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SHRPC628
Concrete Microstructure Porosity and Permeability
D.M. Roy P.W. Brown D. Ski B.E. Scheetz W. May Materials Research Laboratory The Pennsylvania State University University Park, Pennsylvania
v
Strategic
Highway Research Program National Research Council Washington, DC 1993
SHRPC628 Contract C201 Program Manager: Don M. Harriott Project Manager: lnam Jawed Production Editor: Marsha Barrett Program Area Secretary: April 1993 key words: cement paste concrete permeability pore structure pore size distribution porosimetry porosity surface area Ann Saccomano
Strategic Highway Research Program National Academy of Sciences 2101 Constitution Avenue N.W. Washington, DC 20418
(202) 3343774
The publication of this report does not necessarily indicate approval or endorsement of the fmdings, opinions, conclusions, or recommendations either inferred or specifically expressed herein by the National Academy of Sciences, the United States Government, or the American Association of State Highway and Transportation Officials or its member states.
© 1993 National
Academy
of Sciences
350/NAP/493
Acknowledgments
The research described herein was supported by the Strategic Highway Research Program (SHRP). SHRP is a unit of the National Research Council that was authorized by section 128 of the Surface Transportation and Uniform Relocation Assistance Act of 1987.
iii
Contents
Acknowledgments Abstract
..................................................
iii vii 3 7 ... 19
.......................................................... .................................................. of Pore Sizes in Cement Paste .................... During Cement and Mortar Hardening
Executive Summary
A Model for the Distribution Lognormal Simulation
of Pore Evolution
Concrete Microstructure and Its Relationship to Pore Structure, Permeability, and General Durability ............................................ Porosity/Permeability Relationship ......................................
25 43
Relationship Between Permeability, Porosity, Diffusion and Microstructure of Cement Pastes, Mortar, and Concrete at Different Temperatures ...........
76
/4
V
Abstract
A model has been developed that lays the foundation for relating porosity to permeability. This is based on knowledge gained from previous work as well as experimental and theoretical input from the present program. A linear combination of lognormal distributions may be used to define the pore structure. This report contains five papers relevant to this topic.
EXECUTIVE SUMMARY
The objective of the current pore size distribution properties distribution distribution
study was to develop an accurate
mathematical prediction.
descriptor Various
for
to relate to permeability materials present.
and use for permeability
of cementbased of the porosity and properties, Mercury
are affected not only by total porosity In order to model the relationship mathematical descriptor
but also by the size pore size must
between
a suitable
for pore size distribution used method
first be found.
intrusion
porosimetry
(MIP) is a commonly
of determining such as by MIP the basis
pore size distributions permeability. should A suitable
for the range of pore sizes which significantly mathematical descriptor
affect properties
for pore size distributions data but, more importantly,
determined provides
be one that not only fits the experimental interpretation of pore structure.
for the physical Diamond distributions The present lognormal distributions,
and Dolch (Ref. 1, Paper 1, this supplemental in cement pastes determined
report) showed that the pore size as lognormal suggests distributions. that a single
by MIP could be described pressures
work in which higher intrusion distribution is inadequate
have been applied,
to describe
the smaller
pores. A mixture
of two lognormal of of Pores
or a compound
Iognormal
distribution pastes
was suggested and mortars.
to model the distribution However, closer examination
pore size determined
by MIP in both cement
the data used in our model shows that very coarse pores, pores  > 1 ]an, were rarely included. in this size range affect properties, In the present Iognormal extending such as strength and permeability, It appears and should
not be ignored.
study, pores as large as 7 _n are included.
that a mixture of three
distributions
can more closely fit the distribution
of pore sizes over the range of sizes
4 orders of magnitude
from about I nm to about 10 _rn. distributed density if Y = IogX is normally function is, [3] _ as the shape parameter. distributed with mean
A variate X (0 < x < _) is Iognormally and standard deviation ¢_.The probability
P(X) = (2r_s2)'1/2X" lexp[0.5{flog(X)  _)/¢_}2] The range of X is 0 < X < _. Some characteristics _ is defined as the location parameter, distribution are:
of a Iognormal
mean = exp(_ + 0.5o 2) median = exp(_)
mode = exp_  o2) , coefficient variance ., Cement hydration between particles anhydrous are large. of variation = exp(a 2)  i
= mean2[exp(¢_ 2)  I] may be regarded as a process of subdivision of void space, or interstices anhydrous and divide
particles.
At the early stages of hydration, hydration, hydration
the void spaces between bridge the particles
With proceeding
products
3
the large voids between
particles
into smaller in cementitious
pores.
This phenomenology to have a physical is defined
suggests basis.
the lognormal
model of pore size distribution A mixture
materials
of two or more Iognormal
distributions
by a compound
density
function:
=zfiP ,
where fi is the weighting parameter and shape
zfi=l
subdistribution respectively. P(x, _t, _i), _i and c i location i If an attribute of a system
factor of the ith Iognormal
parameter
of the i th subdistribution distributions,
can be described phenomena materials, different
by two or more Iognormal in that system. that different
it is very likely that two or more in cementitious exist for pores in
are occurring
In the case of pore size distributions origins and formation mechanisms
this may indicate size ranges. method
A statistical distributions approach
has been developed estimate
to detect if there is a mixture in the compound
of two lognormal distribution. A similar
and to iteratively
the parameters
can be applied
to a mixture
of more than two lognormal this method by MIP.
distributions. is obtained from a set of P(x) is the
The pore size distribution cumulative cumulative approach probability percentage to obtain
used to demonstrate
data, P(x) vs. x as obtained of pore volume with respect
x is the pore diameter,
to the total pore volume. The graphical of a mixture of two or more lognormal of N(0,1) tabulation [e.g.
first degree estimates
of parameters
distributions corresponding
first requires
the transformation
of x to log(x). Next, the quantfles a standard normal
to P(x) are determined
by consulting
distribution
see ref. 14]. If the cumulative percentage
percentage
is 50%, the corresponding
quantile
is 0; if the cumulative is 16%, the
is 84%, the corresponding quantfle is the negative
quantile
is 1.0; if the cumulative for (100%16%L distribution.
percentage
corresponding
of the quantile
or 1.0; etc. If a plot of log(x)
vs. the quantJJes is to determine segments. distribution.
is linear, x obeys a single Iognormal the weighting factors, by locating
The final step in the analysis between selected neighboring linear of and it is where can be
the intersections by comparing
The goodness The median
of fit can also be checked
characteristics
is often used as an important data. Because
characteristic the median
of a distribution, = 5". fi)(mediani), (
readily determined
from the experimental
median i is the median estimated from _.
of the ith subdistribution, important
which is exp(_ti), the overall median is the inflection
Another
characteristic
point on a plot of pore curve. The is: The
volume vs pore radius. inflection point coexists
The inflection
point is easily approximated between
on an experimental
with the intersection
the first two linear segments. the first and second
corresponding
x value of the inflection
point between
subdistributions
exp [(G2_I  aI112_ / (G2 "¢_1)] In order to check the generality lognormal distribution, of fitting pore size distribution data to a compound Ordinary cement paste,
data from different sources
have been examined.
4
blended results
cement
paste, and mortar
hydrated
for various
lengths
of time have been examined. in cementitious used is adequate materials to provide
The to a
demonstrate Iognormal
that it is reasonable distribution. Further,
to fit pore size distribution the graphical method
compound
initial estimates
of parameters
in the compound in real materials must
distribution. exhibit upper and lower bounds. and Dolch. This is the
Pore size distributions physical assumed diameter involved, basis underlying
the model developed by Diamond on the distribution whether
The lower limit was in the reduced
to have little influence expression.
curve and was neglected this assumption
It is questionable
is valid when small pores are their model is equivalent to a
i.e., when x approaches Iognormal
x1. If the lower limit is included,
fourparameter
distribution,
in which the variate X is confined
to the range L < x < U,
and X = (X  L) / (U  X) is L(_ ¢). An attempt to desc_be pore sizes ranging from about 1 nm to about 10 fan by a single fourparameter simulated assumes assumes is zero. compound distribution lognormal distribution was not successful. Because the
is fitted to the pore size distribution at the smallest pores intruded
determined by mercury.
by MIP, it In other words, it by mercury
100% cumulative that the probability
probability
that the pore diameters
are smaller than those intruded
This, of course, is not the real lower limit of pore size. If the real lower limit of pore size of the MIP porosity are both known, the pore size distribution over the range of
and the percentage pore sizes determined
by MIP can also be simulated to describe
by using the method should
we have developed. significance. The first
The use of the distributions subdistribution of the three
porosity
have physical
may be regarded voids.
as describing
the size distribution
of coarse pores. as describing one represents
Pore sizes may extend to include the size distribution capillary pores. of fine pores.
The third subdistrlbution
may be regarded
Pore sizes may extend to gel pores. The middle
It is the pores that belong to the subdlstribution created products by the hydration process. Because the majority
representing
the finest porosity exists
that are
of this porosity the kinetics
in the hydration Altematlvely,
that are forming,
it is these pores that control structure
of hydration.
from the viewpoint relationships, permeability, significantly calculated
of permeabilltypore of porosity that
or fracture
mechanicspore
structure to
the majority
in this range is not important. only pores having diameters We have demonstrated model and based
With respect greater
it is well recognized contribute
than some value point can be
to permeability. Iognormal
that an inflection
using the compound characteristic
on our analysis. is the mean square pore
Another diameter, •
that may be important of pore diameter
to permeability distribution.
or the second moment
If one combines
the classic Darcy's square pore This is
law and Poiseuflle's diameter a classic
law, one can relate the permeability
coefficient
k to the mean
k = e <D2> / 32 where _ is the porosity and <D2> the mean square porediameter. model describing permeability of porous media, assuming
that pores axe tubes which are
not interconnected. are two indispensable distribution diameter
We have observed that a characteristic variables in all sensible permeability
pore dimension models.
and a tortuosity
factor
If the pore dt_meter the mean square pore The inflection expressed Depending it may be For as on
can be modeled
by a compound
lognormal
distribution,
can be readily determined
using the equation: can be described
<D2> = Z fi exp[2 (iti + _i2)]. in terms of a distribution areas.
point, or the mean square relative pore volumes,
pore diameter,
as relative
pore numbers, influenced
or as relative pore surface by the distribution
the physical beneficial example,
or mechanical
property
in porosity,
to consider
the pore structure relationship
in terms of pore surface relates permeability
areas or pore numbers. to porosity:
the KozenyCarman
K ~ e3/(1  e)2/$2
where e is the total porosity This equation multiplicative volumes terms. requires
and S is the total surface area of the pores. a value for the porosity distribution, expressed in terms of pore surface area. Thus,
property
of the Iognormal
which allows the interconversion
between
and surface This attribute,
areas,
anows, in turn, MIP pore volume data to be expressed with the ability to deconvolute porosity
in appropriate that a basis between
coupled
data, suggests
has been identified the behavior
which may allow a more fundamental materials
understanding
of relationships
of cementitious a refined
and their pore structures. pore size distribution has been developed. Finally, an This
In conclusion,
model for describing
in turn has been integrated experimental The predictions to calculate apparatus
into a model for the prediction determine
of permeability. of specimens
to rapidly
the permeabflities agreement
has been developed. values when used
from the model
show reasonable
with experimental
permeability.
6
A
Model for the Distribution of Pore Sizes In Cement Paste
•
O. Shi, P. W. Brown and S. Kurtz, The Materials Research Laboratory, The PennsylvaniaState University,UniversityPark, PA 16802 ABSTRACT The pore size distribution cement paste over the range of pore sizes interrogatedby high in pressuremercury intrusion porosimetrymay be describedby a mixtureof two lognormaldistributions. The compounddistribution poresizes may be givenas: o(
p(x) =
)2 (lf) [(log xP.2) 2 f exp [(log X'lJ.1 exp 2 ] _r1 xV__'_ 20 2 ]+ a2x'V_'x 2(:12
where p(x) is the probabilitydensity functionof poresol sizex, f and (14) are the weightsof subdistributions, g.1and P2 are thelocationparametersofsubdistributions, 01 and (_2are the and shape parametersof subdistributions. These two subdistributions represent larger and may the smallercapillaryporesrespectively.The changesin the subdistribuUons the compound and distributionas functions curingage and watertocementatio"re discussed. ol r a
INTRODUCTION
The abilitytowedicate the macropropertiesndbehaviorof porousmaterialsin generaland a those of cementbasedmaterialsin particular dependsonthe abilityto mathematically definethe pore structures these materials.In spiteof variety ol limitations, in mercuryintrusion porosimetry (MIP) is e methodcommonlyusedfor determining pore sizedistributions a broadrangeof pore sizes. It is of believedthatthe pore size range amenableto MIP analysis isthat whichaffectsmanymacroproperties. It is of interesttodevelopa modelfor thedistribution pore sizesin cement pastes of determinedby MIP. Previous investigations have shownthatthe poresize distributionsin cement pastes determinedby MIP couldbe describedby iognormaldistribution providedthe pore diametersare transformedto reduceddiametersby the equation:
Xr= (x Xl)(XuXl)/ (Xu x)
where xr is the reduceddiameter,xu and xI are the upperand lower limitsofthe pore size range. The lowerlimit was assumedto havelittleinfkJenceon the distribution curve andwas neglectedin the " reduced diameterexpression[1]. However. furtherwork.in whichhigherintrusion pressureshave been applied,suggeststhata singleIognormaldistribution may be inadequateto includethe smaller pores. Additionally,the assumption the lower limitisnegligible that may be invalidwhen smallerpores are involved. Based on the presentlyavailabledata, it appearsIhatthe pore size distributionin cement paste
7
overthe range ofporesizes determinedyhigh b pmssura IPmaybedescril:xKI a mixture two M by of iognormal distnl:utions. Thesubdistributions mayrepresent thelarger ndsmiler _ a pores, respectively. Thevalidity assuming of twolognormally distributed poresizes canbetestedbya robust statistical method A program [2]. basedonthismethod wasdeveloped todetect hether poresize w a _strroution a mbdure ftwoiognormal is o distributions. isa mixture ftwolognonnal Ifit o distributions, threeparametersssociated itheachofthetwosubdistributions a w areestimated. hethree T parameters foreachd_ion are: theweights fthelarger o andsmaller oresizedistdoutions, p f and(1.q; thelocatio nparametemof thelargerandsmaller oresizedistnbutions, andI_2; p ILI theshape parametersfthelargerandsmaller oresizedistributions, and02; o p 01 Thesizedistd0ution fporesincementpastes eterminedy MIPcanthenbedescribedy a o d b b compound distribution fromthesesixparameters. Thechanges ftwosubdistnbutions, o withcuring ageandwatertocement ratio,aswellas that of thecompoundizedistnbutionreconsidered s a inthispaperasa preliminary tounderstand effort the physical eaningsfthesetwosulPdistritx#tions. m o Itis a common physical occurrence thatphenomena a system in aredescribedythesumo(two b lognormal distnbutions. Thegeneral hysical p interpretation isthattwoindependent phenomenaan c govern thatoccurrence.nthepresent I instance, thissuggestshattheorigins themechanisms t and controlling sizes the oflarger andsmaller apiilar/pores aybedifferent. ther c m O imp,cations ofthis modelmayinclude possibility the ofdescrC_ng thewholerangeofporesizes fromtheporesize distnbutlons determinedydifferent b tachniclues. FUNDAMENTALS OFTHELOGNORMAL ISTRIBUTION D Thenormal distributionrobability ensity p d function, n(.u,o),s: i "X'=, I ex "(x'p')2'
Pt 2a 2 '7
where p(x)isthe probability thaithe random variable, willhavea value is themeanand a isthe x, x,p standarddeviation. mean, 4, ayalsobe referred The 1 m toas thelocation parameter ndthestandard a deviation, may 0, alsobereferred toastheshape parameter. A variate is iognormally x distributed  logy wherey isa positive ifx variate, 0 < y < ,,), which ( is normallydistributed ithmeanI_ and standard w deviationa. We thendefinethatx is Iognormally distributed ndthe probability a density function,(_,a),is: I p(x)= 1 ox_/_z exp'[(l°g x1_)2l 2 20 °
wherex istherandom variable, theporediameternthiscase.Therange i ofxis 0 < x < . p,isdefined asthelocation parameter, is defined a astheshapeparameter. hemean,median T andmode areas follows:
8
mean = exp(p. 0.502) + median,exp(p.) mode = exp(l_ 02")
Figure 1 Isthe comparisonbetweennormaldistributk)n n(O,O.S) nd the Iognormal istribution a d I(O,O.S) 3]. The normaldistribution symmetric [ is about the meanwhilethe Iogrlormal istdbuJion d is positivelyskewed. The normaldistribution adsesfroma theoryol elemanlaryerrorscombinedby a ad_tive process, hile the Iognormat istributionarisesfrom a theoryof elementaryerrorscombined w d by a muItipUcative process. The differencebetween Iognonnat nd normaldistributions descriptor f a as o processis similarto thatbetween the geometricand the arithmetic means as measureof Ioca_n. The derivationof the multiplicative odeladsss fromviewinga posiUve m vadate as a measure ofa discreterandomprocess.Atthe jth step, thechangein thevariateis a randompmpoflionof thevalue of variateat the (j1)th step. Thus,
xj xj.1 = 8jxj.1
where xj isthe value of variateat the jth step, xj.1 the value at the (j1)thstep, and 8] the smallrandom proportionalgrowth/degradation ratethattakes the processfromthe (j1)th step tothe jth step.
0.8
I
i
I
Q6
0.4
0
4 . 2 0 z 2 < wZ 004 OLiJW :S =S=S 4 6 8
Figure 1. A comparison between a normal distribution, n(O, 0.5), and a IognormaJ distirbution,(0, I O.5).The mode,median, and mean of the Iognormal istnbulJon shown. d are
g
It follows that
xj = [['[(1 + 8i)]xo Iog(xj)= Iog(x O)+ T..Jog(18i) = Iog(xo)+ T._ +
where i = 0,1 ........ j. xo is the initialvalue of the vadate. Applyingthecentrallimit theoryto the sum of
p
the small random quantities,8i, resultsin log(x)havingan approximate normaldistribution,.e. x hasa i Iognormal distribution. Many physical and chemical processes, such as corrosion, diffusion, pulvedzation,crushing,and cracking[4.7] may be approximated _ lognormal model. by Accordingto central limittheory, if log(x)obeys a normal distribution n(IJ.,a),then [Iog(x)p.]/a obeys a standard normal distribution, (0,1). Thus, ifx1 obeys lognormaldistributionI(_,a), x2 obeys n standard normal distribution n(0,t), and if the cumulativeprobability p{x1 < x1,q} = p{x2 _;X2,q}, we then have:
x2,q = [log(x1,q)  _]/o
In statistics,x 1,q and x2,q are defined the quantileof orderq of I(p,a) and quantileof order q of n(0,t) respectively. Thismay be rewritten as:
log(x1 = aX2,q+ I_ ,q)
so that the locus of Ix2,q, log(x1,q]is a straightline. Inotherwords,it x1,q and X?,qare quantilesof the same order q of I(p.,a)and n(0,t), then the locusof (x2,q, x1,q) is a straiglll lineon a semilogscale. Suppose now that the cumulativeprobability p(x2 < X2,q},insteadof the quantilex2,q, is ruledon an axis with linear scale; this is the basis of logarithmic probabilitypaper. If plotting the cumulative probabilityP{x < x} againstx on the logarithmicprobabilitypaper results in a straightline, we then reasonably predict that the variate x obeys the lognormal distribution. This is one of the mostuseful propertiesof the lognormaldistribution [3].
MIXTURE OF TWO LOGNORMALDISTRIBUTIONS
The mixtureof twolognormaldistributionis definedby a compounddensityfunction:
p(x =
exp  [(log XlZ1) 2 ] + (lf) _r x_/2zz 1 2 a 12 _r x _ 2
f
exp" [(log x'g2) 2 ] 2(/22
where f is the w6!_ht of the first subdistributionI(I.Zl,al), (lf) is the weigh of the second subdistributionI(p2,a2) Pl and P2 are the locationparametersof two subdistributions, repectively, and <71and a 2 are the shape parameters of two subdistributions,respectively. For the first subdistribution, he statistical t characteristics are: mean 1 = exp(_.l + 0.5 o'12) median 1 = exp(_) model = exp(141  a12) For the second sublognormal distribution,he counterparts are: t ,,
10
For the secondsublognormal distribution,the counterparts are: mean 2 = exp(_2 + 0.5 (;2 2) median 2 ,, exp(i.z2) . mode 2 = exp(p.2  <_2 2) A statisticalmethodhas been presented to detectthe mixtureof two lognormatdistributions, and to estimatethe valuesol f, P'I, P'2,(xl and (_2[2,7,8}. A microprocessorbased computer program has been developed at the Materials Research Laboratory,Penn State University, o implementthis method. Withinthe context of the presenttopic, t this programfirst plotsthe experimental cumlative pore size distribution curve on the logprobability scale. If the curve appearsSshaped, it is likelythat the distributionis a mixtureof two Iognormal distributions. The program then selects a point, which may be but is not constrained to be the inflectionpoint,as the startingpoint in the estimationof the value of l, thecorrespondingcumulative probability.Thispointis also used to separate the wholedataset intotwosubsets. Foreach subsetol data, the programdoes regression analysis on porediametersvs. quantilevaluesof n(0,1). The slope and interceptof the regression line are the valuesol p.and_. Fromthe estimatesoff, (tf), P'I, P2, al and (72.the compounddistribution and the cumulativeprobabilities calculated. Then the program are comparestheexperimental umulativeprobability c and the calculatedcumulativeprobability,and allows the use ol iterativeprocedure until satisfactoryresultsareobtained.
EXPERIMENTALDATA Foursetsof MIP dataolotainecl from the[9,10]literaturehavebeenanalyzed. Sets 1 and 2 are froma cementpastehydratedat a watertocementratioof 0.4 for one and28 days, respectb/ely. he T pore sizes rangelrom 2.9 nm to 700 nm. Sets 3 and 4 arefrom pasteshydrated 38 daysat for watertocement atios0.4 and 0.35, respectively.The rangeof pore sizesfor sets3 and 4 is 1.9 nm to r 140 nm. Comparison calculated distributions of willbe madebetweenset 1 and set 2 to showthe effect of age on pore structure, nd between set 3 and set 4 to showeffectol watertocement a ratioon pore structure. orsimplicity,set 1 willbe referredto as: 1daydata, set 2: 1monthdata, set 3:0.4 w/c data, F and set 4:0.35 w/¢data.
RESULTS In thefollowingfigures,"1"denotes the firstsub.distnbution hichis the size distributionof the w largerpores,and "2"denotesthe secor_dsub.distribution, size distribution smallerpores. the of Figure2a andb provideexamplesshowingthe estimation Ofvaluesof f, 14 and a fromthe MIP data. The values ofp,and (; arethe slopesand interceptsof regression lineswhichwereplottedon a natural Ioganthmicnormal quantilescale, not simply theslopesand intercepts thestraightlines shownon of thatfigure. An interesting pointis that all the valuesoff are near0.9. Thispoint will be discussed further. Rgure3 comparesthe experimentalcumulative probabilities and thecalculatedcumulative probabilities. SE is the sumof square of errors,givenby the equation: S
11
e.._=**.mI >, **.=,:.Q
0 .¢3 O L 90.Om1 t I
,. Experimental Data  0.85 Regressions fol = 2.518 I_l = 0.647 o2= 0.882 lz2= 0.131
(3.
50.01
t
I '
__o
lO.Om
I
t•
,,
% %
0.10m0 01s ....
1
b
% 10 100
Size (nm) eo.om..u>, ...a=•.43 ._0 Q. 90.Q=

Experimental Data Regressions I_1= 1.055 p2 = 0.237
X X X
f _1  0.90 5.354 _z  1.855
_
_
10.01
0.1(_0.01l
a
i
+ 10 100
Size (nm)
Figure Thepa_em 2. f.rL. ndo olXained a proba_lily a from plolforpaste hydrated for(a)onedayat wit ,, 0.4;Co) 8daysat wit, 0.35. 3 12
+
N.tW." t I:'xperimentol 04to
N.IIIB= N.m. _ ,, [xperimentol 04ta
W.m
_.B°
0
re.D
,m.D.
•
_ ¢ [stimated 04ta ••_ ,,
U ._
tO.m1,0_.e.i. e.lm_ •

(stimoted__0ota
IOAI, t._. w,. iLim._
eom
oow
•
....... ,i
IQ.NB
siz.(n.,)'=
N._
si_;. _) (
w.mI I 
"
w.'., \ \
N.IB
\

(xperimentol 0oto (,timot.d Ooto
(xporimentol 0at0 (,timotod 0_o
IO.0l
_
W.mo
_,ll
SO.I° _w.mLz_ O.Ota
. _ _ b . • • • ....
tO.mIll.m. o  t_ • e.otl.
d . .......
,• m
,0
$iZ0 (rim),ol
$iII
(nm)
,m
Figure 3. A comparison of the exl=edmentai and calculated cumulative pmbabiUties based on the use ot two lognonnal distributions to model the pore size distribution (a) one day at w/c ,, 0.4; Co)28 clays at w/c  0.4; (c) 38 days at wlc ,, 0.4; (d) 38 clays at w/c = 0.35.
SSE = I;(px  pc)2
where Px and PC are the expenrnental cumulative probabilities and calculated cumulative probabilities, respectively. SSE can inclicato the goodness of fit. Another way to indicato tho goodness of fit is by plotting the expodrnentat probabirdias against the calculated wobabiities, which is actually the graphical express_n of SSE. Figure 4, which shows the comparison for the MIP curve for 38 days at 0.4 w/c. is a typicalexample of this. FigurO 5 shows tho caJculated SUb.diStributions, as well as the calculated compound distributions, for the 4 data sets. It is worth noting that it is difficult to express the different weights of _subdistributions graphically. Thereforo, we modified the calculated compound distribution to a mixture of two sub distributions with equal weights as follows:
i _ if
p(x).
1
loo(_)(pl .logf) 2 exp[. ] +
1
_g(_)(.2_(1f)) 2 exp( " ]
13
1.00 
0.80 0 N 0.60 /:
i...
/,,,
0 0.4.0 ..,_; CL
E
×
...../..
/
0.20 0.00 / 0.00
I
I
I
I
I
0.20
0.40
0.60
0.80
1.00
Est.
Cure.
Prob.
Rgure 4. An exampleof the goodness fit shownthe samplehydrated38 days at w/c. 0.4. of
Rgure 5 is thegraphicalexpressionof the modifiedcompounddistdbulionS. Rgure 6a showsthe effect of increasinghydration time on the calculatedcompound distribution.The shiftof means and mediansof sub.distributions obvious,as are the twocrossoverpoints wherethe is subdistril:uUonsntersect. i Figure61)shows the effecl of watertocementatio on the calculatedcompounddistribution. r The shiftsin the mean, median and crossover pointare also easilyobserved.
DISCUSSIONAND IMPUCATIONS ASmay be seen from Rgure 2, the f values (weightingfactors)am near 0.9 forthe distribution ol the largerpore sizes. This suggests that, ifthe smallerpores areignored,the pore sizes mayfit a singleIognormaldistribution. As mentionedearlier,previousinvestigations have shownthatthe pore ._
14
O.OJ •
&IS •
"_, lkN, ta.
u :_

Compound distribution Subdistribution8

Compounddistribution Subdistributions
o.m
0.0,1
....
........
o._
_"
> .........
'° sizsC,m) ...... i_'
"
L_I 1
s;'_o (,,,,)
'i_.
:_ u ¢ _o.ol m c w 0
Compound distribution
Subdistributions
.o
_L_S
_ LI,. ._LI@ ¢ • 0
Compound
distribution
Subdistributions
i
OOI
.
J
.
._ :
10
.................
Size (nm)
100
tom
°
o
G, e.BI
.................
Size (nm)
t°
101
Figure5. The probabirdyensityfunctions the calculatedcompound d of dlstnl=utlonnd o4the two a subdistributions asedon the iognormalmodel(a) one day at wlc = 0.4; 28 daysatw/c = 0.4; (c) 38 b daysat wlc = 0_4;(cl)38 clays w/c= 0.35. at
size distribution cementpaste couldbe desatbed as a singleiognormaldistribution in provided that the pore diametersaretransformed toreduceddiameters[1]. By examining MIP data used in that the previousinvestigation (Fig. 6, and Table II in reference1), whichwas obtained forpastes similar to thoseanalyzedin thispaper(w/c ,, 0.4, age = 2861 days), it was observed thatthe smallestpore diameterused tofita singleiognormaldlstdbuttonis 10 rim. It seemsthatin on_r to includesmaller pores, it iSnecessan/tOuSea mixlureof two Iognormal istributions.FromFigureS,it was foundthat d the (_ametersofthe larger poresrange the orderof magnitude10 to 100 nm,whilethoseof thesmeller pores are lessthen 10 rim. Resultsalso suggestthat the f value doesnot changeappmdablywith age or watertocamerara_o,in spiteof the shiftin the crossoverpoint. Thus,0.9 may be an appropriate f value for the la_er pores. Allreal panicleor poresize distribulions musthave some maximumand m_imum size. This was the physical nterpretation i associatedwith the use of reduceddiametersandw_th introduction the of the upperand lowerlimitson theparticleor poresize range[1,5,6]. Rgurs 5 showsthatthe maximumsize does existwhere thecorrepondtngdensity functionapproaches zero, thoug_no maximumsize is explk_tly defined.On the otherhand, based on the cuwently availalMe MIP data, it is impossJl_e locatethe real minumumsize. It might notbe validtoassume thatthe minimumsizeis to negligibleif smallerpores, e.g.thosewithdiametersless than 10 nm, are included.Forthis mason Figure5 leaves thesmallerporedistribution curvesopen at the lowerend. _
15
O.OSO
_. 0.040

day old month old
Age: Mean 1 Mean 2 Median 1 Median 2 Crossover 1 day 386.64 6.58 211.37 6.39 11.52
a
t_
> 0.030
28 day_ 76.17 4.21 57.81 4.17 6.18
•_ c q3 ca 0.020 >,
.120.010 .Q 0
L
x I x "_
%
0.000
100.0
4OO.0
Size (nm)
0.200
I
.m
c o
o 0.150
" c
:3 la.
l
_
....
W/C: Mean 1 Mean 2 Median 1 Median 2 Crossover
_""_
0.35
0.40 0.35
>, "_ o.1oo e. >,
"0050• r,l 0 r's 0 l,_ 13. 0.000 0.0
,mlll
17.46 15.28 2.75 2.44 13.93 12.40 2.44 2.41 "3.61 3.15
20.0
40.0
Size (nm)
q:
Rgure 6. (a) The vafla_ons in the cak:ulated I_mba_fW density functions for Ihe pore size disffibutions
(a)between and28daysatw/c 0.4; b)asalunclion w/cratio I ( o_ ataconstant o138days. age
16
It an a_bute of a systemcan be describedbytwo Iognormal stdbutions,itis veryikely thattwo d phenomenaare ____rdng that system. In the presentinstance,this suggests in that the odgtnsand the formation mechanlsmeoflargerand miler capilla_ poresmay be differenLFigure6a showsthat
the largerporesize distdbution shiftsto the leftmarkedlybetween 1 and28 days. The meanand
2
meo_an the largerpore sizedistributiondecreasefrom387 nmand 211 nmto 76 rim and 58 nm, of respectively. On the otherhand,the decreasesin the meanand medianofsmallerpore size _stnl:ution are relativelysmall The shape of the curve representing the_ pores also changesa
great deal sugge_lng thatmanyof the largerporesdecreasesignificantly size. AlternaJvely,many in of the smallerporesare alreadypresent alteronlyone day of hydration.The obvious speculation isthat the smallerporesresulttramhydra_onwhilethe largerones are formedir_i_ly as interstices between anhydrous particles. Figure6b showsthat the subdistdbutions observed at 38 daysof hydra_on exhibitmedian pore sizes relatedto theirwatertocementratios,0.4 and 0.35. ComparisOn the changes w_th observedin Rgurs 6a, suggests that the watertocemantratiodetermines initialsubdistributions, the whilethe age determinestheevolution the subdistrtbutlons. of However.more samplesneed to be examinedto inveetigate pos___h4e the existence of the (lfferent originsandfonna_n mechanisms of pores in cement pastes. Porosity cememrangesfrom millimeters nanometersin cementand manydifferent in to techniqueshave been usedto determinethe distributions pore sizesin these ranges[11,12]. of Inevitably, hese measureddlstdbulk)ne t overlap. If the uncertainties associatedw#h these overlapping regionscouldbe solved, it may be possible to describethe entirerangeof pore sizesin cement paste. The entiredistritx_ionof pore sizes in cement pastesfrommiimetersto nanometers mightbe a mixtureof multiple lognormal lstdbutions,eachsubdlstdbulion d mpresentlngthe poresize distdbutlon data determinedby one spodflc technique,and reflecting spod_ odginand formation the mechanismof poresin thatcorresponding size range. CONCLUSIONS 1. A mixtureof two iogrlormaldistdbutioneappearsto deschbe poresize (IMdlxjlion detmned by highpmesureMIP analysisand suggests differentoriginsandfonnalionmechanisms of poresin cement pastel. 2. The diametersof the larger poreersnge the orderof magnitude10 to 100 nm, wNle thoseof the smallerporesare less than 10 nm. The sub<istrilxntonofla_11er poreehas a 90% wei_t in the _ 3. sizedistntxltion.
The watertocementratioseems to determinetheinitialsubdistribution, hilethe aging w processatfeds the evolution pore structures. of
4.
Additional amples,including s thoseof blendedcements, needto be exanVned, o furmm t eluddete the existenceof the different originsand formationmechanismsof poresin cement pastel
17
ACKNOWLEDGEMENT & DISCLAIMER The msearcJ1 escribedhereinwas sul:fx)rted d bythe StrategicHighwayResearchProgram (SHRP). SHRP is a unitof theNationalResearchCouncil hatwas authorizedby section128 of the t Sudace Transportation and UniformRelocationAssistance of 1987. Act This paper represents viewsof the author(s) the only,not necessarily reflectiveof the views of the NationalResearchCouncil,theviewsof SHRP, or SHRP's sponsors. The resultsreported here are not necessarilyin agreementwiththe resultsofotherSHRP research activities.They are reportedto stimulatereview and discussion withinthe researchcommunity.
REFERENCES
1. 2. 3.
S. Diamondand W. Dolch,J. Colloid& InterfaceSd., _ E. Fowlkes,J. Am. Stat. Assoc., 74. 561575 (1979).
234244 (1972).
J. AJtchison JJ_.C.Brown,The Loonormal istribution. ambridgeUniv.Press, and D C
Ca_
4. 5. 6.
(1957).
Van NostrandReinholdCo., New York, 1986.
P. Tobiasand D. Trindade,_ R. Irani,J. Phys.Chem., 63. 1603 (1959).
R. Iraniand A. Callas,ParticleSize: Measurement.ntemmtation.andAootication, iley,New I W York (1963).
7. 8. 9. 10. 11. 12.
D. Hosmer, Communications Star., .1,, 17227 (1973). in 2 V. Hasselblad,Technometrics,_ 431444 (1966). D. Shl, M.S. Thesis,Purdue University(1984). A. Kumar,Ph.D. Thes_s, enn. State University P (1987). R. Feldman,this Proceedings. R. Gerhaml, this Proceedings.
18
LOGNORMAL SIMULATION OF PORE EVOLUTION CEMENT AND MORTAR HARDENING
DURING
Dexiang Shi, Weiping Ma and Paul W. Brown Materials Rese_h Laboratory The Pennsylvania StateUniversity University Park,A 16802 P ABSTRACT A model to describe the pore sizes in cement paste and mortar, as determined by hi.gh pressure mercury intrusion porosimetry, has been developed. The model describes porosRy using a compound lognormal distribution. For given material under a given set of curing conditions, the weighing factors and shape parameters of two subdistributions in the lognormal model may be considered as constants, while the location parameters may be related to curing time and the relationship can be quantified. Therefore, it is possible to predict both the pore size distribution in cement and mortarat any age as well as the evolution in pore size during curing. INTRODUCTION Cementidous materials are being used in the immobilization of radioactive waste. Conventional concrete structures are being used as engineered barriers. Low level liquid wastes are being immobilized in cementbased grouts. While these applications differ from those involving normal concrete structures,the porosities of cernentitions materialsare important in determining the ability of a structure to meet its functional requirements, virtuallyregardless of the specific applications. It is the distribution of porosity throughout cement matrix and at cementaggregate interfacial zones that, in concert with environmental variables, determines the macroscopic rate of transport of species. The development of an adequate description of thepore size distributions in cements has recently been accomplished [1]. Our work has shown that the pore size distributions in cement pastes over the size range determined by the high pressure mercury intrusion porosimetry (MIP) may be described by a mixture of two lognormal distributions [1]. The present paperextends the model to cementitious systems containing aggregate. Many physical and chemical processes may be approximatedby the lognormal model [25]. It is a common physical occurrence that a system can often described by a mixture of two lognormal distributions, which .govern two different phenomena occurring in that system [6]. Cement hydration may be reganted as a process of subdivision of void space, or interstices between anhydrous particles [1,5]. In cement paste and mortar, the origins and the mechanisms controlling the sizes of largerand smaller capillary pores may be different, suggesting the Iognormal model of poresize distribution incementpaste andmortarohaveaphysical t basis. Previous investigations ofporeevolution incementpaste haveshownthathedistribution tothesmaller t shifts poresize withincreasing andthat age, themediandiameter andthreshold diameter ofpores decreases with increase age{7].hispaperwill T show that, a givenset for ofcuring conditions, theweighing factors, fand (I0, andshapeparameters. ando2,ofsubdistributionsbe considered Ol may constant, while the location parameters, ot and o2, of subdistributions may be related to curing time. Thus, it becomes possible to predict the evolution in pore size during the curing of cement and mortar and to predict pore size distributions of cemem and mortar at any age. BACKGROUND OF LOGNORMAL DISTRIBUTION A variate X is lognormally distributed with the location parameter tt and the shape parameter0', if • X = logY where Y is a positive variate, which is normally distributed with mean tt and standasd deviation o. A compound lognormal distribution of pore sizes can be expressed as follows:
19
where p(x) is the probability density function for pores of size x, f and (I  f) are the weighing factors of subdistributions" l.tl and _t2 are the location parameters for subdistributions" o! and 02 are the shape parameters for subdistributions. Based on a robust statistical method [8], a program has been developed to detect the existence of a mixture of two lognormal distributions. For cementitious materials, the two subdistributions may represent the larger and smaller capillary pores, respectively [I]. EXPERIMENTAL Cement pastes were prepared having watertocement ratios (w/c) of 0.3 and 0.5. These were cured for I, 3, 7, 14 and 28 days and for I, 3 and 7 days, respectively. Pore size measurements were carried out at these ages using mercury intrusion porosimelry (MIP). The details of MIP can be found in reference [6]. Mortar samples were prepared at a watertocement ratio of 0.47. The cementtosand ratio used was 0.623. Saturated surface dry (SSD) sand was used. Samples were tested after curing for 1, 3, 7 and 14 day_. Triplicate MIP measurements were performed for each sample. RESULTS AND DISCUSSION A Comnound Lolnormal Distributionof Pore Sizes in Mortar Replicate measurements pore size dismbutions in mortarshowed excellent agreement. Figure I of showsthe variauonamong thr_measunmmmts ofthe cumulative size pore distributions ina mortar sample cured for 3 days. To evaluate the parameters of the compound lognormal diswibution, log x is plotted versus (log x p)/o • log x is defined the quantile of the mixture distribution and (log x  p)/o the quantile of standard normal distribution [8]. Figure 2 shows QQ plots for mortar samples cured for 1, 3, 7 and 14 days. The slopes of the two roughly linear segments are initial estimates of Ol and 02, the intercepts of the two segments are initial estimates of $tl and _2, respectively. The initial estimate for f is the deflection point. These estimates are then iterated. Mathematically, the iterationcan start using any one of these five estimates. They may result in different sets of estimated parameters, though they may generate the estimated distributions with the same goodness of fiL Therefore, it is necessary to establish the physical meanings and the reasonable ranges for the five parameters so that the estimation is not only judged by the goodness of fit, but also by the predetermined, physical meanings and ranges, The meaning of the weighing factors, f and (lf), is evident. It is necessary to establish the direct characteristics associated with the shape parameters and the location panmctas. Close examination of Figure 2 shows the linear segments at each end of curves to be almost parallel to each other. This suggests that the values for the shape parameters, Ol and 02 in the lognormal distributions of pore sizes are the same. Figure 3 shows the cumulative probability distributions for the mortars cured for 1, 3, 7 and 14 days. These curves exhibit the same shape behavior, which can be characterized by the slopes of the linear segments in Figure 2. Thus, the shape parameters in the compound lognormal distributions may be considered inde.pendent of curing time. It follows only the location pamn_ters alone may be related to curing un_ while that the shape parameters are related to other factors than curing time. Table 1 shows the estimated parameters. Figures 4ad compare the experiment_y obtained pore size distributions and those calculated using the estimated paramem's. The mean of sum of squaredenms between the two are 0.001, 0.001,.001 and0.002, respectively, indicating very good fits. 0
2O
"_
_
Do,/
X,,v,
"6
o.
t)_ameter (rim)'Q° Figure 1. Reproducibility of porosity measuremeritson mortarspecimens cun_ for 3 days.
°_o ,_o
,:mQuantile¢60 of ,.6ON(0.1)_6o _b
,.6o
Figure 2. QQ plots for mortarspecimens cured for l, 3, 7, and 14 days.
Estimates of parameters in lognormal modelfor poresize disn'ibufion n
oo
1 3 7 14 3.67 3.10 2.80 2.43 1.051.005 1.03 I.0 0.96I.0 0.850.98 0.16 0.I6 0.15 0.14 0.87 0.85 0.85 0.84 _o _ _,° 8 c_, ....... T40ays_
,,,
;b ............... Diometer (nm_° Figure3. Cumulativeprobabilitydiscibudons for mo_ cm'edfor 1, 3. 7, and 14days.
Prediction of Pore Evolution Durine Cement and MortarHardenine From above analysis, it was found that p! and P.2may be related to curing time. while the f, at and o2 may be assumed to remain constant. Figure 5a shows that Pl for mortars cured for 1, 3 and 14 days (can be related to cta'ing time as in days, t). P.l = 3.67403 t('°'ls63'tg) [2]
Figu_ 5b shows that g2 for moru_ cured for I, 3 and I4 days (can be related to curing time): tt2 = 1.07456 exp (0.016661t) [3]
It must be noted that equations 2 and 3 fit the limited, presently available data. Unlike in the use of Iogm,,mal model to describe pore size distribution, there is no physical basis for these equations. The 7day dam were not used to obtain the above expressions. Rather, seven day values were predicted from the above agep relationships. The predicted values are Pl = 2.71 and P2 = 0.96, assuming f = 0.85, Ol = 1.0 and 02 = 0.15. Figure 6 shows the comparison between the
21
experimentally obtained pore size dislribudon and that using the predicted parameters. The mean of sum of.squared em3_ between the two is 0.0011 indicating a very good prediction.
._
0
• _'_

1 Day Estimated
_
O "
%,,,
Estimated
"_o 0
Diameter (,nm)
Diameter (nm)
7 Days ,% _,_. ___ Experimental :__ "_ ,'_ ___
14 Days Estimated Experimental
_,_o 0
o!
tO
I_
o!
I0
IW
Diameter (nm)
Diameter (nm)
Rg,_ 4. Compa.,'iso. between expedmcm,_lly ob_dned CRg,_ 3) and caJcu_:d ix)n: size disu'ibudons usmg d¢ iognormai model.
t_. •
II.IIB_.m
Experimental
(t ** .156349)
* 3.67403
_ M_e=110.(11
n
Predicted
O _
ItLQI•
l,o

• t) • .0745
Ot_
s.6oAge (day) '°'_°
,s.bo
o.0.
.
.....Size i_lom)
. ..
Figure 5. Variations in I.tl and 1_2 with curing.
Figure 6. Comparison between experimentally obtained and calculated distribuuons.
22
'
Figure showsthe 7 cumulative probability distributions for cement pastes fabricated atawatertocementratio 0.3andcuredforI,3,7,14 and28daysandthose 0.5w/cratioementpastes for c curedforI,3 and7 days. The shapes ofthecurves inthefigures appear todependsu'ongly on watertocement butverylittle age. ratio on Figures showsthecorresponding plots. 8 QQ Ata given watertocement thelinear ratio, segments ateachendappeararallel p toeachother. Taken together, Figures and 8 suggest 7 that itshould also reasonable be toassumeconstant shape parameters cementpastes for atdifferent given samecomposition ages, the andcuringonditions. c
"'..,,/c=o.s
O_ I .O114 "4& _'k_. _ • t',_, X
°'.I
3 
.Io.O.3 ,,,, ',';
",,,,
,/e
ol
ll_iorneter
(n
Quontile
of
N(O,1)
Figure 7. Cumulativepore sizedistributions for Figure8. QQ plotsfor cement pastespecimens cementpastes: /c = 0.3 at l, 3, 7, 14, 28 days; havingpore sizedismbutions w shownin w/c = 0.5 at 1, 3, 7 days. Figure 7. Comparing Figures 7 and 8, the 0.3 w/c ratio cement pastesshowlitde change in pore size distribution with curing time. Comparedto pore size dismbutionsfor 0.5 w/c ratio cementpastes, there is significantly less large pore space available for size refinement. These data serve to reinforce the idea that the waterto.cement ratio determines the pore structure during the setting process and tha_it is from this pore structure that the pore evolution occurs [1]. Because the cumulative distributions of the 0.5 w/c ratio paste show noticeable shifts while maintaining the same shape, the method described above was used to predict the pore size diswibution in 3 day old cement paste. It was determined that f= 0.91, Ol  1.1 and o2  0.24. Figure 9 shows the agestl and agest2 relationships. From these relationships, the values predicted for Stl and $*2are 4.19 and 1.15, respectively. Using the above values for the five parameters, the predicted compound lognormal distribution of pore sizes in 3 day old, 0.5 w/c ratio cement paste was obtained and shown in Figure 10. In this instance the mean of sum of squared errors between the experimental and the estimated data is 0.0015. SUMMARY Based on presently available data, interpolation has been used to obtain It.values. In order to predict the long term changes in pore s_ucture, it will be necessaryto obtain sufficient pore size disnibudonsdata to allow exlxapolation. In addition, the relationshipsbetween w/c ratio and the o and St values, and those between curing conditions and o and St values have not been fully elucidated. Further acsessment of the effects of w/c ratio andcuring conditions on the parameters in the compound Iognormal model are needed. However, in spite of these limitations, the present work has shown that it is reasonable to assume constant values for o and f for both cement pastes and mortars to establishment of simple relationships between curing time and St values. Given sufficient data,it should be possible to predict pore evolution duringcement and mortar hardening, and to predict the pore size distributionof cement and mortarat any age.
23
ImJllS,
_l ..
(t ,* .0335962)
.4.35424
0tern
* 
Experlmentol Predicted
1tLm*
•, (t ** .0712061) * 1.24833
, _.
::1 0 I._1O.lm0.01e
E
"_
*
3,
AQe (day)
'_ize (rim)
Figure 9. Variations in Pl and £t2with curing. Figure I0. Comparison between experimentally obtainedandcalculateddistributions. CONCLUSIONS I. 2. 3. A compound lognormal distribution model can be used to describe the pore size distribution in themortarandprovides thebasisforthe predictionof theporesizedistributionat any age. It is reasonable to treatweighing factors and shapeparameters in compound lognormaIpore sizedistributionsfor cementandmortaras constants. Thelocation parameters inthemodel, canberelated _ tocuringime cementand mortar. t for
REFERENCES I. 2. 3. 4. , 5. 6. 7. 8. D. Sift, P.Brown andS.Kurtz,RS Meeting,oston, M B 1988, press). (in I. AJtchison and I. A. C. Brown, The Lognormal Distribution, CambridgeUniv. Press, Cambridge(1957). R. kani, J. Phys. Chem.,63. 1603 (1959). R. Irani and A. CaLlas,Panicles Size: Measurement. Internretation.andApnlicafion_ Wiley, New York (1963). S. Diamond and W. Dolch, J. Colloid and Interface Sci., 38. 234244 (1972). S. Kunz, S. Levinsonand D. Shi, J.Am. Ccram: Soc., (in press). D. W'mslow, J. Mat., 5, 56*.585 .(1970). E. Fowikes, J. Am. Star. Assoc., 74. 561575 (1979).
ACKNOWLEDGEMENT AND DISCLAIMER The research describedherein was suppo,nedy the Strategic Highway Research Program b (SHRP). SHRP is a unitof the National Research Council that was authorized by secdon 128 of the Surface Tnmspo_tion and Uniform Relocation Assistance Act of 1987. This paperrepresents theviews of the author(s) only, not necessarily reflective of the views of the National Research Council, the views of SHRP, or SHRFs sponsors. results reported The here are not necessarily agreement with the resultsof other SHRP researchactivities. They are in repottedto stimulate reviewanddiscussion within the research community.
c
24
CONCRETE MICROSTRUCTURE AND ITS RELATIONSHIPS TO PORE STRUCTURE, PERMF.ABILITY, AND GENERAL DURABILITY D.M. ROY, D. SHI, B.E. SCIIF_ETZ, ND P.W. BROWN A
Introduction The durability of concrete is frequently associated with the transport of dissolved species. Such transport may be considered in terms of permeability. It is well recognized that transport occurs through a continuous network of pores, which exist in the cementitious matrix of concrete, as well as through the porosity which exists in the interracial regions with aggregate. Unfortunately, however, the relationships between concrete permeability and the pore structures through which transport occurs are, at best, qualitative. It is the objective of this paper to describe work leading to rapid and accurate measurement of concrete permeability and the development of models to describe permeability of concrete in terms of pore structure.
Poised
Perm¢obility
Permeability measurements have historically been made with water or various gases including oxygen, nitrogen, argon and air. Darcyian flow has been used as the theoretical basis for the description of the observed flow conditions. This mathematical treatment required information on the sample dimension (crosssectional area and permeation length), flow properties of the fluid, a measurement of the flow rates and an established pressure gradient across the test specimen. The vast majority of experiments have been conducted at low AP in accordance_ with Darcy's derivation and usually with ambient pressure being the lower bound on AP. Experimental designs of this type are limited to values of permeability that are typically to the nanodarcy range. In using apparatus typical this type, water which has permeated through the test specimen is collected on an LVDT, the spring constant of which has been matched to the mass of water that would be collected in a reasonable laboratory experiment [Goto and Roy (1981)]. The resulting displacement of the LVDT by the permeated fluid is monitored and an equilibrium flow rate is determined. The permeability is calculated from this flow rate. One limitation to this particular experimental design is the evaporation of the permeated water from the container which is affixed to the LVDT. A second limitation is that the lower limit of operation for this apparatus is estimated to be 108 darcy.
25
To develop porositypermeability models, measurements on specimens having low permeabilities need to be carried out. To address this need, the pulsed permeability approach was implemented. Transient decays in pressure have been used in the pressurepulse permeability cell to successfully measure hydraulic properties of low permeability materials such as cored samples of rocks and sandstones (Brace et al. [1968], Hsieh et al. [1981], Neuzil et al. [1981]). To date, there has been little work devoted to the application of this technique to cementitious materials (Hooton and Wakeley [1989]), which generally have higher compressibilities and permeabilities. In the transient pressure pulse method, a jacketed sample is confined between two pressurized reservoirs which contain the penetrating fluid. The pores of the sample are also filled with the fluid. A confining pressure higher than the reservoir pressures is maintained on the jacket. When the experiment begins, the pressure in one of the reservoirs is suddenly changed to a higher or lower value and the resultant pressure changes on the high or low pressure side are measured as a function of time. The optimal way of collecting data is to simultaneously measure the pressure change in both reservoirs. Pommersheim and Scheetz [1989] have recently discussed the advantages of this technique. Hooton and Wakeley [1989] have emphasized the sensitivity of test results to environmental variables when measuring water permeabilities of concrete. Figure 1 presents a schematic diagram showing the experimental configuration for the transient pressure pulse test and Figure 2 a detailed, exploded drawing of the cell design. Before the test begins the entire system is equilibrated to a constant pressure P0. Then the pressure downstream reservoir (Pd) is suddenly deccreased to P1, while the upstream reservoir (Pu) remains at P0. Pu will decrease and Pd will rise as fluid is transferred between reservoirs. A constant confining pressure (Pc) is kept outside the sample. By maintaining this pressure at a level considerably higher than P1, leaks are prevented. However, Pe is limited to avoid creep or microcracking. Figure 3 is a schematic representation of how the upstream and downstream pressures change with time for two typical classes of materials. The figure is illustrated for the case where the two reservoir volumes, Vu and Vd, are equal. Nomenclature is provided beneath the figure. The curves marked A. are the pressure decay and pressure rise curves for "tight rocks" such as granite which typically have low permeabilities and compressibilities. Here the response of the two curves is symmetric around a horizontal line drawn to the final pressure Pf reached by both reservoirs. These data collected for an actual sample are presented in Figure 4. As discussed by Pommersheim and Scheetz (1989), the analysis of Brace et. al. [1968] predicts that this pressure will lie midway between P0 and P1, while the analysis of Hsieh et. al. [1981] predicts that Pf will lie more towards the upstream side. The difference is attributable to the fact that Brace and coworkers assumed in their
°
26
development that the compressive storage of the sample was negligible, whereas Hsieh and coworkers did not. Pf can also be estimated from a mass balance knowing the pore volume of the sample and the volumes and initial pressures in the reservoirs (Trimmer [1981]). Model Development
Previous mathematical models for pressure pulse testing have been developed by Brace et. al. [1968], Lin [1977], Hsieh et. al. [1981] and Pommersheim and Scheetz [1989]. As a model system consider the cylindrical sample depicted in Figure 1, having total volume V = AL, where A is the crosssectional area of the specimen and L is its length. The sample is confined between the two pressurized reservoirs, the upstream one at Pu and the downstream pressures are P1 and Po, respectively. The partial differential equation which governs pressure changes as a function of distance and time P(x,t) within the sample is given by: o_p 6)(2 where g k P = = = ,( &p ,_ 2 #\6x) fl' # k 6P at (1)
+
pressure within the sample;
pore fluid viscosity; sample permeability; within the sample, measured from the upstream
x = axial distance reservoir; t = time;
13' =
lumped compressibility.
Equation (1) represents how the pressure P(x,t) varies within the sample as a function of position x and time t. It is a nonlinear partial differential equation subject to one time and two boundary conditions. These are given by: P(x,0) = P0 P (0,t) = Pu(t) P(L,t) = Pd(t) initial condition conditions
boundary
27
where L is the sample thickness, and Pu and Pd are the upstream and downstream pressures, respectively. Assumptions involved in the derivation of equation (1) include: one dimensional mass transfer with constant transport area, constant temperature, and constant physical properties (g, k, [_' and porosity). These assumptions are the same as those stated or implied by previous workers [Brace et. al. (1968), Hsieh et. al. (1981)]. Most of them are likely to be met in laboratory tests with homogeneous corings. Sample cempressibilities will he most likely to remain constant when the ratio of the confining pressure to the initial pressui'e difference, i.e., Pc/ (P1P0)is high [Hooton and Wakeley (1989)]. 13' is a lumped compressibility. It depends on the compressibility of the fluid, 13, the compressibility of the sample, 13s, the effective compressibility of the jacketed sample 13e, and the sample porosity e, according to: 13' = (13e  13s) + e(13  [3e) (2)
A similar equation has been presented by Brace et. al. [1968] and Hsieh et. al. [1981]. Of all three quantities be is the one which is least likely to be known and which is also potentially the largest, especially in experimental configurations where the sample is retained in a flexible rubber or plastic sleeve. In effect this makes 13e, and thus 13', an arbitrary parameter. Neuzil et. al. [1981] found values for this parameter which were several orders of magnitude greater than the fluid compressibility. By introducing the dimensionless distance z = x/L, time 0 = t/T, and pressure P = (P P0)/AP, equation (1) and its attendant conditions become:
6z2 (I)
where
+
a,AdSP/ = _, z ,, o
(II)
P0 = Pu(q) Pd(q)
6o (III)
(3)
AP = P1 p(0,q)
with conditions:
reduced reduced
boundary initial
conditions
p(1, q) =
conditions
p(z,0) = 0
¢
T = 13'ttL2/k is a characteristic time for the transfer of mass from the high pressure to the low pressure side.
28
,
The terms in equation (3) have been labeled (I), (II) and (III). Term (I) represents the transfer of mass between reservoirs caused by the pressure difference. It is present in all formulations of the problem. The unsteady state term (III) corresponds to the accumulation of mass within the sample. If the observed experimental times t are much greater than the characteristic time T, i.e., t >> T, then the accumulation term can be neglected. This is a requirement of a steady state process. However, since the pressures at the two ends of the sample are continuously changing, pressures within the system slowly adjust to accommodate these changes, in effect adjusting to each new steadystate. Such behavior is called quasistatic and the system is said to be at quasisteady state. Term (II) in equation (3) represents the dynamic response to the compression of the jacketed sample. This nonlinear term will be small when the dimensionless compressibility 13'AP is small. Calculations show that term (II) would be small if _' is of comparable magnitude to the compressibility of the fluid, but, as discussed, this is often not the case in practice. Application of these equations to data from Figure 4 should result in a strength line when stated at time vs. Pu  PL k From the slope of this line the characteristic chance time can be determined and subsequently the permeability. Figure 5 represents the processed data and the regression fit to the data. Pore Structure Recent studies by Shi et al. [Shi et al., 1989, 1990a, 1990b] have shown that the pore size distributions in cementitious materials may be described in terms of a mixture of lognormal distributions. A variate X is lognormally distributed if Y = logX where X is a positive variate, (0 < X < **), which is normally distributed with mean _t and standard deviation ¢_ with regard to Y. The probability density function of a lognormal distribution is [Aitchison and Brown, (1957)], p(x) = (2xa2) 1/2 X1 exp[0.5{(log(x)  lX)/o}2]
,
"
The range of x is 0 < x < _t. Ix is defined as the location parameter, a is defined as the shape parameter. The mean, median, mode and variance are as follows: mean = exp(_t + 0.502) median = exp(lx)_ mode = exp(].t  0 2) variance = mean2[exp(o2)l]
29
The mixture of two or more lognormal compound density function: P(x) = _: fi p(x, _t , a i) i Zfi=l
distributions
is defined
by a
where fi is the weighting factor the ithsubdistribution b cri),nd of p(x,IA a Ix and c_ are locationparameterand shape parameterof the ith subi i distribution, respectively. statistical A method was developedto detect if thereis a mixtureof two lognormaldistributions iteratively and estimate the parameters the compound distribution in [Fowlkes, (1979)]. Without a computer program, the iterative estimation of parametersis extremely difficult. However, one can use a simplegraphical ethod to obtainfirst m degree estimatesof parametersfor a compound distribution two or of more lognormaldistributions. method is described s follows.Suppose The a that one has obtaineda set of cumulativeprobability data,P(X) vs. X where X is thepore sizeand P(X) is the relative percentagef pore volume o with respectto the total pore volume. The graphical approach to obtain estimates of parameters of a mixture of two or more lognormal distributions be summarizedas follows. can Step 1: Transform X to log(X). Step 2: Find the quantiles of N(0,1) corresponding to P(X), by consulting standard normal distribution tabulation which can be found in statistics text book. For example, if the cumulative percentage is 50%, corresponding quantile is 0; if the cumulative percentage is 84%, corresponding quantile is 1.0; etc. Step 3: Plot log(X) vs. the quantiles. If one single straight line is found, one can conclude that X obeys a lognormal distribution. If more than a single straight line is observed, it is likely that the porosity can be described by a mixture of lognormal distributions. Step 4: Determine the intercepts and slopes of each linear portion. These correspond to _ti, and ci, i =l,...,n, respectively. From the intersections between any two neighboring linear segments, one can find the weighting factors, fiStep 5: Determine the quality of the fit by drawing lognormal distributions using the parameters obtained and comparing them to the data. the any the the
30
4
An important characteristic of a mixture of lognormal distributions is the inflection point. This is located on the experimental curve at the intersection between the first two linear segments. The corresponding log(X) value is: [a2 lXl  al Ix2] / [a2  all inflection point with of the model fit. and Permeability that from the experimental
7
Comparing the calculated data allows a comparison Pore Structure, Percolation
.
Among the models relating pore structure and permeability, percolation theorybased models are physically the most meaningful. Percolation theory assumes a lattice containing a very large number of lattice points [Stauffer, (1985)]. It is assumed that a point can be randomly occupied or vacant independent of the states of the neighboring sites. However, depending on the situation, additional assumptions can be made which influence site occupancy. Accordingly, occupied sites may be isolated from each other or connected with neighboring sites to form a cluster. When only a small fraction of the total lattice sites are occupied, the probability, p, that a given site will be isolated is high. With increasing site occupancy, the probability of the formation of a large cluster, which extends from one side of the lattice to the other, becomes nonzero. Such a large cluster is called "infinitepath." It percolates through the lattice in the similar way that fluid percolates through porous materials along the network of "infinitepath" pores. There is a statisticallybased critical point (percolation threshold), Pc, below which no 'infinitepath' can form. It is clear that these concepts are relevant to the transport of liquids through the "open" porosity in concrete. In the determination of permeability, only the liquid which flows through the network of connected pores is determined. The network of connected pores is equivalent to the "infinitepath" in percolation theory. Therefore, it is the structure of the infinite network, not the total porosity and its distribution, which controls permeability. It is generally accepted that only pores with diameter greater than some value effectively contribute to permeability. The observed inflection pointon the cumulative pore size distribution determined by mercury porosimetry locates the minimum diameter of pores which are continuous through all regions of the hydrated cement paste [Nyame and Illston, (1980); Mehta and Manmohan, (1980); Hughes, (1985); Goto and Roy, (1981)]. It is this observation which provides the connection between the lognormal model for pore structure, discussed above, percolation theory and permeability.
31
A Preliminary PCrqol_tionPermeability
Model
Most of the percolation models which have been developed have been applied to describing flow in sedimentary rock. This work suggests that a power law may exist between permeability and a characteristic pore dimension, and that a tortuosity factor which may be quantified by using percolation concepts. These are important aspects of modeling pore structurepermeability relationship in cement and concrete. In percolation theory, the relationship: f = C(p'  pc) n can be used to relate f, the fraction of connected pores in the infinite network, to the critical porosity, Pc. C and n are constants, Pc the critical porosity below which there is no flow permeating at all, p' the probability that two pores interconnect, and f is related to tortuosity [Guegeun and Dienes, (1989)]. It has been suggested that n = 1.9 or 2 [Fisch and Harris, (1978); Berman, et al, (1986)]. In the following, the three remaining parameters are calculated. Assuming p' to be proportional to porosity p and represented by Pc', we have f = C'(ppc') 2, where pc'= Pc/c'. Pc' can then be obtained by extrapolating the porositypermeability curve to the point where the permeability equals zero. C' can be obtained by fitting the experimental data to the model. From very limited data on permeability and pore size distribution, we calculated P.C' = 0.15 and C' = 0.23. We chose the second moment of the pore diameter distribution,<D2>, as the characteristic pore dimension. The predicted permeability is (the derivation is omitted here): k = (f/32) p<D2> The second moment of a lognorrnal distribution is exp(2ix + 2a2). In our compound lognormal model for pore size distribution, <D2> = Y_fi exp(2 (IX+ a2)) This approach can be demonstrated using the data shown in Figure 6, which are for a fly ash blended cement (fie = 0.536), mixed at a watertosolids ratio of 0.55 and hydrated for 28 days at 23°C. The value of<D2> was calculated as 2383 nm2. The porosity and permeability were determined to be 0.45 by MIP and 3.86 x 105 Darcy by flowthrough permeability, respectively. The calculated value of the permeability is 1.93 x 105 Darcy. Although the prediction is satisfactory in this case, the model must be validated by comparison to additional data to obtain reliable values for C', Pc, and to verify its general validity.
"
32
S_mmary We have briefly discussed the means for the rapid measurement of permeability, the means by which pore size data obtained from mercury intrusion porosimetry can be quantified, the basis for using percolation theory to treat the pore data, and the development of a preliminary model to describe permeability.
,
33
References J. Aitchison and J.A.C. Brown, The Lognormal Univ. Press, Cambridge (1957). D. Berman et al., Conductances Rev. B, 3_, 4301, 1986. of filled Distribution, Ch. 2_ Cambridge
P
twodimensional
networks,
Phys.
W.F. Brace, pressure,
J.B. Walsh and W.J. Frangos, Permeability of granite J. Geophys. Res. 7_ (6), 22252236 (1968).
under
high
R. Fisch and A. Harris, Critical behavior of random resistor the percolation threshold, Phys. Rev. B, 18, 416, 1978. E. Fowlkes, J. Am. Stat. Assoc., 74, 561575 (1979).
networks
near
S. Goto and D. Roy, The effect of w/c ratio and curing temperature on the permeability of hardened cement paste, Cem. Cone. Res., 11, 575, 1981. Y. Gueguen and J. Dienes, Transport properties percolation, Math. Geology, 21, 1, 1989. J.D. of rocks from statistics and
Hooton and J.D. Wakeley, Influence of test conditions on the water permeability of concrete in a triaxial cell, Pore Structure and Permeability of Cementitious Materials, 15764, L.R. Roberts and J.P. Skalny, Eds., MRS (1989). Hsieh, J.V. Tracy, C.E. Neuzil, J.D. Bredehoeft and S.E. Silliman, A transient laboratory method for determining the hydraulic properties of 'tight' rocksI. Theory, Intl. I. Rock Mech. Min. Sci. & Geomech. Abstr. 18, 245252 (1981). of hardened cement paste, Mag.
P.A.
D. Hughes, Pore structure and permeability Cone. Res., 37, 227, 1985. L.B.W. Jolley, Summation New York (1961). P. of Sorie_, 2nd
revised
ed.,
Dover
Publications,
Mehta, and D. Manmohan, Pore size distribution and permeability of hardened cement paste, in 7th International Congress on the Chemistry of Cement, 1980, Vol. 3, pp. VII 15.
C.E. Neuzil, C. Cooley, S.E. Silliman, J.D. Bredehoeft and P.A. Hsieh, A transient laboratory method for determining the hydraulic properties of 'tight' rocks II. Applieati0n, Intl. J. Rock Mech. Min. Sci. & Geomech. Abstr. 18, 253258 (1981)
34
B. Nyame, and J. Illston, Capillary pore structure and permeability of hardened cement paste, in 7th International Congress on the Chemistry of 17ement. 1980, Vol. 3, pp. VI 181185. J. Pommersheim and B. Scheetz, "Extension of standard methods measuring permeabilities of pressure pulse testing, to be submited publication (1989). for for
D. Shi, P. Brown and S. Kurtz, "A model for the distribution of pore sizes in cement paste," 2334, Pore Structure and Permeability of Cementitious Materials, L.R. Roberts and J.P. Skalny, Eds., MRS (1989). D. Shi, W. Ma and P. Brown, "Lognormal simulation of pore evolution during cement and mortar hardening," 14348, Scientific Ba_i_ for Nuclear Waste Management XIII, V. Oversby and P.W. Brown, Eds., MRS (1990a). D. Shi, P.W. Brown and W. Ma, "Lognormal Simulation of Pore Size Distribution in Cementitious Materials," J. Am Ceram Soc, submitted (1990b). D. Stauffer, Introduction London, 1985. D. Trimmer, permeability tQ Percolation Theory, Ch. 2, Taylor & Francis, of low
Design criteria for laboratory measurements rocks, Geophys. Res. Lett. 8 (9), 973975 (1981).
35
Figure (_aptions Figure 1. Schematic Figure 2. Exploded Figure 3. Theoretical experiment. Figure 4. Typical Figure 5. Typical drawing drawing of the pulsed of permeability permeability cell. for pulsed experiment. experiment. permeability apparatus.
pressuretime
behavior
raw data for pulsed permeability processed data for pulsed
permeability
Figure 6. Cumulative pore size distribution 0.536, cured for 28 days).
of FA cement (w/c = 0.55, f/c =
36
37
:! ,i
ei
38
eJnsseJd
39
0 I0 IJJ 03 ¢0 LU
0  ,_0
a: a.
X
® ®
0
0
0
0
0
0
0
0
40
¢D
41
42
POROSITY/PERMEABILITY RELATIONSHIPS P.W. Brown Department of Materials Science and Engineering Pennsylvania State University Dex Shi Civil Engineering Department Pennsylvanic State University J.P. Skalny W.R. Grace Iotroduq_ign The structure of the porosity in concrete strongly influences its performance. Specifically, porosity determines the rates at which aggressive species can enter the mass and cause disruption. Rates of intrusion are related to the permeability of the concrete. In the most general way, permeability depends on the total porosity. More importantly, however, permeability depends on way in which the total porosity is distributed. Porosity, in turn, is related to the original packing of the cement, mineral admixtures, and the aggregate particles, to the watertosolids ratio, to the rheology, which is related to the degree of dispersion of the solids originally present, and to the conditions of curing. This contribution considers the nature of porosity in cement and concrete, discusses its measurement and the limitations in the interpretation of porosity data. Models developed to describe porosity both in cement paste and concrete are reviewed. With emphasis on permeability models developed for a variety of porous inorganic materials, relationships between pore structure and permeability are discussed in terms of their applicability to concrete. The Nature of Porosity in Cement Paste. Mortar and Concrete From a pragmatic standpoint, porosity of a material is not of interest as an end in itself. Rather porosity is of interest because it directly influences both mechanical and transport properties of cementitious materials. For example, the pore shapedependent relationship between porosity and strength, <_, of the form: <_/o' = exp(be) o
*Materials Science of Concrete II (in press).
.
o
[1]
48
is well known [1], where b is a shapedependent parameter, e the porosity and 0o the ideal strength. This relationship is illustrated in Figure 1 [2]. With respect to durability, the ability of concrete to resist various forms of deterioration is often related to its impermeability. Analysis of the sources of porosity and its connectivity can frequently provide the means to understand the mechanisms by which aggressive species can intrude concrete. This is because the pore structure defines the paths along which liquid or vapor preferentially moves. This, in turn, is of obvious importance with respect to specific durability considerations including the transport of freezable water and electrolytes, such as chlorides, through concrete. It is widely accepted that permeability is determined by microstructure. Microstructure in this context is defined in terms of pore and crack structures. A large number of models have been developed, particularly for sedimentary rocks, to predict the permeability from measurements of pore structures and cracks [312]. For cementitious materials, it is well recognized that both total porosity and its distributions determine the permeability [1316], and that only pores with diameters greater than a specific value contribute significantly to permeability [13, 14, 16]. Figure 2, for example, illustrates the dependence of permeability on the porosity [17]. It has also been observed that the inflection point on the cumulative pore size distribution obtained by mercury porosimetry locates the minimum diameter of pores which form a continuous network through hydrating cement paste [13, 14, 16]. Large variations in permeability of concrete having nominally similar porosities are frequently observed [1315, 18]. Verbeck even implied that the permeability of concrete may not be a fundamental material property [19]. Alternatively Podvaley and Prozenko [20] claimed that the variations should in most instances be considered an objective characteristics of the phenomenon, and that the source of variation in permeability results from small variations in concrete microstructure. As a consequence, it is useful to enumerate the various types of porosity present in concrete and to establish their relative contributions to permeability. There are a variety of "types" of porosity in concrete. These types may be classified in terms of their origin or in terms of their anticipated effect on measurable parameters such as strength or permeability. Sources of porosity in concrete include:
44
1. 2. 3. 4. 5. 6. 7.
gel pores smaller capillary pores larger capillary pores large voids (also included in this category may be intentionally added voids such as by air entrainment) porosity associated with pasteaggregate interracial zones microcracks and discontinuities associated with dimensional instabilities that occur during curing porosity in aggregate
The diameter of a stable gel pore is assumed to be about 2 nm [21]. The reason for the selection of this value is based on the assumption that hydration products cannot precipitate in pores having diameters smaller than about 2 nm. Because the gel porosity resides in the hydration products that accumulate between the liquid phase and the anhydrous cement grains, gel porosity has a major effect on hydration rates but only a minor effect on transport processes involving liquids. However, there is at present no justification for ignoring the other types of pores listed above. Thus, the contribution of each of the remaining types of porosity to permeability must be considered. Unfortunately, deconvolution of the relative contributions of each of these sources of porosity to permeability has not been carried out. Therefore, conclusions reached regarding concrete permeability are frequently based on extrapolation of results obtained for cement pastes. However, it may be reasonable to subdivide the porosity in concrete into two classes: (1) that in the paste matrix and (2) that associated with the aggregate and paste interface. The principle source of the matrix porosity contributing to permeability is that associated with residual space between cement grains which was originally filled with water. The contribution of this source of porosity may be amenable to assessment by investigations of cement paste. However, the contribution of the porosity associated with the interracial zones between paste and aggregate and the microcracks that develop in this interfacial region, which extend into the paste, to permeability must be assessed by determinations carried out directly on aggregatecontaining materials. Two types of porosity can be considered to form the network of capillary porosity present in cement and concrete: large and small capillary porosity. One reason for categorizing porosity in this manner is related to the influence of chemical and mineral admixtures on the two types. Capillary porosity is assumed to have a major effect on transport processes but only a minor effect on
45
hydration rates. The diameters of capillary pores could in theory range from very small values to large ones. However, it has been assumed that the lower diameter limit of capillary porosity is 100 nm [14, 16, 22]. It is worthy of note that there is an apparent discrepancy between the size of a gel pore (2 nm) and the lower bound on the size of capillary pore. According to the IUPAC [23] classification of pore sizes, the diameter of a micropore is 2 nm or less while that of a mesopore is between approximately 2 and 50 nm. Mesopores are of a size range for which electrostatic interactions between the pore walls and the liquid would extend over a significant fraction of the crosssectional area. A consequence of this may be that transport processes through pores having diameters in this range are hindered by electrostatic effects. It is well known that the mineral admixtures affect permeability; the basis for this effect can be understood in terms of the formation of a larger amount of porosity in the mesopore range. However, this view requires further experimental verification for both portlandpozzolan and pc.tlandslag systems. Overview of Porosity Measurement and Jntcrpretation of D_ta Three important types of techniques have been used to experimentally measure the porosity and/or its distribution in porous materials. These techniques are gas adsorption, mercury intrusion, and direct observation techniques including serial sectioning and pore casting followed by optical or SEM observation of the sections or the casts. Vapor or Gas Adsorption This technique involves the adsorption of a gas (including water vapor) on the accessible internal surfaces of a specimen. Because a significant degree of uncertainty regarding the interrelationships among hydration phenomena, pore size distributions, and properties of cement systems remain, studies using this technique have been carried out over the past decades to elucidate them. However, internal surface areas determined by gas adsorption experiments are dominated bythe gel porosity, which has only a minor effect on bulk transport. Mercury Intrusion
A second, important technique to determine porosity is mercury intrusion. In this technique, mercury is forced into porous samples with increasing pressure. Because the mercury is assumed not to wet the internal sample surfaces (the angle of contact between
46
,
a drop of mercury on a cement surface representative of the the internal surface and the surface would be greater than 90°), the intrusion pressure can be related to the diameter of the pore intruded provided the contact angle between the mercury and the sample are known or can be assumed. The value assumed for the contract angle allows the calculation of the diameter of the pore intruded according to the Washburn equation [24]: P = 2_cosO/r [2]
where P is the pressure needed to intrude a pore of radius r, x is the surface tension of mercury, • is the angle of contact. The application of mercury intrusion porosimetry to measure the distributions of pore sizes in cements was pioneered by Winslow and Diamond [25, 26]. Although there are certain limitations to the use of mercury intrusion in the analysis of the pore structures of cements, the technique is very attractive since it measures pores of the general size range that appear to control permeability. Data obtained by mercury intrusion tiorosimetry (MIP) must, however, be interpreted with caution. Pores in the general size range or 50 to 100 nm are of a size for which capillary condensation is of importance. The occurrence of capillary condensation is based on the assumption proposed by Zsigmondi [27] that the equilibrium vapor pressure in a pore of a given diameter can be determined by the radius of curvature of the meniscus of the liquid in the pore. This leads to the familiar Kelvin equation: ln(po/p) =2xM/(SaRT) where Po is the saturation vapor pressure saturation vapor pressure of the liquid in the interracial (surface) tension, M is the density, T is the absolute temperature and Rearranging the Kelvin equation gives: p = po/(e x) [3] of the bulk liquid, p is the a pore of diameter a, x is molecular weight, 8 is the R is the ideal gas constant. [4]
where x is the righthand term in Eq. [3], and shows that the saturation vapor pressure in a pore is reduced with respect to that in the bulk liquid. A consequence of this is that pores in this size range remain filled with liquid at relative humidities below 100%. Therefore, attempts to minimize disruption to pore structures by drying under conditions less aggressive than 105"C, for example, may result in incomplete desiccation.
47
Another important factor complicating interpretation of pore size data for cements is the presence of "ink bottle" pores. Gas adsorption experiments on cements have shown that there is significant hysteresis between the adsortion branch and the desorption branch of the curves [see for example 28]. Katz [29] was probably the first to point out that sorption hysteresis occurs when smaller capillary pores do not empty during desorption with the effect of blocking the emptying of larger capillary pores. Generally similar behavior is observed with mercury intrusion experiments; some of the mercury intruded under pressure remains trapped in cement specimens when the pressure is removed even though is it assumed that the mercury does not wet the specimen surfaces. This is the result of mercury being forced into smallnecked pores. A consequence of this phenomenon is that large pores with small necks appear as many small pores. Cerbesi [3.0] reported that approximately 75% of the pore volume of cement paste interrogated by MIP is composed of pores uniform in cross section. The remaining 25% are "ink bottle" pores. Because bulk transport is primarily affected by the minimum pore diameters, this phenomenon may influence the interpretation of MIP data with respect to permeability. An additional factor that must be considered when pore structures are determined by mercury intrusion porosimetry is that closed porosity is difficult to determine unless the pore walls are damaged by the intrusion process. It is not necessarily undesirable that closed porosity is not intruded because it is unlikely that closed porosity would significantly contribute to transport processes. Alternatively, the rupture of pore walls would result in regions of closed porosity being included in the measurement of porosity because the membranes of hydration product that isolate these regions from the capillary porosity network are destroyed during mercury intrusion [see for example 31]. Another limitation to the interpretation of pore size data is related to the uncertainty in the value of the contact angle used in the Washburn equation. Finally, because specimens are routinely desiccated before mercury intrusion, mesopores will appear to contribute more to the pore size distribution of the fine fraction than is appropriate. Taken together, these phenomena serve to complicate the interpretation of experiments using mercury intrusion porosimetry which attempt to assess both the volumes and size distributions of pores that significantly contribute to permeability.
48
Direct
Observation
of Porosity
There are two types of techniques used to directly observe the porosity in cement paste, mortar, and concretes. The first of these is the direct observation of large pores on a polished section using optical microscopy. The observation of air void spacings is one example of this. However, the observation of finer pores usually involves the intrusion of a monomer and its polymerization or the intrusion and hardening of an epoxy. Porosity can then be observed in polished sections or in thin sections via optical microscopy [32, 33]. The observation of porosity with an optical microscope is frequently enhanced by the use of ordinary or fluorescent dyes [34]. This technique has also been applied to the observation of microcracks in mortar [35]. The observation of porosity by optical techniques is limited by the resolution of the optical microscope. Typically these analyses are carried out at low magnification, 40400X. Optical microscopic observations may also be carried on polished sections from which material is systematically removed by cyclic polishing between observations. Analysis of the pore size data from the serial sections can then be used to assemble a montage of the three dimensional pore structure. A less tedious variant of the technique of preparing serial sections is pore casting. Pore casting has found application in the analysis of the pore systems in rocks using both optical and electron microscopy [36, 37] but very limited application in cements [38]. In this technique the pore structure is filled with a plastic material and the inorganic matrix is dissolved to reveal the threedimensional pore network. The advantage to pore casting is that it is possible to analyze the pore structure as a network. Electron microscopy has also been used to analyze the porosity on polished sections. This is accomplished either by direct observation of the pores or by intruding the pores with a compound containing an element readily detected by energy dispersive xray analysis, such as a chlorinecontaining polymer, followed by an areal compositional analysis for regions high in chlorine. Typically, this can be done with a resolution of 35 v m. Regardless of the specific technique selected, there are two major limitations of direct observation of pore structures. The f'Lrst is the limitation on resolution when optical microscopy is involved. The second limitation is that regarding the ability to intrude epoxy or monomer into small pores. However, regardless of these limitations, direct observations of pore casts, polished sections, and thin sections
49
in concert with image processing have developed technique for pore structure analysis [3943]. Models for Pore Size Di_ribution_ in Cements
into
a powerful
In spite of the variety of limitations, previously discussed, mercury intrusion has come to be regarded as a standard means by which the pore structures of cement pastes are examined. The pressure at which mercury will flow into a pore is related to the size of that pore. Thus, by determining the volume of mercury intruded as a function of intrusion pressure, plots as shown in Figure 3 [25] are obtained. While data of this type are useful in comparing relative pore size distributions in various cement pastes, further analysis is required to extract descriptors of these pore size distributions. Such descriptors can then be used in permeability expressions. The most common method of analyzing porosity data is to determine an averaged pore size. This is the most straightforward approach. However, from the standpoint of those processes that affect cement porosity this may not be the best approach. Rather, the nature of the pore size distributions need to be defined in terms that can be treated quantitatively. This is most readily done by describing pore sizes using a distribution function. The general form of a function that may be used to describe a cumulative pore size distribution is: P(R >r) =
fr °Q
V(r)dr;
P(O) = 1,
[5]
where P(R>r) is the probability that a pore will have a radius larger than r, i.e. the cumulative pore size distribution, V(r)dr is the volume fraction of pore space whose radii are between r and r + dr. The probability that a pore will have a radius larger than zero is unity. Little appears to have been done in terms of developing distribution functions describing the porosity of cement pastes. The exception to this is an investigation by Diamond and Dolch [44]. In this investigation it was reported that the distribution in pore sizes in a hardened cement paste could be described by a lognormal distribution function. This is a significant finding because the data were obtained by mercury intrusion porosimetry. Diamond [45] also measured the variations in pore size distributions with temperature over a range from 6 to 400C. He observed pore size distributions to be initially coarser in pastes cured at elevated temperatures but that the differences became negligible after about 1 month of curing. In
50
,
accord with earlier work, Diamond also observed that the distribution in porosity could be treated as lognormal. Recently, Shi and coworkers [46, 47] have extended the analysis to MIP data obtained at high intrusion pressures. Using robust statistical techniques Shi, et al have observed that is possible to describe the distributions in pore size in both cement paste and mortar in terms of a linear combination of lognormal distributions. The equations used to describe distributions of porosity are of the form: p(r) = Z fi p(r, _ti, ci), Z fi = 1.0 [6]
where p(r) is the probability density function, fi the weighing factor of the itla lognormal subdistribution, i.ti and _i the location parameter and shape parameter in the i th lognormal subdistribution p(r, I.ti, ai), respectively. As hydration proceeds, the location parameters change significantly, while the relative weights of the subdistributions and the shape parameter change relatively little. The significance of this finding is that it is possible to describe the variation in porosity distribution as a function of watertocement ratio and as a function of curing time in terms of the variation of parameters having direct statistical significance. These parameters can be incorporated, in turn, into pore structurepermeability relationships. Techniques Used to Measur_ P_l'mcability
A variety of techniques have been developed for permeability measurement. A number of these are summarized in ref. [48]. The most common technique is the measurement of the amount of water that can be forced through a specimen subjected to a large hydraulic head under conditions which approach steady state. Such permeability measurements suffer from several disadvantages. If a sample is relatively impermeable, the use of a relatively small length is required. This raises the question of representativeness. The solubilities of hydrated cement phases will vary in response to the local hydrostatic pressure. Thus a pressure gradient through a sample can lead to the redistribution of the more soluble phases, Ca(OH) 2 and gypsum, if present. Redistribution of solids can affect the pore structure and, thus, the permeability. A third disadvantage, which is ubiquitous to essentially all permeability measurements, is that specimens having low permeabilities are saturated only with great difficulty. A second, relatively common method for measuring permeability is the rapid chloride permeability method [49]. In this method, chloride ions migrate through a specimen under a potential gradient. The advantage to the method is its relative rapidity.
51
Disadvantages are that there is resistive heating associated with the voltage drop across the sample and that the chloride can rcac_ with aluminam phases and influence the pore structure. One approach to eliminating the problems inherent in the more traditional methods of permeability measurement is to minimize the pressure gradient across the sample. Such a method has been developed to measure the permcabilities of rocks [50]. According to the method, the pressure gradient across the sample is initially zero. A zero pressure gradient is attained by using two pressurized reservoirs. In order to make a measurement, the pressure in one of the reservoirs is rapidly elevated or lowered and the rate of decay in the pressure gradient across the sample is measured. The rate of decay can then be mathematically related to the permeability [50]. While this method offers the advantages of rapidity in measurement at relatively low pressure gradients [51], obtaining fully saturated, low permeability samples remains a problem [52]. Models for the Pcrmeabiliti¢_ of t_¢rnent and (_oncret¢
Consideration of models developed to "describe the permeability of porous media will include empirical models, network models, probabilistic models and models based on percolation theory. Empirical Models
In general, permeability is a measure of the ease with which a fluid passes through a porous body [53]. The most common expression used to describe the permeability, k, is Darcy's Law: k = p.Q/[ A 8g(dh/dz) ] [7]
where Q is the volume of fluid discharged per unit time through the crosssectional area A, I_ is the viscosity of the fluid, 8 is the density of the fluid, g is the acceleration of gravity, dh/dz is the hydraulic gradient in the direction of flow, z. Another simple model is that states that the volume flow through Q = xr4/8ttdP/dl where p. is the viscosity gradient causing flow along of the fluid and a tube of length I. dP/dl is the pressure of Poiseuille [4]. Poiseuille's law a capillary tube of diameter r is
52
These simple models Can be combined to develop an expression for permeability. Assuming the porosity in a crosssection through a material with total porosity p to result from the intersections of pores having different diameters ri, the term A in Darcy's law can be expressed as S/p. S is the crosssectional pore area. In this case, the total volume flow can be expressed in both Darcy's law and in PoiseuiUe's law as: Q = S/e k/gdP/dl Q = Z_(ri)4/SgdP/dl (Darcy's law) (PoiseuiIlie's law) [9] [10]
(The terms g and 8 only result in different units) Combining both equations results in: k = e/S_;_z(ri)4/8 = e(Y_Si(ri)2/8)/S = = e(_(ri)2(ri)2/8)/S e <r2>/8 [11]
where Si is the crosssection area of pores of radius ri, <r2> the mean squared pore radius, or the second moment of the pore radius distribution. This model relates permeability to porosity and the average pore size by assuming that pores are tubes and do not interconnect. Another frequently encountered permeability model is the CarmenKozeny model. This model is sometimes referred to as the hydraulic radius model since it assumes pore diameters to be 4 times the void volume of the medium divided by the pore surface area. It relates the permeability to total porosity and the specific surfaces area of the pores. The mathematical form of the CarmanKozeny model is k = e3/[ko (Le/L)2(1  e)2S 2] [12]
where e is the total porosity, k o is the permeability of an infinitely dilute bed, Le is the average path length for flow, L is the path length (Le/L is often called the tortuosity), S is the specific surface area [52]. Archie's law model [55] relates porosity a power law. This model is expressed as k **eta and permeability using [13]
53
being the total porosity and m a constant. In the Archie model factors as connectivity and tortuosity, which are important to permeability of cementitious materials, are not considered. Each of the above models relates permeability to the porosity in some fashion. It is of significant interest to relate the permeabilities of cementitious materials to parameters that control the development of microstructure. As a consequence, a variety of investigations have been carried out to elucidate possible relationships between pore structures and permeability in cementitious materials. Auskern and Horn [56] compared the pore size distributions obtained by mercury intrusion porosimetry for pastes hydrated at watertocement ratios of 0.35 and 0.55. After 90 days of hydration both the distribution in pore sizes and the total porosities were similar for the pore diameters of 90 nm and below. This suggests that the variation in permeability with watertocement ratios is dominated by the larger porosity. Nyame and Illston [13] reported a linear relationship between the maximum radius of a continuous pore and the permeability of a paste. Mehta and Manmohan [14] found that the permeability of pastes could be correlated with the volume of pores having diameters greater than 132 rim. Goto and Roy [16] observed that pores in the size range from 75 to 750 nm have a major influence on paste permeabilities. However, it has also been established that the techniques used to determine the pore structures of cementitious materials may affect the pore structures themselves. For example, Hughes [15] confirmed the observations of Feldman [31] and others that mercury intrusion significantly damages the pore structure of cement paste. Hughes also reviewed the work of Marsh, which indicated the lack of any correlation between permeability and pore size distribution, and developed a simple tube model to predict permeability. Unfortunately, a generic model having predictive capabilities does not seem to have emerged from these investigations and the capabilities of the models described above appear to be limited. At best it appears that, while there not agreement regarding the relationships between porosity and permeability, the weight of evidence suggests the larger capillary porosity to primarily contribute to the permeability in cement paste. However, care must be taken in generalizing these observations to concrete. P_rmeability Models
The following sections describe number of classes of models which have not been applied to cementitious systems but that have proven successful in predicting permeabilities of catalysts, _of
54
geological materials including analogs in electrical systems. Network Models
rocks and soils,
and of permeability
The DaxcyPoiseuille model, the Archio model and the CarmanKozeny model all attempt to relate permeability to some averaged descriptor of the porosity, or to the total porosity. They do not consider the structures in pore network. In spite of this limitation these models can, in some instances, qualitatively predict concrete permeability [see for example 57, 58]. However, the predictions based on these models are frequently considered to be inadequate [59]. This recognition occurred in the geosciences in the 1950's and led to the development of a "network model" to describe permeability [6062]. Since then, network models describing porous systems have been developed in the areas of geophysics [63], petroleum geology [64, 65], soils [4] and chemical engineering [65]. However, none seems to have been specifically developed in the area of cement and concrete. Network models axe based on the analogy of Darcy's law for fluid flow to Ohm's law for current flow. Seeburger and Nur [59], for example, investigated the effects of confining pressure on permeability and bulk modulus in rocks using a network pore space model as a tool. In their network model, the elements are capillary tubes of given length, cross section and shape. The change of permeability with hydrostatic confining pressure is caused by the effect of the stress field on the shape and resulting flow characteristics of each element. In a model developed by Dullien [54], a network consists of many sub=networks of pores that have a specific smallest entry pore size, Figure 4. Each subnetwork is treated as a flow channel. The volume flow in each channel is determined by the mean squared diameter of pores in that channel. Total volume flow is the sum of that in all flow channels. DuUien's model [3, 54, 70] is written as foliows: k = ¢ <D2>/96 [ 14]
.
where <D2> is the mean square pore diameter and e theporosity. The value of the constant in Eq. [14] differs from that in the classical Poiseuille model, Eq. [11], by a factor of 3. Dullien interpreted this difference as a tortuosity factor. It is doubtful, however, whether the tortuosity factor is a constant. A tortuosity factor is more likely a variable depending on microstructure. The mean square pore diameter in the model is determined from a bivariate pore diameter distribution proposed by Dullien [71], as will be discussed as follows.
55
Mercury intrusion porosimetry can only determine pore entry sizes. Quantitative image analysis can determine the "true" pore sizes, although only in two dimensions. If the size distribution curves determined by these methods overlap over the entire range of pore sizes, a bivariate pore size distribution can be expressed as p(D, De) where D is true pore diameter and D e is pore entry diameter, Figure 5. Dullien developed a simple, graphical procedure to estimate the volume of pores having the true diameter D to D + dD and the entry diameter De to De + dDe. A bivariate distribution was found to be suitable to account for both distributions [3, 57, 71]. From this bivariate distribution, Dullien claimed that the relation between pore entry diameter and pore diameter can be determined. It must be noted, however, that the bivariate distribution cannot be established unless two distributions overlap over the whole range of pore sizes. In less porous materials, such as cement and concrete, usually there are many fine pores, which are not amenable to observation by image analysis. In addition there are very large pores (voids) which can be difficult to measure by mercury porosimetry. Thus, overlap in the whole range of porosity may not be possible. It is also worth noting that the pore size distribution determined by image analysis represents the size distribution of the intersections of pores by a plane. Threedimensional, or the true volume distribution of pores must be estimated using stereological procedures [7277]. Probabilistic Models
Probabilistic models were first developed by Childs and CollisGeorge [67]. Subsequently, models have been developed by Marshall [68] and others [4, 69]. The basis for a probabilistic model is that a porous solid can be divided into two parts by a plane normal to the flow direction and that the two crosssections can be rejoined. If pores are distributed at random and the term f(D)dD is the probability that a pore has diameter within the range D to (D +dD), then the probability that pores with diameter Di to Di + dDi on crosssection i is connected to pores of size Dj to Dj + dDj on crosssection j is f(Di)f(Dj)dDidDj. If the interconnection between pores of the two crosssections is assumed to be completely random, the permeability coefficient can be expressed as: k **e2j'j" D2f(Di)f(Dj)dDidDj [15]
where e is the porosity and D the smaller of Di and Dj. The proportionality factor is 1/32 if circular capillary tubes are assumed [4]. Juang and Holtz [4] noticed that in reality, the connection
56
,
between pores of two crosssections would not be completely random. They added a factor called the "connection function" g(y, Di, D j), where y is the sample length, to control the connectivity and realized that it accounts for tortuosity of flow. When y_ 0, it becomes k = e2<D2>/32, a form of the classical Poiseuille capillary model [4]. As Gueguen and Dienes pointed out [6], the tortuosity concept is related to percolation concept, as will be discussed Models Based on Percolation Theory
In 1957, Broadbent and Hammersley introduced the term "percolation theory" to describe critical phenomenon, or phase transition behavior [78]. The basis for percolation theory can be considered in terms of the site occupancy of a lattice. A primary assumption is that every site is either "occupied" or "empty" based on an entirely random process which is independent of the occupancy of neighboring sites. The probability that a site is occupied is p and (I  p) is the probability that a site is empty. Occupied sites are either isolated from each other or adjacent to neighboring sites to form clusters. If the site occupancy is near zero, most occupied sites will be isolated. If, °n the other hand, the site occupancy is close to unity, then almost all occupied sites will be connected to form a large cluster, which extends from one side of the lattice to the other. This large cluster represents an "infinitepath." It percolates through the lattice in the similar way that fluid percolates through porous materials along the network of connected pores. Increasing the site occupancy from zero to unity results in a critical point (percolation threshold), Pc, above which an "infinitepath" can form. The occurrence of an infinite path is illustrated in Figure 6 for a simple model of fluid flow through a porous medium. The percolation described is called "site percolation" [7983]. There is a counterpart called "bond percolation" [7983]. In this instance, each site on the lattice is occupied, and interconnections between neighboring sites are regarded as bonds. In this instance, p is the probability that a bond is "open" and (lp) is the probability that a bond is "closed." A cluster is a group of neighboring sites connected by open bonds. The percolation threshold, Pc, is the fraction of open bonds, below which an 'infinitepath' cannot form. Fluid flowing through porous materials can be modeled in terms of its passage through a network of interconnected pores. Intermediate between site percolation and bond percolation there is a type of percolation called "sitebond percolation" [79, 80, 84]. The lattice sites are no longer all occupied as in bond percolation. In sitebond percolation, p is the probability that there
57
is a bond between neighboring sites. A cluster is then a group of neighboring occupied sites connected by bonds. The bond percolation threshold decreases from unity, when the portion of occupied sites equals the site percolation threshold, to the normal bond percolation threshold, when the fraction of occupied sites is unity. This type of percolation appears to most closely represent the nature of fluid flow through porous materials. The fraction of occupied sites is equivalent to porosity, the bonds represent the channels connecting pores, and a cluster represents "infinitepath" pores. The channels may consist of pore entries and cracks. In the percolation theory, P is defined as the strength of infinite network. The strength, P, is the percolation probability that a site belongs to the infinitepath. It is actually the fraction of total number of lattice sites that are on an infinite network [79]. A power law expression may be written: P ** (p  pc) t [16]
if p approaches Pc from above where p is the concentration of occupied site or bonds, and Pc is the critical concentration. Transport properties are proportional to (p  pc) cx. ct is the transport exponent. However, t usually differs from a [85] because P counts for both backbone and dead ends. Dead ends contribute to the mass of the infinite network but not to transport properties. However, dead ends entrap fluid. From the standpoint of flow in porous materials, an infinite network consist of two parts: backbones and dead ends. Fluid flows through a porous materials along the backbones and are entrapped in dead ends. Permeability measurement usually only deals with the flowthrough fluid; however, entrapped fluid can significantly affect properties, such as freezethaw resistance of concrete. Therefore, it is necessary to consider phenomena associated with flow in both backbones and dead ends. Computer simulation can be used to differentiate dead ends from backbones and to calculate fractions of backbone and dead ends with respect to the infinite network and numerical studies have been made to quantify backbones [86]. Several of the models previously described above can be considered in terms of percolation concepts. Both percolation theory and Archie's law use a power law to describe the critical phenomenon. Thus, Archie's law may be regarded as a special case in which the percolation threshold is zero [87]. For dense yet permeable materials, the percolation threshold can approacha very low value. For example, rock salt has porosity of only 0.6% but a
58
.
permeability of 7.3 x I06 Darcy [88]). Dullien observed the permeability of sandstone to mercury to depend on the degree of pore prefilling by mercury. That is pores of a given size that were previously filled with mercury contributed to permeability while those that were not filled did not contribute to bulk flow. Dullien concluded that at a low mercury saturation there must be continuous flow channels in the medium. At low saturation, only the largest entry pores are penetrated by mercury. In other words, these flow channels consist only of pores with large entries that can be intruded by the mercury. However, if the saturation is reduced to a very low level, no permeability is recorded [3]. This low saturation must be related to percolation threshold. Thus, Dullien's model as well as Juang's statistical model can be regarded as transitional models between nonpercolationbased models and percolationbased models. Gueguen and Dienes [6, 89, 90] used statistics in combination with percolation theory to correlate pore and crack structures with permeability. Their models assume narrow size distributions and can be expressed as: k = fE<r>2/32, k = 2fe<w>2/15, for pore structure and [17] for crack structure, f is the fraction of connected pores and is proportional to (p  pc) a, <r> is the mean pore radius and <w> is one half the mean crack aperture, and ¢ is the porosity. Unfortunately, the assumption of narrow size distribution is not valid for cementitious materials. However, the model explicitly includes f, the fraction of connected pores and thereby provides a means to quantify the tortuosity factor [6]. Additionally, their model provides insight to crackpermeability relationships; in cementitious materials pores and cracks are not distinct and the effect of cracks on permeability must be considered. Katz and Thompson [5, 91, 92] developed a percolation model using an approach based on the work carried out by Ambegaokar, Halperin and Langer (AHL) [93] on electron hopping in amorphous semiconductors. They showed that transport in a random system with a broad distribution of conductances is dominated by those conductances with magnitudes greater than some characteristic value go. gc is the largest conductance such that the set of conductances {g:g > go) forms an infinite network. Transport in such a system reduces to a percolation problem with threshold ge Kirkpatrick [82] and Shante [94] extended these ideas and assigned the value ge to all local conductances with values g >gc and set all conductances with
59
: ;
values g < gc to zero. They arrived at a trial solution for the sample conductance of the form: g = agc[p(gc) a, Pc] [18]
where P(gc) denotes the probabilityhat a given conductanceis t greater than or equal to gc, and a is a constant.Pc is the critical concentration of conductance, below which no infinite cluster can form. The transport exponent, cc is approximately 1.9 [95, 96]. This model is similar to a sitebond percolation model. Katz and Thompson [5, 92] applied these concepts in the development of a model describing the permeabilities of porous rock. They defined threshold conductance value gc as function of the characteristic length 1c" gc oo lc. Assuming cylindrical pores, the characteristic length is the pore diameter. Then the hydraulic conductance of the sample is the function of the length parameter 1: g(1)  Egc(1)[p(1)  pc] ct [19]
where e is the porosity. As 1 is lowered past the threshold 1c the function g(1) also decreases but the powerlaw term [p(1) pc] 0_ increases as more and more pores are included in the infinite network. Mathematically, this means that there is a maximum value for 1 that places a lower limit on g(l). Physically, because only conductances with characteristic lengths I >_.Ic are included in the calculation, the sample conductance, g(lmax), must be always less than or equal to real sample conductance. In other words, g(lmax) approaches the true conductance as closely as possible. After maximizing, the model is expressed as follows: k = (1/226)1c a/ao, [20]
where 1c is the threshold characteristic length, which is inflection point on the cumulative pore size distribution determined by mercury porosimetry. _ is the electric conductivity of the rock, and ao is the conductivity of the pore solution. They also proposed that electrical conductivity can be determined directly from mercury injection [91, 92]. The result is a pore structurepermeability model which can predict permeability simply from mercury intrusion data as follows: k ** (lmax)2(lmax/lc)ef(lmax), [21]
where f(lmax) is the volume fraction of pores intruded by mercury. lmax is the maxima of 1. The advantage to this percolationbased model is that the use of percolation factors that are difficult to
60
'
determine, such as those used in Gueguea's model (f, p, and pc), is avoided. The disadvantage is that the model is based on the maximizing a lower bound [97]. As a consequence, the calculated permeability is typically less than the measured value. Another disadvantage to this model is that mercury porosimetry may not be able to describe crack structures correctly, although crack structure may be as important as pore structure in terms of their effects on permeability. Garboczi has recently applied Katz and Thompson model to cement and obtained encouraging results [968], however permeability and pore size distribution data have not yet been obtained on the same samples.
61
tmmaz.
A variety of models have been developed to predict permeability from pore structure. A common feature of these models is that a power law may exist between permeability and some characteristic pore dimension. The tortuosity factor has been included explicitly in J'uang's model, Dullien's model (though it is assumed as a constant) and all percolationbased models (in the form of percolation factors). Each model has its rational base. Statistical models consider all pores, whereas the KatzThompson model only considers large pores. Dullien's work provides the the basis for relating entry pore volume and true pore volume. Gueguen and Dienes have considered crackpermeability relationship and explicitly used f, the fraction of connected pores in theirmodels. Alternatively, Katz and Thompson avoid calculating f, which is difficult. Rather, they predict permeability from mercury porosimetry data. Even the traditional CarmenKozeny model has its advantages. This pore structurepermeability model requires as input is a pore size distribution. Although a pore size distribution is more" easily determined than permeability per se, it usually assumes shape for pores. The CarmanKozeny model uses the specific surface area of pores as input. This does not require any shape assumption and can, therefore, avoid a source of error. The determination of permeability is of obvious importance in a variety of disciplines. Investigators in these various disciplines have developed both methodologies for the determination of permeability and models to describe their results relatively independently. It has been the objective of this review to briefly describe measurement methods and models, along with their advantages and limitations, that may have relevance to cementitious systems.
62
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from
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D. Shi, "Discussion on estimation of 3D properties from 2D measurements without shape assumption", in Advances in C_men_ Manufacture and Use, E. Oartner, Ed., Engineering Foundation, New York (1989). D. Shi, Ph.D. Thesis, Purdue University D. Shi, "A probabilistic particles/pores without submitted. (1987).
73. 74.
approach to evaluate distribution of shape assumption," J. Microscopy, 148, AddisonWesley,
75. 76.
E.E. Underwood, Quantitative Stereology, Reading, Massachusetts (1970).
DeHoff, R.T., The statistical background of quantitative metallography, in Quantitativ_ Microscopy. R.T. DeHoff and F.N. Rhines, Eds., McGrawHill, New York (1968). E.E. Underwood, "Surface area and length in volume," in Quantitative Microscopy. Ed. R.T. Dehoff and F.N. Rhines, Eds., McGrawHill, New York (1968). J.M. Ziman, Model_ of Disorder, Press, Cambridge (1979). 370386, Cambridge University
77.
78.
68
79. 80. , 81. 82. 83. 84.
D. Stauffer, Introduction Francis, London (1985).
to. Percolation
Theory, Ch. 2, Taylor & Clusters, Ch. 1, North
D. Stauffer, Scaling Theory of Percolation Holland, Amsterdam (1974). R. Zallen, The Physics New York (1983). of Amorphous
Solid_, Ch.4, John Wiley,
S. Kirkpatrick, in IllCondensed Matter, R. Balian, et al. Eds., Ch. 5, NorthHollan, New York (1979). R. Zallen, in Fluctuation Phenomena, Ed. Montroll, E.W. and Lebowitz, J.L., Ch. 3, HorthHolland, Amsterdam (1987). D. Stauffer, "Percolation and cluster size distribution," in O n Growth and Form, H.E. Stanley and N. Ostrowsky, Eds., Martinus Nijhoff, Boston, (1986). D. Stauffer, Introduction Francis, London (1985). to Percolation Theory_, Ch. 5, Taylor & of percolation law," Phys.
85. 86. 87. 88.
S.S.Manna, "Structure of backbone perimeters clusters," J. Phys. A: Math. Gen. 22, 433 (1989). I. Balberg, "Excludevolume Rev. B, _3, 3618 (1986).
v
explanation
of Archie's
S.N. Davis, in Flow through Porous Media, R.J.M. De Wiest, Ed., Ch.2, Academic Press, New York (1969).
89. J.K. Dienes, in Is_o¢_ in Rock Mechanics, R.E. Goodman and and F.E. Heuze, Eds., Ch. 9, Ame. Inst. Mining, Metall. & Pet. Engr., New York (1982). 90. 91. Y. Gueguen, et al., "Models and time constants evolution," Geophys. Res. Lett., 13, 460 (1986). for permeability
A.J. Katz and A.H. Thompson, "Prediction of rock electrical conductivity from mercury injection measurements," J. Geophys Res., 92, 599 (1987). A.H. Thompson et al., "The microgeometry and transport properties of sedimentary rock," Adv. in Phys., 36, 625, (1987_).
92.
69
93. 94. 95.
Ambegaokar, V. et al., "Hopping conductivity systems," Phys. Rev. B, 4_, 2612, (1971).
in disordered
V.K.S Shant, "Hopping conduction in quasionedimentional disordered compounds," Phys. Rev. B, 2597 (1977). R. Fisch and A.B. Harris, "Critical behavior of random resistor networks near the percolation threshold," Phys. Rev. B, 1_, 416 (1978). D. Berman, et al., "Conductances of filled networks," Phys. Rev. B, 33, 4301, (1986). twodimensional
96.
97.
Le Doussal, "Permeability versus conductivity for porous media with wide distribution of pore sizes," P., Phys. Rev. B, 39, 4816 (1989). E.J. Garboczi and D.P. Bentz, "Analytical and Numerical Models of Transport in Porous Cementitious Materials," 67581 in Scientific Ba_i_ for Nuclear Waste Management XIII, V. Oversby and P.W. Brown, Eds. (1990).
98.
LIST OF FIGURE CAPTIONS Figure 1. The relationship strength [2]. Figure 2. Figure 3. I portland [25]. The dependence between capillary porosity and compressive [17].
of permeability
on the capillary porosity
Cumulative pore volumes intruded depending on age for a Type cement paste hydrated at 24C at a watertocement ratio of 0.4
Figure 4. An illustration of one element in a pore network in which pore sizes may vary [54]. Figure 5. A comparison and pore sizes [73]. of the distribution in the diameters of pore entries
Figure 6. An illustration showing the formation of an infinite path. This illustration represents, in twodimensions, flow paths across a bulk sample in which a pore structure is defined by the application of percolation theory. The hydraulic gradient is from left to right.
_"
70
28
24
1_
0 1O0
80
60
I 40
I 20
0
Capillary porosity (%)
71
100 90 "to 80
!
f ,, ,
7o
" O0 " 50 /
40
•_
0 U 0 10
,
,_,
/
20
20
30
40
Capillary Porosityper
cent.
72
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DIAMETER
DISTRIBUTION (De) =. COMPLETE PORE SIZE
1200r.
_
DISTRIBUTION
(D'
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75
RELATIONSHIPS DIFFUSION MORTAR,
BETWEEN
PERMEABILITY,
POROSITY, PASTES,
AND MICROSTRUCTURE
OF CEMENT
AND CONCRETE
AT DIFFERENT
TEMPERATURES
DELLA M. ROY, MaterialsResearchLaboratory,The Pennsylvania State University, University Pennsylvania Park, 16802. ABSTRACT Permeabilities anddiffusion towater ofionic species incementitious pastes grouts, and mortars important to are keys concrete durability. Investigations have been madeofnumerous materials containing Donlandndblended a cements, andthose ith w finegrained at fdler, room temperature andafterprolonged curing at severalelevatedtemperatures p to 90"C. These u constitute partof studies fundamental aterialrelationships of m performedin orderto address thequestionof longterm durability. In general,hepermeabilit_es f thematerialshavebeen t o found to be low [many <10"8 Darcy (10"13 m.s'l)l after curing for 28 days Orlongerat temperatures upto 60"C. Theresultsobtainedat90"Caresomewhat orecomplex.In some m setsof studiesof blendedcementpasteswith w/c varying from 0.30 to 0.60 andcured at temperatures 90"Cthemoreopenporesu'ucture theelevatedtemperature upto (at andhigher w/c) as evident from SEM microstructuralstudiesas well as mercury porosimetryare generallycorrelated alsowith a higherpermeabilityto liquid. The degreeof bondingand permeability evident inpaste rmortar/rock o interfacial present studies somewhat more conflicting Thebond results. strength (tensile mode)hasbeen shownto beimproved some in materials withincreased temperature. results The ofpermeability studies ofpaste/rock couples showexamples similar with lowpermeabilities, andsomewith increased permeability with temperature. Ionic diffusion studies bring mportant also i bearing tounderstanding the effect ofpore su'ucture. bestnterrelationships chloride The i between diffusion andpore structure to appear relate diffusion tomedian rate poresize. Similar results werefoundwith AASHTO the "chloride permeability" test.
INTRODUCTION The_ ofhaxdened cement pasteo t chemical attack andphysical degradzdion is
theresult_l_,ed composition and microstructuralfactors with environmental xposure e conditions.t't,:j Farm's conwalling the initial,,n_'ostructure developmentaretherefore stronglyrelatedto eventtutl concrete durability.t";J Tim tesismn_ of cementirlonsmaterials to chemical attack andphysicaldegradation is only indite_y related mechanical tothe su'ength of thematerial, strong i.e., materials do not alwtysesist anddisintegrative in r attack forces anyenvironment inwhich they placed. are Nevertheless_ thatigher it u'ue h is strength concretes generally lowpet, have meabillties, and thereby provide will bener esistance r to chemical attack andphysical degradation than Iowsu'ength materials. Thewaterontent w/cratio) c (and ofacement paste probably is the most important factor single indetermining subsequent the porosity andpermeability ofthe hardenedaste,anddecreasing p thewatercontentboth decreases permeabilityandporosity, andusuallyincreases strength. the Theporosity andpore snmcnn'e ofcement pastes major exert conn'ol onthe ingress of potentially deleterious substances. pore The structure andmicrostrucmm constitute major ratecontroiling factorsfor potentially harmfultransport rocesses, whether the s_s being p tran_ is water to riseo ( give t aficalisiiica expansion), ions sulfate (causing sulfate attack), chloride (to eR._ivate protective on reinforcing acids, ions d the layer steel), or oxygen orcarbonioxide d t tZl.
"
76
The factors controlling microstructure structure not andpore have been fully discerned from past knowledge. certain E.g.. supplementary cementing materials orpozzolanas" promoteevelopment fineore d ofa p structureresultlower _ in p_,,e, ability diffusivity (and ofpotentially deleterious far species) beyond which that would bepredictedthe on basis ofthe water/cementirious solids alone. 14] ratio [12" Thediffusion ofions andthe ofpermeation rate offluids across aporouscmendtious c matrix _uitively. tothe are, related volume pores of andthe andinterconnectivity size of these pores.tOJ The basisfor such a statementlies in the fact thatif these two factors were not related to the pores in a porousmatrix but to the solidpart,the observed rates of diffusionof _;10 "i2t_/._c a!_ temperaturein porous cen'_ntitious.materials ould instead resemble w thatof aton'ncdiffuslon m polycrystallineceramicsof I0 "'_m'/sec or lower. The permeabi_ty ofwater hrough t water saturated cementitious materials hasbeen shownto be related porosity tothe andpore size distribution. the [1.21 In case ofionic diffusion in watersann'ated cementitious porous materials, iffusion the d coefficients for moderatelysized, singlycharged generally between I0_ I cations range I andI0"_3 m2/sec while he [3"61 t diffusion coefficients for theseons i inpure watersI0"" i m'_/sec, tlj Theobvious question arises why the thus asto diffusion is retarded through matrix. the One ofthe factors contributing decease the tothe is smaller through area which ionsay the m migr_ in a porousmauix viz. the areaof the pores. This areafactormay explain a two or thn_fold clane.ase diffusion inthe coefficient ofanion across aporousnau'ix r ascomparedo t thatnthe i pu_ aqueoushase. t p I was pointed earlier the out that observc_l reductions are generally muchl_g_p',d_pn orthreefold, vicinity _toI0'* twoin the ofI0 times.onsidering C recent evMuadonsr'.J,''J the p_bable re&son such large for a retardation fromthe arises consu'iction andtormosity pore ofthe path through which anion migratesa watersaturated in porousoan'ix; r Theionwall interaction to substantial leads a decreasediffusion. in Recent papersave h elucidatedthis I0.I point.[II Th=_ are twostages inthe pr_atadonfcementitious o materials whichshoulde b _y con=oiled they critical for are in developing ultimate the resistance material ofsuch to forces ofdegradation: freshtate, I) the s duringixing, m placing andconsolidation; the and2) curing stage. Beyond chemistry the ofthe cemenddous materials, which factors influence earlystage theological properties can significantlyaffectthe physical propertiesof the hardenedpasB which conuol their ultimatedurd_ty. Poor mixing, i_,_,_yate di_on, bleedingsegregationandrelated phenotta_ cangive riseto inhomogencides hat, in the ned paste mic_=ucmre, which can _ pathwaysforrapidtransport f harmfulspecies. o Them am _ _ limiu wwm reductim for which pem_ adequate wodmbility. md sula__ we ccmm_y used to improvefluidity, buttheiruse may also gemate effem as yet. pcxx'lyundmmcaL A combimdon of chemical and physical facu_ are influendMthe in curing stage: e.g., ch_..l_g thechemistry,as by pan_ sulzt_ution of Ign:mlan_ granulatedblastfunug¢ slag or :_lim fume for cemmt can preventexcessive heat¢voludon which would remit ia micmcracHng. This is above and beyond theireffect in generat_g a finer pore mucture. The chemical, physical, and mk:mstrucn_ pmperuesof hardenedcement pastes, therefore, arecriticallyinm_elatedwith respectto theireffectson degr_n. Poro_rv andPore Structure ofCement Pastes • A wide varietyof techniques have of the pore size disuibudon andpore charact_sdcs been usedfor theastes. Although ofpordandement d_adon c p mm_my intrusion pomsimmry (MIP) hassomelimitations" it hasbeen generally recognized the that pore _, w.hjc_.i___n_Asure.s, the same factorswhich is related to conlxol pm_ne.ation of fluids 10115. t l'_'°'W'_ ti ¢ • ,q_l" Gas adsorpdon methods describethe finer pore sizes of gel pon_t_'J butthese arenotbelievedtocontribute ignificandyotheu'anSlX_ateof the s t r various species. he results f..MIP._nts T o reportedherehavebeenobtained . rlwistlh freezed_jsamples treated numm_ damage thespocu'nens to to be_'ore measm.,m_t.L'o_ 77
'
Sometypical resultsof mercuryintrusionporosJmeay studies shown in figures I and are 2. Plotswere rm_ of va_rlous xperimen_ panmemrs, primarily: a) in_rude, volume e d (expressed ascm_/cm_ providing a total porosity) asa functionof porev_dius,and b) dV/cLP asa functionof poreradius. Surfaceareameasurements were also made. One of the most useful parameters hasproved tobe the dV/dPvs._.pgr¢,,_,dius lot. p fromwhichthe"critical poreradius" or the "maximum continuousporeradius t_)could bedetermined. Since the pore radiusandinmasion pressure arerelatedreciprocally, the functiondV/dP may be usedinstead of a directfunction of the poreradius. The radius at which the maximum in theplotoccurs represents thegroupingof the largest fractionof interconnectedpore s,.w.htcheffect, in conn'olsthe n'ansmissivityof the material. The 'median'pore radius to,t_slis also, imilar. t s The critical pore radiusis related to, but notidentical to Diamond's [20'threshold radius, the laner occurring alarger radius. at The aboveplots contrast thefiner sn'ucture pore ofacementpaste con_ninggranulated blastfurnace withapurepordand slag cementpaste (the critical radiusftheformer pore o is about 1/3 of the latter). Figure 3 conn'asts critical pore radii of a seriesof cement pastesof the different w/c curedat different temperatures.The critical pore r_Liusincreases a tenfold by factorwhen increasingthewit ratio of the slag containing materialsfrom 0.3 to 0.6, while the total porosityincreases abouta factorof two (2) in similar materials. Theseresultsand by sh'nilar resultsfrom other workclearly indicatethat there is aneffecton the porestructurefar beyondthat anticipated from the increased porosityalone. Furthermore,the effect differs with. cementcomposition and type. Figure 4 gives comparisonsof mecumulative pore vommes of portland and portlandslag mixtures. A second r_t_scntationof pore size diswibution dam, the median pore size is the pore radius at which 50% of the pore volume is observed in the pore size range considered. In most c_mentitious materials rhe critical po_ radius and the median pore radius have similar values. Pml:x_es of different cen'_ntitious compositions may be conu'asted by comparing the porosity, median pore radius or the critical pore radius. The mercury porosimetrymeasu_ment results for cement pastes,andthose blendedwith fly ash, u'4nulatcd silica slag, fumeandErie qua='= (minusiD showsignificant dtt'ferences. A series ofsampleswerecured ata tempe_nn_of38"Ctheresults ofwhicharegiven inTableI. Re!atiy.eJy.cgmpar,,ble values tothose listed in TableIwereobtained withspecimens cured at 27 C.tte, =aj Except for the pure portland cement, and mixtures with fine quartz, a steady dec'tease in medi:_n pore size shownwithprolonged is curing time. In general,the additionof mineraladmixturesto portland cementleadsto a decreasein pore sizeor an increasein the fraction of porosityin the finer porerangeof 15nm or less.(FigA.l The porosity may increasethrough this incorporation in silica fume and fly ashcasesbutthe as increase inporo=tyis only_hthecluant/.ty pores. o.freer f The _'¢sults an=inkeeping withthose foundpreviouslyorsimilarysteras.[lal effectftheincrease f s The o infinerorecontent p indiz_dy leads to an appat_nt increase in the tortuosity or interconnectivit'y f the pores. o When porosity andmean poreradius, determined MIP,areexpressed function by asa of water/cementitious volurn¢atio solid r (w/s), aninteresting relationship isshown.Figure 5 gives porosity forcementitious data mixtures function asa ofw/s(vol). family A ofcurves is shown,whichisdifferent eachcementitious for material. However,when themean pore radiuss i plotted. function _ a. ofw/s,(Figure he values on a singleinear 6),r, fall l plot. decreasing with dimiaishing wls.[21] Diffusion and Permeability As a key to the factorsinfluencingthe rate of penetntion of chloride ion into hardened cemendrlous materials,and their consequenteffects, the diffusion of C1" ionsthrough hatdenedcement pasteshas beenstudiedby a numberof investigators. [4,5] The diffusion of CI" ionsis stronglyinfluenc_ by the typeof cement,and blendedcement pasteswith 30% flv __ ashor 65% slaggave lower diffusion thanportland cement pastes.5] The durability of [ " blendedcement,= highly ooncenlxated to chloride solution(27.5% C.aCI.,4.3.9% MgCI, .,1.8% NaC1)is another matter, as was reportedby Feldman.[221He als_ found that bl¢'nds 78
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]
]
l
i
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I
0,7
CRITICAl.
PORE
RAOItJ$
aG
W/C
* 0,40
'
a=
i4 DAYS 4S'C
OIFIr[RIrNTIAL
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r i
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r I
, 
[ (
(2J 2_Q
_a _25 7'3 SO 40 30 ZS ?.0
POR[
RADIUS (ANGSTROMS ; 140* WETTING ANGLE)
Fig. 1.
clV/aP plots of comparable portland cement and slag cement pastes (60:40).
CUMULATIVE PORE VOI.UME
t l I I [ _ t [ I I
020,P"
0.1,/
W/C • 0.40
,: 0AYS CEMIrNT/SLAG..,/
?
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Fig. 2.
0 ;..,,,¢¢ r l ZSQ 12S
_ 7_
; I 60 _0
I 40
I 3S
I _
•
_ 2S
t ZO
IS
I=OR¢" RADIUS 111 Cumulative Ix)re volume versus pore radius of portland cement and slag cement (60:40) pastes.
7g
SLAG/CEMENT
/
_:
/ _
'JO0
;
,, .... o
/
/ ,
/
_"..." =r..' ....' o z. II /#' o 4_" // '/"_ ° _o t/._
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Fig. 3
o.,o,_ o.. o, o,
WIC RATIO
Critical pore radius (dV/dP maximum) versus w/c ratio of slag cement pastes cured at different temperatures.
0,_
l
I

/l
/(
___ '_
0.3 O
14 OAYS
_L CEMENT
Ze DAYS 0
2 "°• oz o,
o_,,,_ / ,_ o .I/ _
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o.....o%,,.,,._o _.._..,__.._t.
SLA( W 0.04 • r ! 0 W,'_ o.e • SLAG
• (.1
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_
:_
0.01
I 2T
I 45
I 60
.¢,"
t 90
f
l 27
t 45
oo.,.
I 60 //"
) 90
CURING TEMPERATURE('_) Fig. 4 Cumulative pore volume of portland cement compared with slag cement pastes.
8O
I
I w/l?O.6vCl 4 I wls,
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z¢
o ¢IFA (8012_I e C/CA (70/.I0) "¢IFA (60140) • C/S _, 0.4 ii//' ( 1351651 ,,
Q2
[
0.I 2.0
I, 1.7S
I , I LS 1,25 wol'er/solid (voi)
I' t.O
0.?5
Fig. 5
Porosily as a function of w/s volume ratio; abbre(Hg porosimetry). C=cement, FA=fly ash, SF=silica fume, S:,granulated blastfurnace slag.
i
i
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%
\ %,_\'


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1
. " io2.0 I 1.75
\,
\
\
\
_
,%
I I LS 1.25 waterlsolld ratio (voi)
! 1.0
Fig. 6
Mean pore radiusvs, w/s (vol.) ratio.
.,
£
with 35% fly ash or 70% slag had a finer pore size disuiburion than Type 129nland cement and a Iowa"Ca(OH) 2 content, which improved their durability. Page et.al.t_J rcponed chlo_'j'_le diff_idvit7 fromsodiumchloride whichfollowedickslawwhileKumar and F RoytOJ showedthe comparison given inTable2 for different ofcementpaste types compared withpordand cement(OPC),when CsClwas usedasa d/ffusam. 81
Table1.
PorosityadMed_ Po_Size a forType! Portland ements C Blended td_ w Various dmixtures A andCaredtt 38"C. porosity (%_ wls w/s _?edian Pore Size w/s w/s 0.40 12.5 15.0 12.5 17.5 */s 0.35 12.0 7.5 8.8 0.35 + SP inrn_ w/s 0,30 9.2 5.4 12.5
Compaddm (by v_.) TypeI Portland Cement
Ap (De/s) 7 28 90 180 , 365
w/s 0.40 27.0 23.5 24.5 27.0
w/s 0.35 24.0 22.0 19.0 18.0
0.35 * SP
0.30
16.5 17.0
21.5 14.0 19.0 12.8 13.6
14.0
35%TyI_ [ PC + 65%BI_ Furnace lag S
7 28 90 180 365
190 11.5 10.0 8.0 6.0
14.5 12.5 6.5 5.7 4.5
13.5 2.75 2.45 2.40 2.50
37 2.65 2._5 2.55 2.65
90% Type[ PC 10%Silica Fume
7 28 90 180 365
27.7 27.5 24.0 23.0 22,0
20.5 16.5
8.0 7.5 6.2 ,:.2 8.0
4.1 4.2
75%Typel PC + 12.5%5_un Minusil 12.5%10tin1
90 180 365
20.5 19.5 23.5
17.0 16.5 18.5
8.5 8.5 10.0
5.5 5.0 90
70%TypeI PC + 30%FlyAsh
7 28
26.6 26.0
25.0 21.3
29.0 9.2
100 6.;
Minusil= finepowdered qua_ (SiO2).
Table 2 Chloride Diffusion Coefficients with CsC1 Diffusion w/c = 0.35
Cemmt & Blended OPC Slag 65 Si Fume Fee Quartz 25 Fly Ash 30
Dxl09 cm2S'I 28 Days 75.1 9.62 2.9 55.8
90 Days 57.2 4.87 1.12 67.7 
_
82
The rcvas¢ of the a_,.sponof ions orchemical speciesinto a cement pasteis the movement of water through the paste and remov.alof specie_i_,!eaching, which dependson the pore su.ucmm and wat_ permeability or me paste.t',.o._._._'qAs water permeationinvolves the u'anspor¢ f species undera pressuregndiem, leachinginvolves the transportof species under o a concenwadon gradient, e.g., in the case with very purewater in contact with cement paste. Soluble ions, articularly p monovalent ones, avebeen h found tobereleased a diffusion by mechanism, whiletherelease of other rate ions isgenerally slower,ontrolled a c by combination ofmechanisms.[ 12]
P.r, mmlgilx
Numerous experimental have studies been madeofthe effect ofwater/cement ratio, curing temperature andother•actors • pgrositv, sizeistribution f onthe 4, port d andpermeability of • "_ • • * pastes andmortars ofcementmous atenals.[ m '15.2"1.25,8lpermeabdtty The to water as w measured numerouspecimens on s andwascalculated the from flow asfollows: rate (viscosity ofH20)(flowate) r (sample length) Permeability = (cross sectional ofsample) area (pressure difference the across sample l Inonestudy it [4] wasshownthat. although porosities total ofcement pasteamples s curedat 60"C are smallerthan in those cured at 27"C,thepore volume larger than 750]kradius is greater in the 60 C samples and it related to higherpermeabilitiesalso in the latter.[q Plots of log permeability vs. w/c in Fig. ) show a nearly linearincrease with w/c. Commonly it has been the experience that well cured materials with low w/c have low permeabilities below the limit of measurement of many,.tzpesof apparatus.[15.21._.31This ! would be expected fromoriginal predictionsof Powerst_'J and others that the "capillary" porostty is essentially "zero"in cement paste materialswith w/c <0.40, and that the remainin,., porosityis fine gel pores. In one study of slagcement pastes[15] ater permeability w measurements which were made on samples taken directlyafter curing,mildly surfacedried. and epoxied into rings, showed that Rermeabilitiesof all the 0.40 and 0.50 w/c slag cement samples were below 10"_Darcy [I.tm':] no measurable flowunder the given test conditions) ( upto60"C. • Inothertudies s arelationship water em_ability between p andmeanpore radius was
found. [21]Figure8 shows the approximately relationship betweenog linear found l water
permeability andmeanpore radius, the for samematerials Figs.and6,which asin 5 include pastes ofdifferent w/cmadeofpure portland cement, ofblendsith ash,ilica and w fly s fu,ne. andslag.inally, F aseries oflinear relationships found wasalso between he t rapid chloride "permeability" (coulombs chargeransported) t andmeanpore radius type for Icement aste p
iOS
.IO "4
._
IO7
permeabittty and.wlc
g
"o7 /
l
T 0.35
I I 0.40 0.45 W/¢
I 0.50 83
IO'W
I
1
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I
T.
//
/
t co _' i _t
m
o
Fig. 8 Water per_eability vs.mean pore radius
/ /
8 ,o, _
.I
•
•
I 30
of pas=es from Fig. 5
I I I iO 20 tte_m Porei_Ivs (nml
I..,,L,.... I 6000 
I
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\ \ \ \

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4000 
_\\ \x Q
Fig.
9
(rapid Coulombs chloride permeabillry) charge cransporl:ed vs. water permeability, pastes of Fig. 5
ZOO0 
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_ ";_._.._,L I I I 17 I ,o' ,o ,o"4 to' ,oiio' _ ,0 _  _
, i I
water Permeability cm,s"4
e_......._
%0
andforeachofthree levels offly ashsubsrimuon. Withineachmaterial,chloride the u"anspon rate increased linearly withmean IX_S, iZ_. There werenotenoughdata slag for andsilica fume toestablish relationships, clear t"JTherelationships between "rapid chloride permeability" andwater pe:meability follow similar trends, asshown inFig. Surprisingly, 9. the silica fume material exhibited higher chloride uansportnot consistent with the low water permeability;, however, not enough samples of silica fume (or slag,) were investigated to make valid comparisons withthe other blended ruaterlab. Additional studies required are tovalidate these relations for all types of materials. Discussion Conclusions and As discussed above, permeabilities towater anddiffusion ofionicpecies s in cementitious grams, pastes andmortarsre a important keystoconcrete durability. Therefore investigations have been made of numerous materials containing portland and blended cements, and those with finegrained admixtures (fly ash, slag, silica fume), at room temperatureandafter prolongedcuringat severalelevatedtemperatures to 90"C These up constitutepart of studiesof fundamentalmaterialrelationshipsperformedin order to address the question of longtermdurability. In zeneral,the permeabilitiesof the materialshavebeen '13m •s"I after curing for 28 days or longer at found to be low [many < 10"8Darcy ( I0" )] temperatures up to 60"C. The results obtained at 90"C are somewhat more complex. Porosity, mean poreradiusandporesizedistributionin cementitiousmaterialsarevery important microstructuralcharacteristics; theyarerelated to a seriesof properues materials, of suchas flexural sta'ength,racture toughness, f durability, and resistivity to ionic diffusion. The work discussed here revealsthefactthatthe poresmactureof materials in questionis essentiallyaffected by the fineness,w/s ratio,chemicalcomposition,andpozzolanicreaction. Chloride ion diffusion under an appliedelectricfield appearsto be affectednotonly by the pore smactu_ of the materials, butalsoby thediffusion mechanism. 84
' :
The relationship between porosity, pore structure and ionic diffusion was suggested as follows: cc= [Ca rCb]3/e whereCa andCb are constants; e isporosity, medianporeradius, ratio ris ctffi oftheoretical to effective diffusion.[ ValuesforCa andCb weregenerated 6.16] fortheneatportland cement oastesnd C, = I03 + 2.6andCb ffi a 0.41 0.13forCI"diffusion ± andC a = 4.6± 2.5andCb = 0.62 0.0_forCs ± wereobtained overthetemperature rangeof27 to60 C. A relationship hasbeenfoundbetween mean poreradiusnd"rapidhloride a c permeability," aswellaswater permeability. Additional studies arerequired torefine these relationships and determine their applicability to a variety of ceracnridous materials.
Acknowledgement The research described herein was supported by the Su'ategic Highway Research Program (SHRP). SHRP is a unit of the National Research Council that was authorized by section 128 of the Surface Trauspormtion and Uniform Relocation Assistance Act of 1987. REFERENCES 1. P.K. Mehta and D. Manmohan, Prec. 6th Int. Congr. Chemistry of Cement, Vol. HI, Theme VH, 15, Editions Septima, Paris (1980). B.K. Nyame and J.M. Illston, Proc. 6th Int. Congr. Chemisu'y of Cement. Vol. III, Theme VI, 181185, Editions Septim& Paris (1980). H. Ushiyama and S. Goto, Proc. 6th Int. Congr. Chemistry of Cement, Moscow, 2(1), 331337, Su'oyizdat, Moscow (1974). S. Goto and D.M. Roy, Cem. Concr. Res. 11(5), 751757 (1981). C.L Page, N.R. Short, and A. El Tarars, Cem. Concr. Res. 11, 395406 (1981). A. Kumar and D.M.Roy, Proc. 8th Intl. Congr. Chemistry of Cement, Brazil, V.V, 7379 (1986). R.Parsons, HandbookofElectrochemical Constants. Butterwonhscientific S Publications, Table79,85 (1959). H.G.MidgleyandJ.M.Illston, Concr. Cem. Res.14. 453614(1984). A.Atkinson andA.K.Nickerson, AERE Harwell,OE Report D No.DOEARW/83, 137pp. K.Anderson, B.Torstenfelt. andB.Allard, Scientific forNuclear Basis Waste Management3.235242, Ed.J.G. Moore,PlenumPress, (1981). NY R.Heitanen, T.Jaakola, andJ.K. Miettinen, 8thInt.yrup. S Scientific for Basis Nuclear WasteManagement,Boston, MA (Nov.2630, 1984). D.M. Roy,Proc. 8thIntl. Congr.Chem.Cement.Brazil, 362380 V.I, (1986). D.M. Roy,R.Malek,andP.H.Licasu'o. Concrete Durabiliw. K.andB. Mather International Conference, SPI00, AC[ Vol.2,14591476 (i987).
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8. 9.
I0.
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85
14. 15.
D.M. Roy and R.I.A. Malek, Proc., Intl. Workshopon Granulated Blast Furnace Slag in Concrete, Missasauga,OnL(1987), 12pp. D.M. Roy and K.M. Parker,Proc.CANMET/ACIFirst Intl. Conf. on the Use of Fly Ash, Silica Fume, Slag and Other MineralByproducts in Concrete, Vol. l, Ed. V.M. Malhoa'a,pp. 397414; ACI SP79, ACI, Detroit (1983). A. Kumar, Diffusion and PoreStructure Studiesin Cementitious Materials,Ph.D. Thesis in Solid State Science, The PennsylvaniaState University, University Park. PA 16802 (1985). R.F. Feldman, Theme 4.1, Proc. 8th Intl. Congr.Chem. Cement, Brazil, V. I. A. Kumar and D.M.Roy, Cem. Concr. Res. _ 7478 (1986).
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R.I.A. Malek, D.M. Roy, and Y. Fang, Port Structure,Permeability, and Chloride Diffusion in Fly Ash and Slag Containing Pastes and Mortars(this Symposium in press). S. Diamond, (1973). Port Structureof HardenedCement Paste as Influenced by Hydration Temperature,pgre Structure Pro_oerties Materials,Proc. Intl. and of Syrup. Prague, Sept. 1973, IB73B88. S. Li and D.M. Roy, Investigationof RelationsBetween Porosity. PoreStructure. andCI Diffusion of Fly Ash and BlendedCementPastes:Cem. Concr. Res..L.6., 749759 (1986). R.F. Feldman, Proc. 5th Intl. Syrup. Monterey,1981, 261288. E.L Whim, B.E. Sch¢¢tz, D.M. Roy, K.G. Ziammrman, and M.W. Grutzo:k,pp. 474,78in Scientific Basis for NuclearWasteManafen'_nt_ Vol. 1; Proc., Materials Rese, _h Society, Ed., G.J. McCarthy,Plenum, NY (1979). a M.W. Barnes, D.M. Roy, and C.A. Langton,_i:ientific Basis for NuclearWaste VIII, pp. 865874, Eds., C.M..Iantzen, J.A. Stone, and R.C. Ewing (1985); Materials ResearchSociety Symposium Proceedings, Vol. 4.4. B.E. Scheetz, E.L. White, D. WolfeConfer,and D.M. Roy, 7th Intl. Congress Chemistry of Cement, Pans (1980), Vol. Ill, Communciations, VI170VI175. M.W. Grutzock. B.E. Sch_t2, E.L White, and D.M. Roy, Borehold and Shaft Plugging Proceedings OECDAJSDOE,Columbus,OH (79 May 1980), 353368, OECD, Paris, France (1980). LD, Wakel¢y and DM. Roy, A Method forT_dng the PermeabilityBetween Grout and Rock. Cera. Concr. Res. L2,,533534 (1982). D.M. Roy, E.L. White, and Z. Nakagawa, Effects of Early Heat of Hydrationand F, posunt to ElevatedTemperatures Pro[:smies Mortarsand Pastes with Slag x on of Cement, ASTM, STP, 858, Tcm_rature Effectson Concrete. 150167 (1985). T.C. Powers, J. Am. Ceram. SOC. _ 16 (1958).
20.
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B.E. Sch¢*tz and D.M. Roy, pp.933942 in Scientific Basis forNuclear Waste M.gOggtllIlt_,Vol. VIII; Proc., MaterialsResearchSociety, Vol. 44, Eds., C.M. Jantzen, J.A. Stone and R.C. Ewing (1985). B.E. Scheetz, D.M. Roy, and C. Duffy (in press).
86
Concrete Chairman
and
Structures
Advisory
Committee Liaisons
James J. Murphy New York State Department Vice Chairman Howard H. Newlon, Jr.
of Transportation
Theodore 1L Ferragut Federal Highway Administration Crawford F. Jencks Research Board
r
Virginia Transportation Members Charles J. Arnold Michigan Department Donald E. Beuerlein Koss Construction Co. Bernard C. Brown
Research Council (retired)
Transportation
"
Bryant Mather USAE Waterways Eaperiment of Transportation Thomas J. Pasko, Jr. Federal Highway Administration John L. Rice Federal Aviation
Station
Administration
Iowa Department
of Transportation
Suneel Vanikar Federal Highway Administration Ready Mixed 11/19/92 Expert Task Group
Richard D. Gaynor National Aggregates Association/rNational Concrete Association Robert J. Girard Missouri Highway David L. Gress University of New Hampshire Gary Lee Hoffman Pennsylvania Brian B. Hope Queens University Carl E. Locke, Jr. University of Kansas Clellon L. Love.all Tennessee Department David G. Manning Ontario Ministry of Transportation Robert G. Packard of Transportation Department of Transportation and Transportation
Department
Amir Hanna Transportation Richard Research Board
H. Howe Department of Transportation (retired)
Pennsylvania Stephen
Forster
Federal Highway Administration Rebecca S. McDaniel Indiana Howard Department of Transportation
H. Newlon, Jr. Research Council (retired)
Virginia Transportation Celik H. Ozyildirim Virginia Transportation Jan P. Skalny
Research Council
W.R. Grace and Company A. Haleem American Officials Tahir Association
(retired)
Portland Cement Association James E. Roberts California Department
of State Highway and Transportation
of Transportation
John M. Scanlon, Jr. Wiss lanney Elsmer Associates Charles F. Seholer Purdue University Lawrence L. Smith of Transportation
Lillian Wakeley USAE Waterways Experiment
Station
Florida Department John 1L Strada
Washington Department
of Transportation
(retired)