Colloid and Surface Chemistry

C H A P T E R

19 Colloid and Surface Chemistry 19.1 INTRODUCTION Much of what will be considered in this chapter is surface chemistry. Chemically, a surface layer (interfacial or interface layer) is the boundary between two phases. The boundary is a few molecules thick. Two examples are a cellulose fiber in contact with aqueous solution and an oil phase in contact with a water phase in an emulsion. Colloidal chemistry is one branch of surface chemistry. Surface chemistry and physics are important in colligative properties of solutions, capillary action, papermaking chemistry, water treatment, refining behavior, and foaming.

19.2 COLLOID CHEMISTRY

to the particles themselves. The dispersion medium forms a continuous phase; both of these terms are used to describe the principal phase. Because a gas in a gas does not exist as discrete phases, there are eight (3
3 e 1) different types of colloids (Table 19.1). Aerosol is a colloidal solution having a gas as the dispersion medium and a

TABLE 19.1

Two-Phase Colloidal Systems

Dispersed Dispersion Phase Medium

Name

Examples

Liquid

Gas

Liquid aerosol

Fog, mist, hair spray

Solid

Gas

Solid aerosol

Smoke, dust, allergens

Gas

Liquid

Foam

Head on beer, foaming

Liquid

Liquid

Emulsion

Italian salad dressing, milk

Solid

Liquid

Sol, paste

Ink, mud, clay slurries

Gas

Solid

Solid foam

Foam rubber, styrofoam

Liquid

Solid

Solid emulsion

Pearl, ice cream

Solid

Solid

Solid dispersion

Acrylonitrile butadiene styrene (ABS), paper, pigmented plastics

Colloids A colloid is a stable combination of particles of one substance that are dissolved or suspended in a second substance; the particles have at least one of the principal dimensions (somewhat arbitrarily) from about 1 nm to 1 mm. (The time frame of stability is also somewhat arbitrary.) The small size of colloidal particles means that a high percentage of the molecules will be on the surface, so surface chemistry is of vital importance to their properties. A colloid may be considered to include the gas, liquid, or solid in which the particles are dispersed in addition

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381

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382

19. COLLOID AND SURFACE CHEMISTRY

solid as the dispersed phase. Fog is an aerosol of water droplets; smoke is an aerosol of solid particles. An emulsion is a sol in which the suspended particles are liquid droplets and the continuous phase is also a liquid; the two phases are immiscible, otherwise a solution would form. A colloidal suspension is a sol of solid particles suspended in a liquid. Foam is a colloidal system of gas bubbles dispersed in a liquid or solid. Styreneebutadiene copolymer and paper are both colloidal solids. This size range includes soluble polymers of a few thousand g/mol at the small extreme to most fillers and pulp fines at the large extreme; weak chemical bonds can hold objects in this size range together because of the high surface areas.

Colloid Surfaces The surfaces of colloids are of utmost importance as the interaction of the particles with each other and the principal phase is of primary concern. The surface-to-volume ratio of a given particle shape is inversely proportional to the length of the principal axis. For TABLE 19.2

example, in a sphere the volume increases in proportion to r3 but the surface area increases only in proportion to r2. A cube of 1 m on each side has a surface area of 6 m2/l000 kg or 0.000006 m2 g. A cube of 1 cm (1/100 the length of the larger cube) has a total surface area of 6
l04 m2 g or 0.0006 m2 g (100 times the specific surface area of the large cube). For a small molecule such as Al2O3, about 1 in 100 molecules will lie on the surface of a 0.1 mm particle and about 1 in 10 of a 0.01 mm particle. It takes energy to create surface area of particles. The energy required is related to the surface tension of a material. (One speaks of surface tension of a liquid against a gas, usually its vapor, and interfacial tension of two liquids against each other.) The surface tension (g) of water at 20 C is about 72 mJ/m2. The work (W) or surface excess free energy (G) required to make new surface area (A) is given as follows: DG ¼ DW ¼ 2gA

(19.1)

Table 19.2 demonstrates this concept with 1 mol of water at 20 C. On the first line of the table, the 1 mol of water forms a single sphere.

Colloidal Properties of 1 mol of Water Versus Spherical Particle Size Particle Area (cm2)

Total Area (cm2)

Total Surfacea Energy (J/mol)

Specific Areab (m2/g)

Particle Radius

Particle Number

Particle Volume (cm3)

1.63 cm

1

18

33.2

33.2

0.00048

1.8$104

1.00 mm

4300

4.19$103

0.126

540

0.00619

3.0$103

0.10 mm

4.30$106

4.19$106

1.26$102

5400

0.0619

3.0$102

0.01 mm

4.30$109

4.19$109

1.26$105

5.4$104

0.619

3.0$101

1.00 mm

4.30$1012

4.19$1012

1.26$107

4.3$105

6.19

3.0

0.10 mm

15

4.30$10

4.19$10

15

9

6

4.3$10

61.9

3.0$101

0.01 mm

4.30$1018

4.19$1018

1.26$1011

4.3$107

619

3.0$102

1.00 nm

4.30$1021

4.19$1021

1.26$1013

4.3$108

6192

3.0$103

0.1925 nm

6.02$1023

2.98$1023

4.66$1015

2.8$109

40,300

3.0$104

a

1.26$10

From Eq. (19.1). This is applicable for spherical particles of specific gravity 1.0; for other materials, divide this number by the specific gravity of the solid material for the given particle radius. b

383

19.2 COLLOID CHEMISTRY

As this water is divided to form smaller spheres, the surface area increases, as does the surface excess free energy. As the surface free energy is a bulk property, it has little meaning for very small particles; however, for the last entry, corresponding to separation into individual molecules, this value (40.3 kJ/mol) corresponds well with the heat of vaporization of water (40.7 kJ/mol at the boiling point and lower at room temperature). This energy provides a driving force for the coalescence of small water droplets. Table 19.2 is also a good reference for the approximate specific surface area of particles (based on particle diameter), for a first-order approximation (see the second footnote). Emulsifying agents act to reduce the surface tension between two dissimilar liquids. Soap emulsifies oil and water by decreasing the interfacial tension of the oile water interface via fatty acid molecules that have affinity for both phases. (The fatty acid may be called a compatibilizer.) The high proportion of molecules on the surfaces of small particles means that colloidal particles behave much differently than larger materials. For example, the flat surfaces of kaolinite clay tend to be negatively charged, whereas the edges are positively charged below pH 7, which explains why clay tends to coagulate at low pH [it is described as a house of cards structure (Hunter, 1987)]. The edges of clay particles will absorb phosphate ions (PO4)3 and obtain a negative charge. This negative charge causes them to repel each other in suspension, making the clay much easier to disperse (thinning). Calcium ions have an opposite effect (thickening).

Micelle Formation The classic behavior of soap molecules in water is a good example of a very practical application of colloidal chemistry. (Both individual molecules and aggregates of soap molecules are colloids but with different properties.) Soap

molecules are sodium or potassium salts of fatty acids (Fig. 2.31, Vol. 1). At very low concentrations, soap particles are individually dissolved in the water and contribute to the colligative properties (such as increased osmotic pressure) according to the number of moles present. As the concentration increases to the critical micelle concentration, CMC, soap particles abruptly agglomerate into spherical structures called micelles. Micelles are groups of about 20 to several hundred molecules with the nonpolar (hydrophobic) hydrocarbon tail toward the center and the polar (hydrophilic) head toward the surface in contact with water (Fig. 19.1). The CMC is typically 102 to 103 mol/dm3 for ionic surfactants and 104 mol/dm3 for nonionic surfactants. Several CMC values are given later in the section on surfactants. If the solution is diluted, the micelles dissociate into individual molecules; hence they are termed association colloids. It is the hydrophobic center that “dissolves” grease and oil when washing with soap. Well above the CMC, micelles begin to change shape and may form liquid crystals and other mesomorphic shapes. The biological double-layer membranes of cells are also related to micelles.

M+

M+

M+ –

–

–

M+

M+

– –

– M+ –

– M+ –

–

– M+

M+

– – M+

FIGURE 19.1

– –

–

M+

M+ Soap molecule array in a micelle.

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19. COLLOID AND SURFACE CHEMISTRY

Solution Properties of Colloids Since Freundlich’s classic work (1926), colloids are classified as lyophilic (solvent loving) colloids when the dispersed phase is dissolved in the continuous phase. (If the dispersed phase is a very large or cross-linked polymer, such as some starches or gelatin, then a gel may form. In the case of a gel, the dispersed phase is also continuous.) Lyophobic (solvent hating) colloids occur when the dispersed phase is suspended in the continuous phase; they are thermodynamically unstable. If the dispersed phase is water, the two terms are hydrophilic colloids and hydrophobic colloids, respectively. In papermaking systems, the solvent is almost always water. These terms are arbitrary, but some properties of these colloids can be contrasted after Alexander and Johnson (1949); they are sometimes referred to as reversible and irreversible colloids, respectively. High concentrations of lyophilic dispersed phase (such as watersoluble proteins) are usually stable and often increase the viscosity of the continuous phase substantially; rehydration after desiccation leads to dispersion (reversible); coagulation requires very high levels of electrolytes and usually leads to a viscous residue. On the other hand, lyophobic dispersed phases (such as clay particles, metal oxides, or silver halides in water) are easily precipitated by low levels of electrolytes, are irreversibly coagulated on drying, tend to give granular precipitates, and have high levels of light scattering (if they are not translucent). In 1857, Michael Faraday observed and described some of the fundamentals of colloidal systems. He studied colloidal gold (a wellknown occurrence at that time) prepared by reduction of gold salts and proved that the solutions contained very small gold particles. The resultant colloid was ruby red or blue in color; it exhibited what was to be later called the Tyndall effect, a bluish opalescence that appears when a bright, narrow beam of light passes

through the solution (due to light scattering). He showed that the addition of salts caused the particles to increase in size (aggregate) and even to deposit gold in the vessel. He found that the addition of gelatin would prevent the gold from forming large particles with the addition of salts. We will see that similar phenomena occur in papermaking systems with fiber fines or fillers in place of the gold. Most colloids have charged surfaces from anionic or cationic functional groups, which play central roles in their behaviors. Vegetable fibers have negative charges on their surfaces due to the carboxylic acid groups of hemicellulose and cellulose. Mineral fillers and many polymers used in colloidal systems also have charges. These charges may be positive from cationic groups (from polymers with amine groups or metal cations) or negative (from phosphate groups in potato starch, carboxylate groups in many anionic polymers, sulfate groups, and carbonate groups, to name several examples). The amount and type of surface charges are critical to the stability and solubility properties of colloids. The type and amount of electrolytes (especially the amount and valence of metallic cations), pH, and temperature play critical roles in the solution properties of charged colloids. These factors will be considered in detail presently.

Microscopy of Colloids The resolution of optical microscopy is limited by the wavelength of light. The resolution is about 0.15 mm under the best of conditions and perhaps double this for routine work (about 500e1000 magnification as the unaided human eye can distinguish objects about 0.1 mm apart). A technique known as dark-field microscopy can be used to detect small particles, but with a low level of detail. In this technique, light is directed perpendicular to the direction of viewing. With no particles present, the light does not reach the objective. Lyophobic (insoluble and of different index of refraction as the solution)

385

19.2 COLLOID CHEMISTRY

particles (0.02 mm and larger) can scatter enough light that some of it will be visible. Although detail is lacking, the motion of colloids can be followed to study flocculation, sedimentation, and electrophoretic mobility. Zsigmondy used dark-field microscopy extensively in his classic work on colloidal gold for which he received the 1925 Nobel Prize. Light scattering is an important property of colloids and will be considered in detail. Scanning electron microscopy can be applied to colloid particles but not colloid solutions.

+ –OOC

There are four electrokinetic phenomena of charged surfaces in solution; the first is much more important than the others. Electrophoresis is the movement of charged surfaces (with associated ions and water) in the stationary liquid induced by an external field. Sedimentation potential is the charged field generated by charged particles moving in a stationary liquid. Streaming potential is the generation of an electric field by movement of the liquid along stationary charged surfaces. Finally, electroosmosis is the movement of liquid relative to stationary charged particles induced by an external electric field. The net charge on particles in aqueous solutions can be measured by the process of electrophoresis, which is the basis of some wet end chemistry sensors. When an electric field is applied to two metal plates across a solution of charged particles, the particles will move in response to the force set up by electrostatic attraction (between oppositely charged objects) or repulsion (between like charged objects) (Fig. 19.2). Negatively charged particles move toward the positive plate (anode), and positively charged particles move toward the negative plate (cathode). Uncharged particles or particles with no net charge do not respond to electric fields. For

C

NH3+

H +

–

R –OOC

C

NH2

H +

–

R HOOC

Ionic Interactions and (External) Electric Fields

–

R

C

NH3+

H

FIGURE 19.2

An amino acid at its isoelectric point (top), as an anion (center) at higher pH, and as a cation (bottom) at lower pH. The arrows show the direction of movement for the applied charge.

most charged particles, it is possible to adjust the solution so that the particle has no net charge. This is accomplished by changing the pH or changing the composition of electrolytes in solution. When a particle has no net charge it is at its isoelectric point, and it will not move in the electric field. Electrophoresis is an important tool of biochemistry used to separate groups of proteins and other molecules; it is also one method of measuring zeta potential (effective surface charge). Many amino acids are zwitterions, dipolar ions or inner salts, and represent structures with no net charge. Fig. 19.2 (top) shows a representative amino acid at its isoelectric point (around pH 8). Although it has two opposite charges, there is no net charge. With increasing pH (middle), the amine spends more and more of its time deprotonated (as this is an equilibrium reaction), and the molecule has a slight to moderate negative charge. With decreasing pH, the carboxylate salt is protonated (a hydrogen atom is bound to it) to a higher and higher percentage of the time to give the molecule a positive charge. The solubility of proteins

386

19. COLLOID AND SURFACE CHEMISTRY

(and other materials) is usually lowest at their isoelectric point.

Electrical Double Layer

Cellulose fiber surface

Most materials involved in papermaking have charged surfaces. For example, wood fibers in aqueous suspensions have a net negative surface at pH above 3.5 due to the carboxylic acid groups of cellulose and hemicellulose, which exist as their carboxylate salts. We will consider the behavior of such a fiber in the development of surface charge properties. If metallic salts are added to a suspension of wood fibers, the wood fibers will absorb (bind) a certain portion of them (this is an equilibrium reaction) and become less negatively charged or even positively charged depending on how many are absorbed (Fig. 19.3). The positively charged ions (counterions, as their charge is counter or opposite to the particle) and water form the electrical double layer at the surface. In 1879, Helmholtz hypothesized that counterions would be held firmly to charged surfaces, depending on the type and concentration of

HELMHOLTZ GOUY–CHAPMAN STERN

FIGURE 19.3

Electrical double layer.

counterions in the surrounding solution. In 1910, Gouy and, in 1913, Chapman independently concluded that the counterions would spread diffusely from the surface due to thermal motion. In 1924, Stern modified the double layer to include some tightly bound ions of Helmholtz and some loosely bound ions of the Gouye Chapman model (Fig. 19.3). The model holds that the distribution of counterions is more highly concentrated at the surface and less concentrated with increasing distance from the surface to yield a Boltzmann distribution (of statistical mechanics). The “thickness” of the double layer is given by 1/k where k is the ionic radius from Debyee Huckel theory. 1/k is a function of the dielectric constant, ε; the universal gas constant, R; temperature, T; Faraday’s constant, F; and the concentration (c, mol/m3) of each ionic species (i) of valence z as follows:
0:5 1 εRT P ¼ (19.2) k F2 ci zi

Zeta Potential The slip plane is the plane defined by the distance at which the structure with its chemically bound water and ions moves in bulk through the solution as indicated in Eq. (19.2). It is the plane at which the zeta potential is valid. The zeta potential is the “modified” or “effective” surface charge. The equation shows that with increasing concentration of electrolyte, the slip plane will contract toward the particle surface and the zeta potential will become less negative, until the isoelectric point is achieved, and may even become positive. Each type of particle (softwood fibers, hardwood fibers, parenchyma, TiO2 filler, clay filler, etc.) will have its own zeta potential or even a zeta potential distribution. The valence of the cation is of exponential importance in decreasing the negative charge on anionic surfaces (as determined by precipitation). This was independently observed by

19.2 COLLOID CHEMISTRY

Schulze in 1882 and Hardy in 1900 and is referred to as the SchulzeeHardy rule. Later work showed that charge neutralization is proportional to the sixth power of z (more detail is found below). Other factors such as the size of the ion and the size of the hydration layer modify these numbers somewhat. Despite this enormous influence, other factors may have strong influences as well, such as the formation of coordinate complexes or insoluble precipitates. For example, Cu2þ ions form strong complexes with amines and may impart more of a charge to polyamines than Al3þ ions because the coppereamine interaction is much stronger than ionic interactions. In ammonia solution, copper ions exist as Cu(NH3)2þ 6 . High ionic strength (corresponding to conductivity > 1000 mmho) suppresses the zeta potential and its usefulness as a control parameter in papermaking.

Coagulation Under many conditions, colloidal particles can clump together to form large particles that are no longer stable to suspension; this is the process of coagulation. Coagulation is analogous to the formation of a liquid from a gas or the precipitation of a solid from solution. In all three cases, it is largely a matter of the thermodynamic stability of the products and activation energies to be overcome. The stability of a suspension depends on whether the repulsive forces between particles are larger than the attractive forces between particles and the energy of the various states. In some cases the solution is unstable to begin with, and it is only a matter of time before coagulation occurs. Conversely, an unstable or stable colloid can sometimes be formed from two continuous phases by a large amount of agitation. Attractive forces (Levine, 1978) are due to any of the normal secondary chemical forces (as opposed to covalent bonds) that hold materials

387

together. The forces between identical particles are usually induced dipoleedipole interactions such as the weak van der Waals force (based on the work of 1873), which is proportional to 1/r7; they depend (only to a small degree) on the properties of the solvent. Even a material such as argon is subject to van der Waals forces, as these are the attractive forces between atoms of argon in its liquid or solid form. The energy of this interaction is the London (based on the work in 1930) or dispersion energy and is proportional to 1/r6. The magnitude of this interaction at the most favorable distance is typically 0.5e2 kcal/mol. These forces are very dependent on distance but act only at short range. Hydrogen bonding may be another important attractive force at higher consistencies with energies of 2e8 kcal/mol. Two molecules are prevented from being “sucked into each other” by repulsive forces, Born repulsion, predicted by the Pauli exclusion principle, which act at shorter range than van der Waals forces and are proportional to 1/r8d1/r18. The bottom curve of Figs. 19.4A and 19.4B shows how these forces act in the gaseliquid equilibrium of a pure material. The bottom curve is in the form of the LennardeJones 6e12 intermolecular potential (for Ar or N2), h i where n ¼ 4ε ðs=rÞ12  ðs=rÞ6 . (n is the sum

of the very short-range repulsive potential and short-range attractive potential, ε is the depth of the minimum potential, and s is the intermolecular distance where n ¼ 0.) At a given intermolecular distance, two molecules form a (somewhat) stable dimer (or liquid or solid) depending on the temperature (average kinetic energy of the species). At high temperatures the atoms or molecules overcome the binding energy and exist as a gas. Liquids are incompressible because of the high dependence on distance of the short-range Pauli exclusion repulsive forces. In colloids with charged surfaces, relatively long-range repulsive forces have two origins: stabilization of the particles

388

19. COLLOID AND SURFACE CHEMISTRY

Potential Energy, eV

0.02

(A) Pauli exclusion

Repulsion

Very strong electrostatic

0.01

0.00 Attraction

London dispersion

–0.01 0

FIGURE 19.4A

Potential Energy, eV

0.02

1

2

3 4 5 6 Intermolecular Distance, Angstrom

7

8

9

Individual potentials for Pauli exclusion, London dispersion, and electrostatic repulsion.

(B)

Repulsion Strong electrostatic repulsion Moderate electrostatic repusion No electrostatic repulsion

0.01

0.00

Attraction –0.01 0

1

2

3 4 5 6 Intermolecular Distance, Angstrom

7

8

9

FIGURE 19.4B Lennard-Jones 6e12 intermolecular potential for Ar (bottom curve) and modifications with moderate (middle curve) and strong (top curve) electrostatic repulsion of colloid particles.

by the solvent (hydrogen bonds and London energy) and double-layer ionic interactions. In the former, if particles have large layers of hydration, they cannot approach each other. (In the case of micelles, it has been shown that these colloids form because of the solvente solvent interaction, which is increased when the hydrocarbon chains of soap molecules are “kept together,” which is much larger than the nonpolarenonpolar interaction inside the micelles.) The ionic interactions are electrostatic forces that obey Coulomb’s law. The forces are

proportional to 1/r2, and the energy of interaction is proportional to 1/r. These are relatively weak forces that act over relatively long ranges. The dielectric properties of the solution may be instrumental to the types of reactions that occur; this is not critical in dilute aqueous solutions but may be very important as the solids content of the sheet reaches 50% and higher in the dryer section. (The exact interaction of electrical double layers of two particles can be considered with various degrees of additional sophistication.) The additional consideration of electrostatic interactions in Figs. 19.4A and 19.4B is considered

19.2 COLLOID CHEMISTRY

in the upper two curves. The electrostatic forces operate over a much longer range than the other forces. With moderate electrostatic charges (middle curve), the long-range repulsive forces can be overcome. With high electrostatic charges (top curve), the long-range repulsive forces cannot be easily overcome. When two particles combine, the electrostatic charges rearrange because they must occur at the surface of particles. This rearrangement will mean that the entire short-range attractive potential will be realized. In fact, it is not necessary to consider the Pauli exclusion forces when considering the stability of colloids (as these act only at short ranges after the weak chemical attraction forces have caused coagulation or coalescence). In the DLVO (from Derjaguin, Landau, Verwey, and Overbeek) theory, colloid stability is considered in terms of the long-range repulsive forces and the short-range attractive forces. With increasing temperature, pure materials go from solid to liquid to gas (decreasing particle size). With increasing temperature, colloids often go from solutions to solids (protein coagulation, such as occurs when cooking an egg) or from small particles to large particles. The apparent contradiction lies in the fact that increasing temperature in colloidal reactions is overcoming repulsive forces, whereas increasing temperature in the vaporization of a pure material is overcoming attractive forces. Increased agitation or increased temperature may cause colloids to form from larger particles if the London potential is weak, just as in a liquid. At great distances there is no interaction between identical colloid particles. As they approach each other, the electrostatic repulsive forces act at relatively long distances. Pushing the particles together causes the van der Waals force to increase until the particles attract each other and combine. (The Pauli exclusion repulsive forces act to prevent the particles from approaching closer than in normal solids and liquids.)

389

Therefore coagulation depends on decreasing the electrostatic repulsive forces and/or forcing particles to be in close proximity to each other. Small amounts of polymers can sometimes be used to prevent coagulation. For example, gelatin prevents coagulation of gold particles by steric stabilization, whereby particles are prevented from getting close to each other by adsorbed layers of gelatin. Work by Neuman, Berg, and Claesson (1993) indicates that steric stabilization of cellulosic surfaces (that does not behave according to DLVO theory) may be much more important than ionic interactions. The contribution of this phenomenon in papermaking chemistry needs more consideration in future work. This finding explains why the use of the zeta potential is not always helpful in papermaking chemistry and why too much polymer can reverse flocculation. The electrostatic potential depends on the usual factors of electrolyte concentration and composition, pH, temperature, and degree of agitation. For example, when the zeta potential approaches zero, the electrostatic forces are decreased; even with a zeta potential of zero there may be electrostatic repulsion, as the particles tend to polarize each other and the double layers affect each other; therefore the maximum coagulation often occurs within þ5 mV of the isoelectric point (i.e., where the zeta potential is zero). A compressed double layer (resulting from higher levels of electrolytes and/or highvalence cations) also decreases electrostatic repulsion; generally the effectiveness toward coagulation of Mþ:M2þ:M3þ is 1:75:625 according to the SchulzeeHardy rule. Within a given valence, a large ionic radius is a little more effective toward coagulation than one of small ionic radius. Overbeek (1952) demonstrated these concepts in his work (reprinted in Hunter, 1987 and Shaw, 1980). For example, the critical coagulation concentrations, ccc, for a sol of As2S3 is 58 mmol/L of LiCl, 51 mmol/L of NaCl, and

390

19. COLLOID AND SURFACE CHEMISTRY

50 mmol/L of KNO3 for monovalent ions; 0.72 mmol/L of MgCl2 (10% higher for the sulfate salt) and 0.69 mmol/L of ZnCl2 for divalent ions; 0.093 mmol/L of AlCl3 (barely higher for the sulfate salt) and 0.08 mmol/L for Ce(NO3)3. The same approximate ratios are realized with two other sols as well in this work, with one of the sols positively charged and precipitated by CI, SO4 2 , and other negative ions. (Theoretically, the CMC decreases to the sixth power of z (Hunter, 1987); for z ¼ 1, 2, 3 this is 1:64:729.) If too much electrolyte is present, charge reversal is possible and coagulation may be reversed. It is interesting to note that aluminum behaves according to this rule despite its complex chemistry with water. One wonders how polyelectrolytes behave as they may have numerous charges per molecule. Up to this point this section has considered identical colloidal particles. With different particles there can be very strong attractive electrostatic forces if some particle are negatively charged and others are positively charged. In this case coagulation is very quick.

Flocculation in the Papermaking System Flocculation in the papermaking system is analogous to coagulation, except that a charged polymer is used either to decrease the repulsive forces or to act with several particles at one time (bridging) to achieve aggregation. Consider the use of cationic polymers in a suspension of wood fiber fines with negative surface charges. Without polymers, the fines repel each other due to the like charges. The addition of a lowmolecular-weight cationic polymer will decrease the zeta potential so that fines may flocculate. Flocculation can also occur by the bridging mechanism, whereby small amounts of cationic polymer attach to the particles and create local neutral charges (a patch), although the overall particle may have a net negative charge. Two patches, each on a different particle, may form

a bridge even though the overall zeta potential is still appreciably negative. The molecular weights of polymers are important to their use. Usually a minimum molecular weight is required for a particular application. High molecular weights allow direct bridging of particles. Sometimes two component polymer systems are used, with one polymer having a low molecular weight (perhaps a few tens of thousands) to provide suitable charge on a part of the surface and a second, highmolecular-weight molecule used to provide bridging between patches. High shear forces in solution must be avoided if high molecular weight is required in an application as shear forces will cleave large molecules. The use of branched polymers (for a given overall molecular weight) decreases their effectiveness toward bridging particles. Like coagulation, flocculation can be reversible with shear forces (mixing or agitation), especially if the flocculation is weak, such as when barely enough polymer is added to initiate flocculation. If too much polymer is added, charge reversal or steric stabilization may occur. One area that has been overlooked by the paper industry, but offers great potential, is the use of diblock and other block polymers. This approach has the potential of allowing fillers to attach directly to fibers and fines to increase opacity. Also, fillers (of different indexes of refraction) could be made to attach to each other to increase light scattering. (Strictly speaking, coagulation and flocculation are both the clumping of small particles [like or not] together into groups; the terms are usually used interchangeably by colloid chemists, although coagulation implies a stronger interaction that is generally not reversible. [Admittedly, this is contradictory in terms of how these behave to shear forces in the papermaking system.] Coalescence is the fusion of two small particles into one large particle where the original particles are indistinguishable. Oil droplets of an oil-in-water emulsion may coalesce into

391

19.4 SURFACE TENSION AND SIZING

larger oil droplets. The large materials may settle from solution if they are more dense, by sedimentation, or rise to the top if they are less dense, by creaming.)

19.3 POLYELECTROLYTES Polymers with charged groups may be called polyelectrolytes. Anionic groups are usually carboxylate salts and occasionally sulfonate or phosphate salts; cationic groups are usually amines or quaternary ammonium salts (quats). The charge density (often measured as percentage of monomers containing a charge) is an important criterion for polyelectrolytes. A polymer with a high charge density (above 30%) tends to be completely “unraveled” in solution.

these values. Capillary action (which is the ultimate depth of penetration) is demonstrated by the height of water in glass tubes of decreasing diameter (Fig. 19.5). It is the same force that draws fibers together during papermaking and is also relevant to paper drying. Capillary action is the result of a pressure gradient between the water phase and the air with water vapor phase. The pressure gradient (P) is equal to the surface tension (g) difference between two phases (a and b) divided by the radius (R) of the liquid phase for a spherical interaction. The surface tension of water against air (see Chapter 25, Volume 2) is 73 dyn/cm at 18 C, 66 dyn/cm at 60 degrees, and 59 dyn/cm at 100 degrees. The capillary equation, derived independently by Young and Laplace in 1805 (Levine, 1978), is Pa  Pb ¼ 2g=R

19.4 SURFACE TENSION AND SIZING Mechanism of Sizing Action

This equation is modified to give the actual capillary rise for water by solving for the force of water and the wettability of the glass by the water.

The Lucas (1918) equation (also referred to as the Washburn (1921) equation) shows that the liquid penetration (depth of penetration, l) into a material is a function of the size of capillaries or pores in a material, r; the contact angle of the liquid with the solid, q; the surface tension of the liquid, g; the viscosity of the liquid, h; and time, t. The equation is l2 ¼ rtg cosq=2h

(19.3)

Lucas used this equation to calculate pore sizes in paper based on the speed of the rise of organic liquids in paper strips. Lucas used organic liquids as they would not change the pore sizes by swelling or hydration. By assuming complete wetting ðcos q ¼ 1Þ, lower limits of the pore size in paper were determined to be 0.5e6 mm. Later investigators used water and obtained pore sizes of about one-tenth of

FIGURE 19.5

Demonstration of the capillary effect with glass tubes of various diameters placed in water.

392

19. COLLOID AND SURFACE CHEMISTRY

If the water completely wets the glass, then q ¼ 0 degree. Here, r is the capillary tube radius, r is the density of a phase, g is the acceleration due to gravity, and h is the height of the water.   g ¼ 1 2 ra  rb ghr=cos q =

For example, for a watereair interface at 20 C in a capillary tube with an inside diameter of 0.5 mm, the capillary rise will be 6 cm if the glass is completely wetted. The capillary rise is generally the most accurate method for measuring the surface tension of liquids. The contact angle is a measure of the adhesive force of the liquid with the surface relative to the cohesive forces in the liquid. The following equations indicate this relationship with examples in Fig. 19.6: if adhesive > cohesive then 0  q < 90 if adhesive < cohesive then 90 < q  180 For example, water on a freshly waxed surface “beads up,” an example of a low adhesive force between water and the surface (wax). In the case of water in glass tubes, the adhesive force is higher than the cohesive force (the contact angle is <90 degrees) and the meniscus is concave; this leads to capillary rise. In the case of mercury in glass tubes, the adhesive force is lower than the cohesive force (the contact angle is >90 degrees); this leads to capillary depression. Cellulose is easily wetted by water, and water on cellulose gives a low contact angle that approaches zero; this causes the water to be drawn into the capillaries. The

90 deg.

FIGURE 19.6

purpose of internal sizing is to present a surface to the water that results in a high contact angle. This is accomplished with nonpolar functional groups. Internal sizing agents are generally amphipathic (having polar and nonpolar moieties on the same molecule) materials. The polar portion (more significantly, it is chemically reactive) attaches to the fiber or fines directly through a covalent bond or indirectly through a mordant such as alum. As the adhesive strength of water to the sized surface is now less than the cohesive strength of water, the water does not penetrate the pores of the fibers. (Surface sizing with starch physically plugs the surface capillaries of paper, which is its chief mechanism of sizing even though starch is hydrophilic.) Some observations will be considered in light of this theory. Hexane has very little cohesive strength, that is, a low surface tension, and easily penetrates paper, whether sized or unsized. Lowering the surface tension of water (by use of a surfactant) will cause a decreased capillary action (sizing would be observed to improve) directly as indicated in Eq. (19.3); however, this will cause the contact angle to decrease, which has the effect of decreasing the observed sizing. Usually the latter effect induces a larger relative change, so that the use of surfactants will decrease the observed sizing to a modest degree (see Chen and Biermann, 1995, in Chapter 10, Volume 2). Inverse gas chromatography has been used to characterize surface energy; in pulp and paper this has been accomplished with treated and

>90

<90

Three contact angles of a droplet on a flat surface.

393

19.5 SURFACTANTS

untreated pulps (Pyda et al., 1993). Another technique that has been used is dynamic contact angle analysis (Huang et al., 1995). The contact angle of buffer solutions at various pH values on individual wood fibers was studied by Jacob and Berg (1993). Their study indicates that the change in surface ionizable groups brought about by variation of pH affects the wettability of the fibers. More recent work of some workers refutes this approach, however.

Capillary Condensation (Stamm, 1962) Above 90% relative humidity (RH), wood and paper can adsorb small amounts of water vapor as free water due to surface tension effects of water. The RH must reach 99.5% to fill pit chambers and the tips of fibers and 99.9% to fill fiber lumens of wood. A water droplet with a positive radius (concave surface) has a slightly higher vapor pressure than a flat surface of water. A water droplet with a negative radius (convex) has a lower vapor pressure, which allows condensation to occur. The radius of the pores in which water will condense is calculated by a variation of the Kelvin equation: r ¼

2gV RT lnðpo =pÞ

where r is the radius in meters, g is the surface tension of the liquid (0.073 J/m2 for water at 20 C), V is the molar mass of the liquid (1.8$105 mol/m3 for water), R is 8.134 J/ (mol$K), T is the temperature in Kelvin (293), and p/po is the relative vapor pressure of the liquid. At 20 C and 50% RH, the pore size is 1.6$109 (1.6 nm); at 90% RH, the pore size is 1.02$108 m or 0.01 mm; at 99% RH, the pore size is 0.1 mm; and at 99.9% RH, the pore size is 1 mm. Possibly,

pocket ventilation at the last few dryer cans must be particularly effective (to give a sufficiently low vapor pressure of water) to get the last water out of paper during drying. (There is an equation [derived by Oswald in 1907] that is analogous to the Kelvin equation but applies to the solubility of particles in solution. A small particle actually has a slightly higher solubility than a larger particle. If the solubility is sufficiently high, with aging, small particles decrease in size, whereas larger particles increase in size. This is the basis of aging precipitates in some analytical chemistry experiments. The surface energy of solidesolution interfaces is about 1 J/m2.)

19.5 SURFACTANTS Introduction Surfactants are surface-active agents that aggregate near or have a strong effect on modifying the interface between two materials. This occurs because of their dual nature: hydrophobic and hydrophilic. The hydrophilic moiety may be anionic (carboxylate, sulfate, or phosphate), cationic (quaternary ammonium salt), ampholytic (cationic and anionic), or nonionic (Span, Tween, Triton) depending on the type of charge(s) carried, if any. Performance of surfactants depends strongly on their surface activity and micelle formation. Fig. 19.7 shows the effects of some chemicals on the surface tension of water. The effect of NaOH in increasing the surface tension is unusually high among the electrolytes. The hydrophobic moiety must be large enough to “resist” the aqueous phase. For example, 5 g/L of ethanol will lower the surface tension of water at 20 C (73 mJ/m2) by about 2 mJ/m2, 5 g/L propanol by 5 mJ/m2, 5 g/L butanol by 7 mJ/m2, 5 g/L pentanol by 22 mJ/m2, and 5 g/L hexanol by 35 mJ/m2.

394

19. COLLOID AND SURFACE CHEMISTRY

100 NaOH 18 C

Surface tension, mJ/square meter

90

80

Sucrose 25 C

70 60 50

nPrOH 25 C Phenol 20 C

40

HAc 30 C EtOH 40 C

30 20 0.1

1 10 Concentration of “surfactant”, %

100

FIGURE 19.7 The effect of various chemicals on the surface tension of water. Data from CRC Handbook of Chemistry and Physics, 67th ed.

Anionic surfactants are generally less expensive than cationic ones, although the latter sometimes have biocidal action. Span and Tween materials (Fig. 19.8) are formed from hexahydric alcohols (Span, derived from sorbitol), fatty acids, and alkene oxides (Tween). Tween 80 is called polysorbate 80 when used in pharmaceutical and food products. The Span materials tend to be less water soluble than the Tween materials. The Triton family is shown in Fig. 19.8. Surfactants are often named according to their use. The same material could be a detergent, a wetting agent, an emulsifier, or a dispersant. The majority of all surfactants are detergents. Detergents are often alkyl sulfates. Alkyl aryl sulfates used to have widespread use, but they are not readily biodegradable. Detergents are used with silicates to help bind interfering metal ions, phosphates to help prevent flocculation (scum formation), and other materials to keep them free-flowing.

Critical Micelle Concentration The CMC of surfactants depends on several factors (Shaw, 1980). The most important factor is the strong waterewater interaction (the hydrophobic effect) that is allowed when water does not interact with individual fatty acid chains in solution; the nonpolarenonpolar interaction in the center of the micelle does not provide the thermodynamic energy required for micelle formation. Most ionic surfactants have a CMC that depends on the hydrocarbon chain. In Table 19.3, all of the C-12 ionic surfactants have a similar CMC. Nonionic surfactants usually have lower CMC values. Longer chain fatty acid portions increase the hydrophobic effect; an example was already given with the lower chain alcohols. After about 18 CH2 groups, an additional effect is not noted as these would coil on their own in solution by themselves. For example, the CMC of sodium

19.5 SURFACTANTS

OH

HO

SPAN O

CHOH

CH3(CH2)16COOCH2

(OCH2CH2)xOH

HO(CH2CH2O)w

O

CH(OCH2CH2)yOH

CH3(CH2)16COO(CH2CH2O)ZCH2 TWEEN 80

w + x + y + z = 20

R

(OCH2CH2)nOH

R = C9H19; n = 9 for Nonoxynol–9 Example: Triton N series

395

0.0056 M in 0.01 M NaCl, 0.0015 M in 0.1 M NaCl, and 0.0007 M in 0.3 M NaCl. Increasing the temperature will increase the CMC somewhat due to thermal motion. Many surfactants that form micelles have a solubility below their CMC. Thus at a certain temperature, known as the Krafft point, the solubility increases dramatically as the micelles are quite soluble. For the sodium alkyl sulfates, the Krafft temperature increases from 16 C for 12 carbon atoms, to 30 C for 14 carbon atoms, to 56 C for 18 carbon atoms.

Monomolecular Films Some surfactants that have low solubility in water form monomolecular films on the surface of water. Very small amounts of oil form iridescent surfaces on water due to the thin films formed. Usually these are alcohols or carboxylic acids of long-chain fatty acids. These are routinely used to combat mosquitoes in wet areas, decrease evaporation from bodies of water, etc. These concepts have application to internal sizing of paper. The hydrophilic portion is oriented toward the water and the hydrophobic tails form a layer on top, where they stabilize each other.

R = CH3C(CH3)2CH2C(CH3)2–; n = 9 for Octoxynol–9; Ex-: Triton X–100

FIGURE 19.8 One type of Span (top), Polysorbate (Tween) 80 (middle), and the Triton family.

alkyl sulfates is: with 8 carbon atoms, 0.14 M; with 12 carbon atoms, 0.0086 M (with about 40 molecules per micelle); and with 18 carbon atoms, 0.00023 M (with about 78 molecules per micelle). Some CMC values are given in Table 19.3. Addition of salts decreases the CMC of ionic surfactants because it has a tendency to screen the electrostatic repulsion at the surface of the micelle. In the case of sodium alkyl sulfate with 12 carbon atoms, the CMC decreases to

Sulfated Polyoxyethylated Alcohols Schwuger (Rosen, 1984) is a good reference for the structure versus performance of sulfated polyoxyethylated alcohols and was used for the following paragraphs. The use of ethylene oxide (EO) to form alkyl ether sulfates from fatty alcohols provides a surfactant with unique characteristics, including favorable interfacial and application properties, especially with mixtures of other surfactants. Although alkyl ether sulfates are expensive anionic surfactants, they are widely used in industry. Alkyl ether sulfates have characteristics of both anionic and noncharged surfactants. Ether groups in anionic surfactants lower the Krafft

396

19. COLLOID AND SURFACE CHEMISTRY

Critical Micelle Concentration Values of Various Surfactants (103 mol/L)a

TABLE 19.3

Total Number of Carbon Atoms in the Fatty Acid Chain Base Molecule

8

10

12

14

16

18

20

ANIONIC CH3 ðCH2 Þn  COO Naþ ; 25 

12

þ



CH3 ðCH2 Þn  CH2 OSO3 Na ; 40 C 

þ

140

33



CH3 ðCH2 Þn  CH2 OSO3 Na ; 25 C 

CF3 ðCF2 ÞnCOO K

þ

8.6

1.0 2.2

0.58

0.23

8.1 29

CATIONIC CH3 ðCH2 Þn  NH3 þ Cl ; 25 C þ



13 

CH3 ðCH2 Þn  NðCH3 Þ3 Br ; 25 C þ 

68



CH3 ðCH2 Þn  NðC5 H5 Þ3 I ; 25 C

20

5.6

0.94

AMPHOLYTIC CH3 ðCH2 Þn  NH2 þ COO ; 25 C

18

1.8

0.99

0.087

0.18

0.018

NONIONIC CH3 ðCH2 ÞnðOCH2 CH2 Þ6OH

9.9

Span materials Tween 20 ethylene oxide units a

15 (in benzene) 8

From Shaw (1980), Everett (1988), and Hunter (1987).

temperature. Although the Krafft point (in this case defined as the temperature of solubility of a 1% solution of surfactant) of Ca dodecyl sulfate is 50 C, one EO group (the anion is C14 H29 OCH2 CH2 OSO3  ) lowers it to 15 C. A second EO unit lowers it to below 0 C. Metal counterions also play an important role in the action of a surfactant. Tetradecyl (C14) sulfate has a Krafft point of 21 C as the sodium salt and 67 C as the calcium salt. For this reason, in many applications (such as laundry detergents) ionic surfactants are often used with complexing agents or other methods to bind or remove higher weight metal ions. As calcium ions are often unavoidable in pulp and paper processing slurries, anionic surfactants often contain EO units when used in our industry. Calcium or magnesium ions can improve

the washing effect of alkyl ether sulfates (relative to sodium ions); this effect is attributed to compression of the electrical double layer at the interface. Tetradecyl (C14) sulfate is said to be a particularly effective laundry detergent and does not require the use of phosphate to complex Ca2þ and Mg2þ.

Other Aspects of Surfactant Structure (Rosen, 1984) With ionic surfactants, the CMC decreases with increasing level of electrolyte concentration. With nonionic EO surfactants, electrolyte level has little effect. In pure nonionic EO surfactants, an increase in the number of EO units results in an increase in the Krafft point; an increase in surface tension at the CMC also results.

397

19.7 EMULSIONS

The nature of the aliphatic chain of aliphatic EO surfactants is very important. When three short chains are used instead of one long chain for surfactants containing 10 carbon atoms in the aliphatic chain and 7 EO units, the cloud point is 22 C compared with 75 C and the CMC is 6 mM compared with 0.85 mM. This unusual behavior is attributed to the formation of a bilayer micelle in double-chain hydrophobes. When sodium dodecyl sulfate (SDS) in water at 25 C is subjected to increasing NaCl concentration (0e0.5 M), the aggregation number in the micelles increases from about 70 to 145. In 0.80 M NaCl, the aggregation number is over 1000 and the micellar shape is a rod.

19.6 FOAM Foams are large air bubbles separated by thin films of liquid with thicknesses in the range of those of colloids. Foams are relatively unstable with lifetimes that increase with increasing viscosity of the liquid phase, which decreases the rate of water drainage at the junction of three gas bubbles, the plateau borders. Foams are important because they are used in froth flotation deinking and because they are detrimental in many other aspects of pulping and papermaking (such as in brown stock washing). Froth flotation of minerals uses a surfactant (the collector) to attach to the mineral particles, making them hydrophobic, and a foaming agent to stabilize the foam that is formed.

Foam Formation Agents Agents used to induce foam are selected empirically, although a few rules can act as guidance. Usually mixtures of surfactants have a synergistic effect toward inducing foam formation. Surfactants used near their CMC are

particularly effective as they can form monolayers. Proteins are sometimes useful in foam formation, as anyone who has beaten an egg white or cream knows. These foams are formed by denaturing of the proteins.

Defoaming Agents Chemical defoamers have been discussed in Chapter 4, Volume 2. Foams can sometimes be destroyed by blowing hot air on them. This lowers the viscosity of the liquid and helps evaporate liquid at the interfaces. Some surface active chemicals that do not stabilize the foam can displace the surfactants that do stabilize the foam. Thus low-molecular-weight alcohols or fatty acids (4e6 carbon atoms) can act as defoamers. Ca2þ may decrease the foaming tendency of fatty acid soaps by rendering them insoluble, like taking a bath in hard water.

19.7 EMULSIONS Emulsions easily fall into two categories: an oil-in-water (O/W) or water-in-oil (W/O) emulsion, depending on the continuous phase. The type of emulsion that forms depends largely on the volume ratio of the two materials, with the more abundant phase forming the continuous phase. The emulsion can be diluted with the same type of material as the continuous phase. Milk, an O/W emulsion, is diluted with milk; mayonnaise, a W/O emulsion, is diluted with cooking oil. As mentioned, emulsions are stabilized with surfactants (emulsifying agents) that have affinities for both phases; these decrease the energy required to make new surfaces between the two phases, the interfacial surface tension. Destabilization of an emulsion is an example of coagulation (or coalescence) of colloids.

398

19. COLLOID AND SURFACE CHEMISTRY

19.8 LIGHT SCATTERING BY COLLOIDS Light scattering (Shaw, 1980) is an important method of monitoring and studying colloid suspensions. Although the theory may not be necessary for most pulp and paper technologists, some aspects will be presented here as a foundation for future discussions. (The wavelength of visible light is about 0.45 mm for blue light and 0.7 mm for red.) There are three recognized types of light scattering of individual particles. Small particles (with each dimension less than about 5% of the wavelength of the light) act as point sources of light and obey Rayleigh scattering, for example, a solution of large polymers such as proteins. Light scattering by larger particles in a dispersion medium of similar index of refraction is Debye scattering. Light scattering by larger particles in a dispersion medium of much different index of refraction, such as in printing papers of high opacity, is Mie scattering.

than red light. When the incident light is white, high levels of scattering filter the blue light from it, so the remaining incident light is red. However, the scattered light itself appears blue. Thus the sky is blue during the day, but the setting or rising sun appears distinctly red (do not look directly into the sun as this may cause permanent damage to the retina of the eye). Dilute or low-fat milk has a blue appearance as do the deep footprints in some types of cold, fluffy snow. This type of light scattering can be used to give absolute molecular weights (Debye, 1947), but we will not consider this now. Suffice it to say that the amount of light scattered (and, therefore, the sensitivity) is proportional to the square of the molecular weight. The lowest molecular weights observable are around 50,000, and the maximum molecular weight can be around 107 for spherical particles. Doppler light scattering (where the shift in wavelength is observed) can be used to determine whether or not the particles are in motion.

Scattering by Large Particles Rayleigh Scattering Rayleigh described the scattering of light by smoke in 1871. Light of intensity Io and wavelength l interacting with a small particle of polarizability a induces oscillating dipoles in the particle. The particle will then emit light of the same wavelength, but in any direction. If the light is not polarized, the light emission, I, is given as a function of the distance from the particle, r, and the angle relative to the incident beam, q as    Ir2 8p4 a2  1 þ cos2 q ¼ Rq 1 þ cos2 q ¼ 4 Io l In reality, there are many particles, and these will cause secondary scattering, so the overall scattering may be more complex in relatively concentrated materials. As Rayleigh scattering is proportional to 1/l4, blue light is scattered about eight times more

Light scattering by large particles is very complicated due to the high level of destructive interference. Mie described the physics of light scattering by spherical particles in 1908.

Neutron Scattering Neutron scattering (Everett, 1988) is analogous to light scattering, but the smaller wavelength of neutrons (0.1e1 nm) can be applied to concentrated dispersions impossible to study with light scattering, especially in solutions of high opacity.

19.9 ANNOTATED BIBLIOGRAPHY Alexander, A.E. and P. Johnson, Colloid Science, Oxford University Press, Oxford, 1949.

399

EXERCISES

Debye, P., J. Phys. Chem. 51:18(1947). Einstein, A., Investigations on the Theory of Brownian Movement, Methuen, 1926; Dover, 1956. Everett, D.H., Basic Principles of Colloid Science, Royal Soc. Chem., Letchworth, 1988. Freundlich, H., Colloid and Capillary Chemistry, Methuen, London, 1926 (from the 1909 German). Ibid, Capillary Chemistry (Ger.), Vol. 2, Akad. Verlag, Leipzig, 1932. Hiemenz, P.C., Principles of Colloid and Surface Chemistry, 2nd ed. Marcel Dekker, New York, 1986, 815 p. This is an advanced book that is a very good starting point for serious theoretical considerations of the title topic. Huang, Y., D.J. Gardner, M. Chen, and C.J. Biermann, Surface energetics and acid/base character of sized and unsized paper handsheets, J. Adhes. Sci. Tech. 9(11): 1403e411(1995). Hunter, R.J., Foundations of Colloid Science, Vol. 1, Clarendon Press, Oxford, 1987; p 95 gives Overbeek’s work. Jacob, P.N. and J.C. Berg, Contact angle titrations of pulp fiber furnishes, Tappi J, 76(5): 133e137(1993). Contact angles are determined as a function of pH to indicate the forms of ionizable groups on the surface of four different types of pulp. (It is not a titration.) These results are a little esoteric; more pragmatic information would be obtained by determining zeta potentials of these fibers as a function of pH. Levine, LN., Physical Chemistry, McGrawHill, New York, 1978. Probably any introductory physical chemistry book could be used. Lucas, R., Kolloid-Z 23:15e22 (1918). Neuman, R.D., J.M. Berg, and P.M. Claesson, Direct measurement of surface forces in papermaking and paper coating systems, Nordic Pulp Paper Res. J. 8(1):96e104(1993). Overbeek, J.T.G., in Colloid Science, Kruyt, H.R., Ed., Vol. 1, Elsevier, Amsterdam, 1952.

Pyda, M., M. Sidqi, S. Keller, and P. Luner, An inverse gas chromatographic study of calcium carbonate treated with alkylketene dimer, Tappi J. 76(4):79e85(1993). Rosen, M.J., Ed., Structure/Performance Relationships in Surfactants, American Chemical Society Symposium Series No. 253, Washington, DC, 1984. This is very useful. Shaw, D.C., Introduction to Colloid and Surface Chemistry, 3rd ed., Butterworths, London, 1980. This work is good mix of theory and explanation. Page 184 has Overbeek’s work reprinted. Stamm, A. J., Wood and cellulose-liquid relationships. North Carolina Ag. Exp. Station Tech. Bull. No. 150, Sept., 1962, 56 p. This is a very good overview of the wood and fiberewater relationship by one of the pioneers of the field. It includes adsorption, swelling, capillary flow, and diffusion by wood and paper. Tanford, C, Physical Chemistry of Macromolecules, Wiley and Sons, New York, 1961, 710 p. This is the classic reference on the title subject of use to some advanced areas of wet end chemistry. Washburn, E.W., Phys. Rev, 17: 273e283(1921).

EXERCISES 1. Describe how soap removes grease during washing. 2. What is electrophoresis? 3. What is the significance of charge on wood fibers as related to wet end chemistry? 4. Does the DLVO theory describe steric stabilization of colloid suspensions? Explain. 5. Describe the difference in mechanism of action of internal and external sizes. 6. How does propanol break up foam? How does hot air break up foam?

400

19. COLLOID AND SURFACE CHEMISTRY

7. Why is the sky blue? 8. What is zeta potential? Does one value describe the zeta potential for the entire wet end? Explain.

phenomenon), which is the random motion of particles in liquids and is due to thermal energy. By treating it as a “random walk,” the displacement of a particle along an axis is, on average, given as a function of its diffusion coefficient, D:

APPENDIX Sedimentation Rate of Spherical Particles The sedimentation rate of particles will influence the drainage rate of pulp slurries. The driving force for sedimentation is the mass minus the buoyancy of an object. The rate of sedimentation will depend on the terminal velocity. An object of mass m, with a specific volume v, and density r, in gravity field g will have a terminal velocity as follows: mð1  nrÞg ¼ fdx=dt Stokes’ law applies for dilute colloids and gives f ¼ 6pha for spherical particles so that   dx=dt ¼ 2a2 ðr2  rÞg 9h Particles with irregular shapes will have slower sedimentation for a given mass (volume) because the surface area increases. Frictional ratios of particles (to the equivalent volume sphere) are given in some locations (Shaw, 1980). Eq. (19.1) is similar to one of the above, except that the force originates from electrostatic attraction instead of gravitational action.

x ¼ ð2DtÞ0:5 D is related to f as Df ¼ kT. This theory is used to predict the behavior of polymers in solution. Each segment of the polymer is treated as a step of the random walk with an angle of (for atoms with tetrahedral angles between substituents) 109.5 degrees. The end-to-end distance of the molecule is then given as a function of the length between backbone atoms and the number of such atoms as follows: lð2nÞ0:5 Flory (1969) made on approximation for the root mean square of the radius of gyration for many carbon backbone polymers as 1/2 (in nm) z 0.06 M1/2, where M is the molecular weight of the polymer (Flory P.J., Statistical Mechanics of Chain Molecules, Interscience, New York, 1969). As already mentioned, polymers with a high charge density do not behave in this random pattern because the like charges will repel each other.

Miscellaneous Brownian Motion and Radius of Gyration Einstein (1926) studied Brownian motion (named after the botanist who studied this

The HLB scale was developed by W.C. Griffin (1954), J. Soc. Cosmet. Chem. 5:249.