SURFACE FREE ENERGY MEASUREMENT OF AGGREGATES AND ITS APPLICATION TO ADHESION AND MOISTURE DAMAGE OF ASPHALTAGGREGATE SYSTEMS

DING XIN CHENG Ph.D. Candidate in Civil Engineering, The Texas A&M University, College Station, TX, USA DALLAS N. LITTLE Kelleher Professor, Associate Director International Center for Aggregates Research, Civil Engineering, The Texas A&M University, College Station, TX, USA ROBERT L. LYTTON Benson Chair Professor, Director - Center for Infrastructure Engineering, Civil Engineering, The Texas A&M University, College Station, TX, USA JAMES C. HOLSTE Professor, Associate Dean for Graduate Studies and International Programs (College of Science), Department of Chemical Engineering, Texas A&M University, College Station, TX Abstract A protocol for measuring the thermodynamic surface free energy of aggregates using the Universal Sorption Devices is presented. Surface free energy, which is the reflection of material surface physical chemistry characteristics, can be used to evaluate adhesive fracture and moisture damage characteristics within the asphalt-aggregate system. Three widely used aggregates were tested using the Universal Sorption Device. The materials possessed very different surface free energies. By knowing the surface energy of the asphalt and aggregates, the most compatible asphalt-aggregate combination can be selected that will increase the ability of the asphalt pavement to resist adhesive fatigue fracture and moisture damage and maximize fracture healing.

Key Words: Surface free energy, universal sorption device, vapor adsorption, spreading pressure, asphalt-aggregate adhesion, and moisture damage

Introduction Asphalt pavement performance is related to cohesive and adhesive bonding within the asphalt-aggregate system. Cohesive and adhesive bonding is in turn related to the surface free energy characters of the asphalt and aggregates. Actually, surface free energy theory has been widely used in colloid lubrication, adhesive coatings, and the painting industry for many years. The surface free energy of a solid (or a liquid) is defined as the work needed to create new elemental area under a vacuum condition. Here, the thermodynamic changes in the surface free energies of adhesion and cohesion are related to separation of the interface between the asphalt and the aggregate (adhesive fracture) or fracture within the binder or mastic (cohesive facture). On the other hand, it is also true that thermodynamic changes in surface free energy are required to heal a fracture between the surfaces of the asphalt and the aggregate or within the mastic. Thus, it is very important to be able to measure the surface free energies of asphalt and aggregate, which are required to calculate the work of adhesion and cohesion. By knowing the characteristics of cohesion and adhesion within the asphalt mix, one can use them to evaluate the potential for fracture, healing, wettability, and stripping within asphalt concrete pavements. Also, by changing the surface free energy of the asphalt-aggregate system, one can improve the performance of the pavement. Unlike liquids, the surface free energy of aggregates can only be measured by indirect methods. This is primarily because of the irregular shape, rough surface texture, and high surface energies of aggregates. The Universal Sorption Device (USD) is an indirect method that can accommodate surface peculiarities of aggregates and can be used to measure their surface energies. Principles in Aggregate Surface Free Energy Testing The surface free energy components of the aggregates are mainly comprised of a non-polar component and an acid-base component [2]. The non-polar component of surface free energy is comprised of the Lifshitz-van der Waals forces, and the acid-base component is comprised of the acid-base intermolecular forces.

Equation 1 is used to describe the total surface free energy and its components: = LW + AB Where, = Surface free energy of the asphalt or aggregate, LW = Lifshitz van der Waals component of the surface free energy, AB = Acid-base component of the surface free energy. The Lifshitz-van der Waals force contains at least three components: London dispersion force (Eisenschitz and London, 1929; London, 1931), Debye (1921) induction force, and Keesom (1921) orientation force. The London dispersion force is the attraction between neighboring electronic shells. It is an induced dipole to induced dipole interaction. The Debye induction force is produced by a dipole inducing a dipole in a neighboring molecule. The Keesom orientation force is the interaction of two dipoles orienting themselves in relation to each other [3]. The acid-base interaction includes all interactions of electron donor (proton acceptor) - electron acceptor (proton donor) type bonds including hydrogen bonding. To quantitatively predict and treat the acid-base interaction, Good (1992) postulated a resolution of the acid-base term into an (Lewis) acidic surface parameter and (Lewis) basic surface parameter [4]. The relation among the AB and its components is shown in equation 2: AB = 2 + Where, + = Lewis acid component of surface interaction, and - = Lewis base component of surface interaction. Several methods are proposed in the literature to measure the surface free energy of the asphalt-aggregate system. Elphingstone (1997) [5] measured the surface free energies of a various kinds of asphalts using the Wilhelmy Plate technique and checked results with the Pendant Drop method (the pendant drop apparatus is at the University of Tulsa). Dr. Wenduan Li (1997) [6] used gas adsorption method to measure the surface free energies of certain kinds of Europe aggregates. In order to more accurately measure surface free energy of aggregates, a new protocol using the USD was developed. The (2) (1)

USD employs a Magnetic Suspension Balance from Rubotherm, which gives more accurate mass readings than previously thought possible and also can significantly reduce the environment influence. The methodology by which the USD is used to measure surface free energies of aggregate takes the following steps: 1. Use three solvents whose surface energy components are known. The solvents, nhexane (non-polar), MPK (methyl propyl ketone/2-pentanone, mono-polar) and water (bi-polar) were selected as the gas solvents. 2. Measure the specific amount of solvent adsorbed on the surface of the absorbent, and simultaneously measure vapor pressure p at the surface of the aggregate. 3. Correct the adsorption data for solvent vapor buoyancy by using the generalized Pitzer correlation [7]. 4. Calculate the specific surface area of aggregate by using the BET equation 3. c 1 P 1 P + = n( P0 P) nm c P0 nm c (3)

5. Calculate the spreading pressure at saturation vapor pressure, e, for each solvent using Gibbs adsorption equation 4. RT e = A
Po

P dP
0

(4)

Where, e = Spreading pressure at saturation vapor pressure of solvent, R = Universal gas constant, 83.14 cm3 psi/gK, T = Absolute temperature, Kelvin, A = Specific surface area of absorbent, Po = Saturated vapor pressure of solvent, N = Specific amount adsorbed on the surface of the absorbent, and P = Vapor pressure. 6. Express the work of adhesion of liquid on a solid in terms of the surface tension (surface energy) of the liquid and the equilibrium spreading pressure of adsorbed vapor on the solid surface as shown in equations 5 [8], 6 and 7:

W A = e + 2 l = G sl
LW AB G sl = G sl + G sl = 2 sLW lLW + 2 s+ l + 2 s l+

(5) (6) (7)

e + 2 = 2 sLW lLW + 2 s+ l + 2 s l+
7. Calculate the surface free energy.

Use equation 8 to calculate LW from a non-polar liquid on the surface of the asphalt or aggregate: s
LW

( e + 2l ) 2 4lLW

(8)

If one mono-polar basic liquid and one bi-polar liquid are selected, use equation 9 and 10 to calculate the values of +s and s: =
+ s LW 2 ( e + 2lm sLW lm ) 4lm 2 LW ( e + 2 lb 2 sLW lb 2 s+ lb ) + 4 lb

(9)

(10)

Calculate the total surface free energy of the aggregate s by equation 11: s = sLW + 2 + (11)

Development of USD The main components of the Universal Sorption Device include: Rubotherm magnetic suspension balance system, computer, Messpro (computer software), temperature control, high quality vacuum, vacuum regulator, pressure transducer, solvent container, and a vacuum dissector. The simplified USD setup diagram is shown in Figure 1. The Rubotherm magnetic suspension balance has the ability of tomeasure sample mass up to 200 g, which is well beyond the requirement for measuring the surface free energy of aggregate. The size of aggregate tested is that which passes the No.4 (4.75mm)

sieve but is retained on the No. 8 sieve (2.36mm). The aggregate sample holder as shown in Figure 2 is made of a fine aluminum screen. The total and component surface analyses of the these solvents; n-Hexanes, methyl propyl ketone, and distilled water (25o C ); were obtained from the literature [9] and are listed in Table 1. Aggregate Testing Three aggregates, Texas Limestone, Colorado Limestone, and Georgia Granite, were selected for surface free energy analysis. After wet sieving, about 150 g of each aggregate were collected. The aggregates were washed again using distilled water and then put into 1200 C oven and dried for at least 8 hours. The aggregate sample was then moved into a vacuum desiccator at about 1 torr and 1200 C for at least 24 hours to de-gas. The aggregate sample container shown as Figure 2 was washed carefully with distilled water and acetone and dried in an oven at 1200 C for 1 hour. The weighted aggregate sample was then placed in the container. The temperature control circulator was connected with the high-pressure steel chamber. Next the Magnetic Suspension Balance was activated and recalibrated. Then the vacuum pump was used to evacuate below 1 torr for 1 day while the chamber was heated to 600 C. The chamber temperature was reduced and maintained at 250 C under the vacuum of below 1 torr for eight hours. The Messpro computer program was then initiated to control testing and acquire data. At this point solvent vapor was injected into the system until pressure reached the first predetermined value by using a microadjustment valve. After the steady-state adsorption mass was reached, the pressure was changed to next setting point. The process was repeated while using the computer to record the absorbed mass and vapor pressure until the saturated vapor pressure of the solvent was reached. Testing is repeated with the remaining solvents in the order: n-hexane, MPK, and water. Testing Results The BET theory is used to calculate the specific surface areas (SSA) of aggregates, which is the surface area per unit weight of absorbent. To illustrate, Figure 3

shows the BET plot of the adsorption isotherm of bi-polar solvent distilled water and the Colorado Limestone Sample 1. Within the BET plot, P represents the vapor pressure; Po represents the saturated vapor pressure; and n is the specific amount of absorbate adsorbed on the unit mass of absorbent. From the plot, one can calculate the monolayer adsorption capacity (mass) of absorbent using the slope and the intercept of the plot. Then, the Closed-packed Hexagonal model is used to calculate the specific surface area of the absorbent. The specific surface areas of the samples are calculated using the adsorption of the three solvents and are listed in Table 2. For similar size groups, the descending order of SSA are Texas limestone, Colorado limestone, and Georgia granite. The SSAs of the limestones are considerably greater than that of Georgia granite which means that the two limestones have a relative rougher surface texture compared to the Georgia granite. The saturated spreading pressures [10] of solvents onto aggregates are calculated using Gibbs equation and the results are listed in Table 3. Surface free energy measurement results are summarized in Table 4. The surface energy of two kinds of asphalt, AAD and AAM [11] are also listed in Table 4. Several interesting trends are clear from Table 4: 1. A large difference exits in surface free energies among aggregates of different mineralogical types. The Georgia granite shows high acidic surface free energy while the limestone shows higher basic components of surface free energy. 2. Although the two limestones have clearly different surface free energy properties, similarities are evident when compared to the other aggregates. 3. The difference between duplicate samples was larger than expected. These differences are most probably due to random variability in mineralogy between or among samples and the fact that each sample is a composite comprised of hundreds of particles. Table 5 presents the summary of surface free energies and standard deviations for the three aggregates tested.

Cohesion and adhesion The free energy of cohesion Gic is the formation of a cohesive unit area of union between two bodies of the same material under the vacuum conditions shown in Figure 4 and equation 12 [11]. GiC = 2i (12)

The free energy of cohesion has two components, GicLW and GicAB, shown as equation 13. GiC = GicLW + GicAB Similarly, the free energy of adhesion corresponds to the formation of an adhesive union of two unlike bodies in the vacuum shown in Figure 5. Adhesion is defined by equations 14 and 15.
a Gij = ij i j a aLW aAB Gij = Gij + Gij

(13)

(14) (15)

Where ij is the interfacial surface free energy. Similarly, there are two components for interfacial surface free energy as described in equation 16. ij = ij
LW

+ ij

AB

(16)

For the Lifshitz-van der Waals component of surface free energy, the Berthelot geometric mean holds [12]. ijLW = ( iLW jLW ) 2
aLW Gij = 2 iLW jLW = GicLW G cLW j

(17) (18)

For the acid-base components of the surface free energy, equations 18 and 19 are valid due to complementarity in acid-base interaction. ijAB = 2( i+ j+ )( i j )
aAB Gij = 2 i+ j 2 i j+

(19) (20)

Fracture is the reverse process of cohesion or adhesion. For the reversible and isothermal process, work needed to create the unit area of fracture is equal to the negative

value of cohesion or adhesion. If the value of free energy of cohesion or adhesion is negative, it means the two phase of the material tend to bind together and the higher magnitude of free energy of cohesion or adhesion gives the higher cohesion or adhesion. For the general case, the free energy of adhesion for two different materials in contact within a third medium is explained by equation 21.
a G132 = 12 13 23

(21)

By using surface free energy, the cohesion of asphalts and the free energy of adhesion in asphalt pavement is calculated using equations 12, 13, 15, 18 and 20. The results are shown in Table 6. From Table 6, several conclusions are drawn: 1. All the free energy of adhesion or cohesion is negative which means all the materials tend to bind together under vacuum condition (or phases stick together spontaneously). 2. At the temperature of 25 0C, the descending order of free energy of adhesion among the liquids is water > AAK-1 > AAD-1. This means that the three aggregates tested are hydrophilic, but AAK-1 has more relative adhesion potential in the presence of water than AAD-1. This gives theoretical support to the fundamental knowledge that water disrupts the asphalt aggregate bond (strips) due to its favorable afinity to bond with the aggregate surface. Furthermore, different asphalt binders have different adhesion characteristics which influence the fracture fatigue life and moisture damage potential of the pavement. 3. Per unit SSA, the adhesion potential for both asphalts AAD and AAK are greatest with Georgia granite, followed by Texas limestone and Colorado limestone. However, limestones have nearly three times more surface area which gives the biggest adhesion between the asphalt-aggregate system. . This idea can be better explained by using Gibbs free energy per unit amount of aggregate material (mass) which is the energy needed to pull the asphalt away from the unit mass of aggregates by tension [13]. Equation 22 is used to

calculate the Gibbs free energy per unit amount of aggregates. The results are listed in Table 7. ergs ergs cm 2 G = SSA gm gm cm 2 (22)

The results show that for unit amount of aggregate the Gibbs free energy is in following order: Texas limestone > Colorado limestone > Georgia granite. 4. AAK-1 like AAM-1 has higher acid-base components of surface free energy (acid-base parts of cohesion) and lower Lifshitz-van der Waals components of surface free energy (LW parts of cohesion) than AAD-1. According to Little et al, (1999) [14], AAK-1 like AAM-1 is a better healer than AAD-1.

Water stripping Moisture is a very important factor in the deterioration of the asphalt pavement. Terrel and AL-Swailmi (1994) [15] identified three mechanisms of moisture damage in SHRP-A-403 report: (1) Loss of cohesion (strength) and stiffness of the asphalt film that may be due to several mechanisms; (2) Failure of the adhesion (bond) between that aggregate and asphalt (often called stripping), and (3) Degradation or fracture of the aggregate, particularly when the mixture is subjected to freezing.

Stripping as an adhesion failure may occur either at the pavement surface or internally within the mixture (White, 1987). At the surface, stripping begins at the weak points such as joints, areas of poor quality control areas or areas of high air content void due to low compaction. Gradually, the mastic bond with the surface of the coarse aggregates degrades. The asphalt film may be separated from the aggregate by emulsification. Shute et al. (1989) provides the following factors that appear to affect adhesion.

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1 2 3 4 5 6 7

Surface tension of the asphalt cement and aggregate, Chemical composition of the asphalt and aggregate, Asphalt viscosity, Surface texture of the aggregate, Aggregate porosity, Aggregate cleanliness, and Aggregate moisture content and temperature at the time of mixing with asphalt cement.

All of the above factors are very important in the adhesion analysis. Curtis (1993) [16] points out that both siliceous and calcareous aggregate can be strippers, but both can also be non-strippers. The siliceous aggregate has slick, smooth areas, which may give rise to stripping. Different aggregates have very different textures (SEM from Curtis et al, 1990). In our research, the value of adhesion between asphalt and aggregate can be directly calculated using thermodynamic theory, which more directly explains why striping occurs on some asphalt aggregate system while some other systems are not prone to stripping. The adhesion calculation actually considers all the factors listed. Adhesion uses surface free energy/ surface tension which reflects the physical and chemical interaction of the surface. Surface purity and moisture content of aggregate definitely influence adhesion. Specific surface area calculated by using BET theory reflects the surface texture of aggregate. For example, it can be used to explain why granite is more likely to strip than limestone based on adhesion theory according to the following steps: 1. Stripping may occur in both asphalt (AAD-1/AAK-1) granite systems and asphalt (AAD-1/AAK-1) limestone systems. According to the adhesion results from table 7, the adhesion between the water and aggregate (granite or limestone) is higher than that of asphalt (AAD-1 or AAK-1) with aggregate (granite or limestone). 2. Stripping may not occur in either asphalt-granite systems or asphalt limestone systems if no moisture can get into the interface of asphalt and aggregate.

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3. The granite has a much smoother surface texture according to table 5. At the same gradation , the limestone has three times more surface area and almost three time Gibbs free energy (according to Table 7) than granite. Thus, it is much easier to induce adhesive fracture at the asphalt-granite interface under the same wheel load and environmental stresses, i.e., granite is more likely to strip.
4.

The new interface at fracture will be occupied by water and will not heal according to the results of table 6. Gradually, the larger areas of adhesion bond failure occur and HMA endure premature failure due to water-induced stripping.

Conclusions Based on the results of surface free energy and the work of the adhesion analysis, stripping may occur in both the asphalt (AAD-1/AAK-1) - granite systems and the asphalt (AAD-1/AAK-1) - limestone systems. But water is required at the asphaltaggregate interface to induce stripping in each system. According to the magnitude of adhesion (per unit area) and specific surface area, asphalt is more likely to strip from the Georgia granite than from either the Colorado or Texas limestones. Thus, the surface energy match between asphalt and aggregate is very important. The surface energy adhesion analysis will help match appropriate asphalt-aggregate systems to in order reduce stripping potential. Further research on the surface free energies of different aggregates will build a very useful database for pavement material selection. Also, the surface free energy changes due to anti-stripping agent will be very useful for analysis of water induced stripping.

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References 1. Adamson, Arthur W., Physical Chemistry of Surfaces, 6th, 1997, PP18-40 2. Fowkes, F. M., Determination of Interfacial Tensions, Contact Angles, and Dispersion Forces in Surfaces by Assuming Additivity of Intermolecular Interactions in Surfaces, Journal of Physical Chemistry, 66,382 (1962) 3. Maugis, D., Contact, Adhesion and Rupture of Elastic Solids, Springer, 1999, PP312 4. Good, R. J., and van Oss, C. J., The Modern Theory of Contact Angles and the Hydrogen Bond Components of Surface Energies, Plenum Press, New York, 1 (1991) 5. Elphingstone, G. M., Adhesion and Cohesion in Asphalt-aggregate Systems, Ph.D. dissertation of Texas A&M University, 1997 6. Li, W., The Measurement of Surface Free Energy for Aggregates SHAP RB, Final Report of Cahn Balance Thermogravimetry Gas Adsorption Experiments, 1997 7. Smith, J.M., van Ness, H. C. and Abbott, M.M., Introduction to Chemical Engineering Thermodynamics, McGraw-Hill Companies, Inc. 5th, 1996, PP85-89 8. Zettlemoyer, A.C., Hydrophobic Surfaces, Academic Press New York and London, 8, 1969 9. Good, R. J., Contact-Angle, Wetting, and Adhesion: A Critical Review, Journal of Adhesion Science and Technology, 6 (12): 1269-1302 1992 10. Smith, J.M., van Ness, H. C. and Abbott, M.M., Introduction to Chemical Engineering Thermodynamics, McGraw-Hill Companies, Inc. 5th, 1996, P538 11. Good, R.J., and van Oss, C.J., The Modern Theory of Contact Angles and the Hydrogen Bond Components of Surface Energies, Modern Approach to Wettability: Theory and Application, Plenum Press, New York, 1991, 1 12. Good, R.J., Surface Free Energy of Solids and Liquids: Thermodynamics, Molecular Forced, and Structure, Journal of Colloid and Interface Science, Vol. 59, No. 3, 398, 1977

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13. Curtis, C.W., Lytton, R.L., and Brannan, C.J., Influence of Aggregate Chemistry on the Adsorption and Desorption of Asphalt, Transportation Research Record, No 1362, 1 9, 1992. 14. Little, D.N., Lytton, R. L., and Williams, D., Propagation and Healing of Microcracks in Asphalt Concrete and Their Contribution to Fatigue, Asphalt Science and Technology, pp. 149, 1999. 15. Terrel, R.L., Water Sensitivity of Asphalt-Aggregate Mixes, SHRP-A-403, 1994
16.

Curtis, C.W., Ensley, K. and Epps, J., Fundamental Properties of Asphalt-Aggregate Interactions Including Adhesion and Absorption, SHRP-A-341, 8, 1993

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Table 1. Surface Free Energy Components of the Solvents, (erg/cm ).

Absorbate n-hexanes MPK Water

18.4 24.7 72.8

LW 18.4 24.7 21.8

AB 0 0 51.0

+ 0 0 25.5

0 19.6 25.5

Table 2 Specific surface area of the aggregates. Aggregates Georgia granite #4-#8 -1 Georgia granite #4-#8 -2 Texas Limestone #4-#8 1 Texas Limestone #4-#8 2 Colorado limestone #4-#8 1 Colorado limestone #4-#8 -2 Specific Surface Areas (m2/g) 0.10 0.11 0.44 0.43 0.31 0.26

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Table 3 Equilibrium Spreading Pressures of Solvents onto Aggregates. Aggregates Spreading pressure, e, (ergs/cm2) n-Hexane 73.02 50.08 44.16 41.81 38.73 41.05 MPK 22.90 23.62 44.77 34.24 40.71 38.89 Water 98.66 115.53 102.89 139.57 93.15 88.66

Georgia granite #4#8* -1 Georgia granite #4#8 -2 Texas Limestone #4-#8 1 Texas Limestone #4-#8 2 Colorado limestone #4-#8 1 Colorado limestone #4-#8 -2 *-- The size of the aggregate

Table 4. Surface Free Energy Results of Samples ( Testing temperature = 25oC; Units in ergs/cm2 or mJ/m2).
Aggregate or Asphalts Gergia Granite 1 Gergia Granite 2 Texas Limestone 1 Texas Limestone-2 Colorado Limestone 1 Colorado Limestone 2 AAD-1 AAK-1 38.49 9.75 0.00 0.71 0.09 0.05 0.2 0.8
+

28.97 162.97 233.34 337.75 215.55 197.35 7.3 7.6

-

66.79 79.72 1.27 30.89 8.61 6.06 2.42 4.93

AB

163.85 102.56 89.06 83.96 77.52 82.34 27.8 22.6

LW

230.64 182.28 90.33 114.85 86.13 88.40 30.22 27.53

Table 5. Sample Mean and Standard Deviation of Surface Free Energies and Specific Surface Areas (Unit for surface free energy: ergs/cm2).
Aggregates Gergia Granite Texas Limestone Colorado Limestone 24.1 0.4 0.1
+

s s 20.3 96.0 94.8 0.5 285.5 73.8 0.0 206.5 12.9

-

73.3 16.1 7.3

AB

S 9.1 20.9 1.8

SSA LW 2 s s m /g s 133.2 43.3 206.5 34.2 0.1 0.01 86.5 3.6 102.6 17.3 0.4 0.01 79.9 3.4 87.3 1.6 0.3 0.04

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Table 6 Adhesion between Asphalt-aggregate System and Aggregate-water (unit: ergs/cm2).

AAD-1 G Georgia Granite -121.71 Texas Limestone -98.08 Colorado Limestone -94.28
LW

AAK-1
Total LW AB Total LW

Water
AB Total

G -35.30 -18.33 -14.24

AB

G G G G G G G -157.01 -109.74 -44.60 -154.34 -107.78 -148.54 -256.32 -116.41 -88.43 -33.51 -121.94 -86.85 -176.67 -263.52 -108.52 -85.00 -27.12 -112.13 -83.49 -147.71 -231.20

Table 7 Gibbs Free Energy per Unit Amount of Aggregate (unit: ergs/gm)
AAD-1 Gibbs free energy Georgia Granite Texas Limestone Colorado Limestone G 126180.1 425495.7
LW

AAK-1 G 162779.3 505009.4

Total

G 36599.2 79513.7
AB

G 113768.7 383642.7
LW

G 46243.2 145365.4
AB

G 160011.8 529008.1
Total

268040.2

40491.8

308532.0

241675.1

77110.1

318785.1

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, ,3.0 , !7088:70 .43974 ,3/ 20,8:702039 309 . 70,/ 3 ., 9,70 074 54 39 8:85038 43 -, ,3.0 -7,9 43

54 39 ,3/ 20,8:7 3

$4 ;039 ;,547 8:55

Figure 1 Universal Sorption Device (USD).

27.5 mm

Figure 2 Aggregate Sample Holder.

55 mm

%02507,9:70 .43974

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2.50 P/n(Po-P), (g/mg) 2.00 1.50 1.00 0.50 0.00 0 0.05 0.1 0.15 P/Po 0.2 0.25 0.3 y = 7.3183x + 0.275 R2 = 0.9984

Figure 3 BET Water Vapor Adsorption onto Colorado Limestone Sample - 1.

i 1cm i V acuum
2

Figure 4 Process of cohesion

j 1 cm i
2

V acuum

Figure 5 Process of Adhesion.

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