretations A level of 20 mg/m2 NaCl is actually only
in use. Some speak about NaCl while oth- 0.025 mg NaCl in the patch. Even salts
ers mention mixed salts or just chlorides, that are harder to dissolve will be present
and each has a different calculation factor. in such concentrations that should not
provide any solubility problems.
Typical layman’s understanding of salt.
NaCl, Salt, and Soluble iStock photo. Not all salts are equally soluble in
Contaminants water; there is a great difference in solu-
Our vocabulary is full of words that bility. While NaCl can be dissolved to
have a double meaning. If you ask people create this electrolyte by splitting into 357 g/L, its chemical cousin silver
what salt is, they virtually always reply by ions. Within a solution, NaCl is no longer chloride (AgCl) can be dissolved only
referring to the stuff we put on our French present as such; it has split into sodium for 0.00089 g/L. This is stated as the
fries (Figure 1). If you ask, what is “so- and chloride ions. This also indicates that solubility product K sp. At these con-
dium chloride?” they say it is salt. This it is not possible to have just chloride ions centrations, the solution is saturated
statement is true, but, the other way on a surface. and equilibrium is reached between
around is not. Think of it as follows: a cow
is an animal; however, an animal does not FIGURE 2
have to be a cow. The same is true for
NaCl (common salt). NaCl is a salt; how-
ever, salt does not have to be NaCl. Here
the extensive meaning of the word “salt”
starts to cause a problem.
The chemical meaning of the word
salt is a lot broader than the common
word. Salt is a neutral product formed by
a neutralization reaction between acids
and bases. The reaction product is an
ionic compound. This means that when
the product is dissolved in water, it splits
into an anion (negatively charged parti-
cle) and a cation (positively charged
particle). Both the anion and the cation
can be inorganic or organic, as well as
mono- or polyatomic (one or multiple
atoms combined). The breakdown into a
cation and anion produces an electrolyte
in water. Only the products that dissolve
in water and not those that disperse will NaCl in crystal structure as present on surfaces. Fotolia photo.

November 2009 MATERIALS PERFORMANCE 37


C O AT I N G S & L I N I N G S Measuring NaCl, Salt, and Soluble Contaminants with Bresle
Patches—Part 1

dissolved and non-dissolved. A dissolved factor that is adjusted during calibration. sured as NaCl. The statement “mea-
salt produces ions and forms an electro- When taking a conductivity reading of sured as sodium chloride,” means that
lyte. The non-dissolved salt does not the solution acquired with the Bresle not only NaCl is measured but also all
produce ions and does not produce an method, all dissolved salts are measured, other dissolved salts.
electrolyte. This means there is no sig- even the small dissolved portion of the To have a traceable result, an easy
VQÅKIV\ QVKZMI[M QV KWVL]K\Q^Q\a -^MV insoluble salts. reference salt has to be selected. NaCl is
calcium carbonate (CaCO3) is a salt, a This electrolyte is what can be mea- chemically a reference salt. Not only is
very insoluble salt, but nevertheless a sured by a conductivity gauge. The it suitable as a reference salt, but it also
salt. It has a solubility of 0.014 g/L. higher the concentration, the higher the is the biggest cause of problems and has
Figure 2 is an illustration of NaCl in its conductivity. The conductivity of an the highest share in concentration, mak-
crystal structure as present on surfaces. electrolyte not only changes by concen- ing it the ideal salt to report. At present,
tration, but also by variation in the ions there are multiple interpretations in use.
Determining Solubility present. The same concentrations of The most common used is the reference
To determine if a salt is soluble, there NaCl or potassium chloride (KCl) pro- to NaCl. Some others are mixed salts
is a chemical rule. In chemistry, a con- duce electrolytes with a different electric and chloride. With the Bresle method,
centration in mg/L is not interesting, conductivity. Conductivity is thus quan- this relates to the respective factors 6, 5,
because of the difference in weight be- titative and qualitative dependent. Tem- and 3.6. Here, factor 6 calculates as
tween different atoms and molecules. The XMZI\]ZMIVLXZM[[]ZMIT[WQVÆ]MVKM\PM NaCl, factor 5 as mixed salts, and factor
amount of molecules is what is of interest measurement. With higher temperature 3.6 to an industry-fantasized possibility
to a chemist. Look at it as bolts and nuts. comes a higher enthalpy. Enthalpy is a of having only chloride ions present.
A bolt is heavier than a nut; to have as measure of the heat content at subatomic Even when test methods are speci-
many bolts as nuts means that you need level. Very simply stated, this means that ÅMLQ\_W]TL[\QTTJM^MZaPMTXN]TQNITT
1 kg of nuts to screw onto 2 kg of bolts. A the hotter a subatomic particle gets, the involved parties stated the salt concen-
chemist looks at a concentration in more active it gets, as does its reactivity tration the correct way. Not stating the
mol/L. The term moles can best be com- and interactivity. A microwave oven does answer with the right interpretation can
XIZML\W\PMLMÅVQ\QWVZMIK\Q^MWZ_WZS- not put heat in your food; it imparts more cause serious differences in the result. If
ing units. In chemistry, the solubility is energy/activity, which in turn produces \PM[XMKQÅKI\QWV[IZMQVKPTWZQLMIVL\PM
stated in three groups: heat. The higher the temperature in a measurement is made as NaCl, there is
A salt is soluble if it dissolves in water solution, the higher the conductivity. I[QOVQÅKIV\LQNNMZMVKM\PI\KIVTMIL\W
to give a solution with a concentration of Modern conductivity gauges are compen- extreme costs caused by unnecessary
at least 0.1 mol/L at room temperature. A [I\MLNWZ\PQ[\MUXMZI\]ZMQVÆ]MVKM<W cleaning.
salt is insoluble if the concentration of an determine conductivity, reference salts
aqueous solution is <0.001 mol/L at room are used. This is done by having a solu- What is the Correct
temperature. Slightly soluble salts give \QWV_Q\PIÅ`MLKWVKMV\ZI\QWVWNIX]ZM Interpretation of Data?
solutions that fall between these extremes. reference salt, usually KCl. Referring to the total salt mixture on
+WVL]K\Q^Q\a Q[ I VWV[XMKQÅK UMI- a surface as NaCl is an interpretation.
Conductivity surement method; it detects all soluble Let us, however, compare it to measuring
The method of measuring the conduc- salts, with all different varieties. The salt \ZINÅKRIU[<PMTMVO\PWNI\ZINÅKRIUQ[
tivity of an electrolyte is not the same as mixture that is found in the measure- not measured, but calculated. It is a
the procedure used to measure conductiv- ment cell usually is not made up of one multiplication of the amount of cars
ity of copper wire. Conductivity is mea- type of salt. This multi-ion electrolyte times their length. You never know,
sured with a sine wave potential across requires an interpretation when the PW_M^MZ _PQKP KIZ[ IZM QV \PM \ZINÅK
\_WLMÅVMLXTI\M[[M\I\ILMÅVMLLQ[\IVKM conductivity has to be reported as a jam, so you don’t know the exact length
from each other. Between these plates, the concentration. This interpretation is one WNMIKPKIZAW]KIVTWWSI\[ITM[ÅO]ZM[
ions in the electrolyte conduct the current of the biggest misunderstandings when in the car industry and calculate an aver-
backward and forward. The size and measuring. The results, according to age car length from this, but what about
distance between the plates determine the ISO 8502-61 and ISO 8502-9,2 have to the old cars? Second, cars are just like salt
cell constant. This constant is also the be reported as mg/m2 soluble salts mea- deposits—region specific. Americans
38 MATERIALS PERFORMANCE November 2009
C O AT I N G S & L I N I N G S

drive Hummers, Europeans drive Mer- Conclusions 2 ISO 8502-9, “Preparation of steel substrates
cedes, and Asians drive the Tata Nano. before application of paints and related
Part1 has presented a general under- products—Tests for the assessment of surface
There is no real comparison and unifor- standing of salts and also explained many cleanliness—Part 9: Field method for the
UQ\a<PM\ZINÅKKWV\ZWTTMZ[NWZ\PMKWI\- misunderstandings. The Bresle test has conductometric determination of water-
ing industry, in this case ISO, gave the been introduced, along with many as- soluble salts” (Geneva, Switzerland: ISO).
[WT]\QWV)\ZINÅKRIU[\I\MLQVTMVO\PQ[ pects of salt solubility and solution con-
calculated by the length of just one car, a ductivity. Part 2, to be published in the N. FRANKHUIZEN is a commercial technician at TQC,
1949 Cadillac Deville, the length of which Nijverheidscentrum 14, Zevenhuizen 2761JP, The
December 2009 issue of MP, will cover Netherlands, e-mail: nico@tqc.eu. He is chairman
is known worldwide. This means that the sampling procedures, measurement tech- of NEN NC 342.035, The Dutch mirror committee of
IUW]V\WNKIZ[QVIVa\ZINÅKRIU_WZTL- niques, the effect of climate on test results, ISO TC 35, Paint and Varnishes. He has 10 years of
wide can thus be multiplied by a standard and comment on commercially available laboratory experience in the field of chemical
^IT]MIVLITT\ZINÅKRIU[IZM\PMVKWU- test kits. pretreatment and corrosion protection followed by
parable. The same goes with salt mea- work at TQC.
surement—soluble salts in g/m 2 are References
measured as NaCl. 1 ISO 8502-6, “Preparation of steel substrates
before application of paints and related
products—Tests for the assessment of surface
cleanliness—Part 6: Extraction of soluble
contaminants for analysis—The Brestle
method” (Geneva, Switzerland: ISO).

November 2009 MATERIALS PERFORMANCE 39


art 1 of this article1 presented a

Measuring P general understanding of salts and


also explained many misunder-
standings. The Bresle test was
introduced, along with many aspects of

NaCl, Salt, salt solubility and conductivity. Part 2


covers sampling procedures, measure-
ment techniques, the effect of climate on
test results, and comments on commer-
cially available test kits.

and Soluble Dilution


Contrary to solubility, dilution is a
major cause for possible errors. To make

Contaminants it possible to measure the soluble salts


with an electronic conductivity meter,
usually 15 mL of the sample liquid is
required to fully submerge the instru-
ment’s probe (Figure 1). Since the actual

with Bresle volume of sample liquid in the Bresle


patch is only 2.5 mL, it means that the
result has to be multiplied by a factor of
6. Any errors that were made during

Patches—Part 2 certain stages of the test will be multiplied


by a factor of 6 as well.

Effect of Dilution on the


Test Results
N. FRANKHUIZEN, TQC, Zevenhuizen, The Netherlands
The average residue of 0.15-mL test-
ing liquid remaining in the patch after
removing the test sample, and the inac-
Salts on a substrate can have serious effects on curacy and improper use of syringes are
some causes for errors, but the majority
coating performance. This two-part article discusses of the problems are caused by diluting the
sample liquid as it is often done in a
separate 15-mL cup. Good analytical
understandings and misunderstandings about salt practice shows that the number of steps
required to obtain an accurate test result
contamination, describes the Bresle test and the has to be limited as much as possible.
Dilution to 15 mL was required in the
complexities involved in obtaining accurate data, XI[\\WKZMI\M[]NÅKQMV\Y]IV\Q\aWN[IUXTM
solution to submerge a conductivity
and explains the importance of correct data probe and to prevent extreme static dis-
turbance from the plastic measuring
beaker. Static disturbance is caused by
interpretation. Part 1 was published in the the “insulation” from the use of a plastic
cup. The disturbance is best explained as
November 2009 issue of MP. the echo of the measuring signal. Usually,

34 MATERIALS PERFORMANCE December 2009


C O AT I N G S & L I N I N G S

FIGURE 1

in analytical laboratories, measurements


are carried out in a glass apparatus and
at a volume preferably >100 mL. All
conductivity gauges on the market are
QVÆ]MVKMLJa\PQ[[\I\QKLQ[\]ZJIVKM<PQ[
can lead to a difference of up to 5 μS/cm
per conductivity measurement. Diluting
(a) (b)
the sample liquid by a factor of 6 auto-
matically implies that the test result has The Bresle Patch: (a) 0.9-mg NaCl—2.5-mL water and (b) patch inflated with 15-mL
water.
to be multiplied by a factor of 6 as well.
In practice, this means that each devia-
tion or error will by multiplied by 6. The dilution is not applied and the measure- concentration is lower than the measured
5 μS/cm mentioned above could end up ment is made directly on the pure solution concentration, because there are also
in a 30 μS/cm error! New techniques, from the patch, the 0.15 mL residue will other salts present that are interpreted as
however, make it possible to measure in not affect the result. New gauges can al- NaCl. The same is true for the two other
smaller samples using the direct sample ready measure in 2 mL solution with a commonly used interpretations. None say
procedure (DSP). resolution of 0.1 μS/cm. When measur- exactly what is at the surface, but state
ing in a volume of 2.5 mL, the same as what would be present when assuming
Gauge Accuracy the nominal volume of the patch, there is only NaCl is present. This assumption is
During the evaluation of our study I[QOVQÅKIV\KPIVOMQVKITK]TI\QWVNIK\WZ what makes the Bresle method so usable.
results, the need for a higher accuracy Use of a 2.5 mL sample leads to the NaCl is the same worldwide, but the
proved to be a hot issue. The accuracy elimination of the normal calculation preset salt mixture varies by location.
KIV JM QVKZMI[ML QV \_W _Ia[ ÅZ[\ Ja factor 6. The concentration of soluble Interpreting the result as one type of salt
taking a closer look at the gauge. Previous salts measured as NaCl is equal to the gives a reproducible method. One must
available handheld or mobile conductiv- conductivity in μS/cm. This not only consider the fact that it is the presence of
ity gauges had a resolution of 1 μS/cm, makes the determination easier but is also a soluble salt that creates the possibility
with an accuracy of 1%. Calculation ac- more reliable. Results can now be given to form an electrolyte, which in turn
cording to ISO 8502-62 means that the with a 1 mg/m2 uncertainty and resolu- causes corrosion. Nonsoluble salts are not
ÅVITZM[]T\PI[IZM[WT]\QWVWNUOU2, tion of 0.1 mg/m2, increasing the accu- I [QOVQÅKIV\ NIK\WZ QV \PM NWZUI\QWV WN
with an inaccuracy of 6 mg/m2. There- racy 60-fold. corrosion.
fore, when a measurement result is 18
mg/m2 of soluble salts measured as so- Reporting of Results Alternative Methods of
dium chloride (NaCl), the actual value The stakes are high when looking at Measurement
Æ]K\]I\M[ JM\_MMV  IVL  UOU2, []ZNIKM KTMIVTQVM[[ J]\ UW[\ [XMKQÅKI- There are different options in measur-
giving a 33% chance that the actual sol- tions never state how the result should be ing, for example, derivatives from the
uble salt concentration is above the limit reported. Just stating according to ISO *ZM[TMUM\PWL\PI\IZMQWV[XMKQÅK<PM[M
of 20 mg/m2. (Standards such as Norsok 8502-6 and -93Q[VW\[]NÅKQMV\,QNNMZMV\ measurements don’t look at the sum of
already use these concentrations.) test kits give different factors; carefully KWV\IUQVI\QWVJ]\I\WVM[XMKQÅKQWVNWZ
Increasing the gauge’s resolution to reading the test kit’s manual is essential. instance chloride. Determining chloride
0.1 μS/cm contributes to a higher accu- Even making a small change in volumes can be done in multiple ways. Many meth-
racy when determining the soluble salt or patches, without correcting the factor, ods, however, require either large equip-
concentration. This, however, is only one can make entire measurements useless. ment or multiple handlings, but some of
part of the analysis. The acquired results of any soluble salt them can easily be used. Ion selective
Besides gauge resolution, dilution also measurement have to be clearly formu- electrodes and spectrophotometric deter-
QVÆ]MVKM[\PMUMI[]ZMUMV\<PMMIZTQMZ lated. When the concentration is given as minations are examples of tests used in the
mentioned 0.15 mL of residue remaining mg/m2 soluble salts measured as NaCl, it ÅMTL;XMK\ZWXPW\WUM\ZQKLM\MZUQVI\QWV[
in the patch causes an error up to 5% in does not imply that there actually is this are not new. Swimming pools have been
the 15-mL diluted solution. When this amount of NaCl present. The actual checked by this method for many years,
December 2009 MATERIALS PERFORMANCE 35
C O AT I N G S & L I N I N G S Measuring NaCl, Salt, and Soluble Contaminants with Bresle
Patches—Part 2

FIGURE 2

surement. During tests, these patches


contribute, on average, 0.7 mg/m2 solu-
ble salts measured as NaCl per patch.
High-quality patches such as the latex
membrane square patches contain less
salt residue. These patches pass multiple
wash cycles in a clean room-quality pro-
duction plant to ensure that almost no
contaminants are present.
The ISO 8502-6 standard states in
)VVM`)\PI\WVTaKMZ\QÅMLXI\KPM[UIa
be used. This annex describes a stress test
to ensure patch adhesion and wash abil-
ity. In ratio to the nominal volume of the
patch, it has to be injected with an excess
of water. Time to leakage has to be de-
termined and eight out of 12 patches must
pass in order for the type of patch to be
approved. This test must be carried out
A direct sampling kit.
by an accredited laboratory and the pro-
L]KMZU][\JMIJTM\WXZW^QLMIKMZ\QÅKI\M
of the test. The high-quality patches have
although the measured concentrations are ÅKQMVKaJ]\IT[WMTQUQVI\M[\PMUW[\MZ- passed these tests. Most of the non-square
much higher in these applications. A con- ror-sensitive part of the old procedure. patches fail this test by 100%, as only one
centration of 50 mg/m2 NaCl equals a To achieve this, only 2.5 mL of deionized third of the required volume can be in-
KWVKMV\ZI\QWVWNfUO46I+TQV\PM water are injected into the patch. This jected into the patch before leakage starts.
patches test solution, depending on the also reduces the calculation factor to 1. When measurements are taken using
used volume and patch. The chloride The reading from the gauge therefore VWVKMZ\QÅMLXI\KPM[ITTIKY]QZML^IT]M[
concentration is ~2.5 mg/m2, which is doesn’t have to be multiplied to get the _QTTJM][MTM[[7VTaKMZ\QÅMLXI\KPM[UIa
much lower than normally measured with soluble salt measured as NaCl concentra- be used. Some patches also face problems
these alternative methods. Measuring at tion in mg/m2. Because the measurement with poor and irreproducible adhesion
low concentrations brings a few problems is made in the gauge’s own measuring making the test surface irregular. Often
along. The composition of a sample varies cell, all static disturbance is also elimi- 20% extra surface area is exposed be-
in multiple and mostly unknown ways— nated, increasing the reliability of the cause the water creeps under the edges of
this sample composition is called the ma- analyses even further. Figure 2 illustrates the patch. This value is not corrected and
\ZQ` 1WV [XMKQÅK LM\MK\QWV UM\PWL[ IZM a direct sampling kit. causes even bigger errors in the results.
matrix sensitive. Acidity, the presence of All errors caused by using inferior patches
[QUQTIZQWV[IVLUIVaW\PMZNIK\WZ[QVÆ]- Quality Materials lead to higher results, which added to-
ence the accuracy of these methods. There is a large difference among the OM\PMZ ][]ITTa OMVMZI\M I [QOVQÅKIV\Ta
soluble salt test kits on the market. Not higher and erroneous result.
Direct Sampling only the gauge but also the patches differ
Procedure in shape and quality. A test patch should Climate
The new direct sampling procedure be as clean as possible. Any salts that re- Each report produced on soluble salt
eliminates the use of the 15-mL measure- main on the patch during its production levels should include climatic conditions
ment solution. Measurements can now be XZWKM[[ QVÆ]MVKM \PM \M[\ [QOVQÅKIV\Ta and substrate temperature. The ISO
directly made in the solution that is ex- The original Bresle patch is square and 8502-6 standard stipulates that the test be
tracted from the patch, eliminating the some of the alternatively shaped patches done at 23 °C and at a relative humidity
dilution step. This not only increases ef- KWV\ZQJ]\M[QOVQÅKIV\Ta\W\PMÅVITUMI- WN )VaLM^QI\QWVNZWU\PMLMÅVML
36 MATERIALS PERFORMANCE December 2009
C O AT I N G S & L I N I N G S

parameters has to be reported and agreed The combination of the new technique 3 ISO 8502-9, “Preparation of steel
upon by both inspector and customer. and high-quality gauges and patches substrates before application of paints
and related products—Tests for the as-
;]ZNIKM\MUXMZI\]ZMIT[WQVÆ]MVKM[\PM makes these kits especially useful for es- [M[[UMV\WN[]ZNIKMKTMIVTQVM[[¸8IZ\!"
test, meaning that this parameter also tablishing salt contamination. But, what- Field method for the conductometric
needs to be recorded. The lack of these ever procedures are used, it is essential to determination of water soluble salts”
/MVM^I;_Q\bMZTIVL"1;7
recorded values will also render the ac- perform the test properly and to ensure
quired results invalid. that accurate data are obtained.
N. FRANKHUIZEN is a commercial technician at TQC,
Nijverheidscentrum 14, Zevenhuizen 2761JP, The
Conclusions References Netherlands, e-mail: nico@tqc.eu. He is chairman
This article has shown that there is a 1 N. Frankhuizen, “Measuring NaCl, Salt, of NEN NC 342.035, the Dutch mirror committee of
and Soluble Contaminants with Bresle ISO TC 35, Paint and Varnishes. He has 10 years of
lot of science behind proper testing for
Patches—Part 1,” MP "XX laboratory experience in the field of chemical
salt contamination. Inspectors can ben- 36-39. pretreatment and corrosion protection followed by
MÅ\NZWUZMILaUILM\M[\SQ\[\PI\UISM 2 ISO 8502-6, “Preparation of steel work at TQC.
these tests quite simple. Updated Bresle substrates before application of paints
kits are now available with the DSP, en- and related products—Tests for the as-
[M[[UMV\WN[]ZNIKMKTMIVTQVM[[¸8IZ\"
abling inspectors not only to work faster Extraction of soluble contaminants for
but also to produce more accurate results. analysis—The Bresle method” (Geneva,
;_Q\bMZTIVL"1;7

December 2009 MATERIALS PERFORMANCE 37

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