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Journal of Dispersion Science and Technology, 27:155–163, 2006 Copyright # Taylor & Francis, Inc. ISSN: 0193-2691 print / 1532-2351 online DOI: 10.1080/01932690500265672

Journal of Dispersion Science and Technology, 27:155–163, 2006 Copyright # Taylor & Francis, Inc. ISSN: 0193-2691

Influence of Oil Content in Paraffins on the Behavior of Wax Emulsions: Wetting and Rheology

M. A. Rodrı´guez-Valverde, R. Tejera-Garcı´a, M. A. Cabrerizo-Vı´lchez,

and R. Hidalgo-A ´ lvarez

Departamento de Fı´sica Aplicada, Facultad de Ciencias, Universidad de Granada, Granada, Spain

J. Nolla-Anguera, J. Esquena-Moret, and C. Solans-Marsa

Instituto de Investigaciones Quı´micas y Ambientales de Barcelona (IIQAB), Consejo Superior de Investigaciones Cientı´ficas (CSIC), Barcelona, Spain

R. Mujika-Garai, C. Aguilar-Garcı´a, F. Jua´ rez Arroyo, and I. Covia´ n-Sa´ nchez

RYLESA (Repsol-YPF Lubricantes y Especialidades SA), Madrid, Spain

For decades, paraffin emulsion has been used in chipboard panel manufacturing for the

purpose of making it both water and damp proof. A most important variable when assessing

the effectiveness of the emulsion as a water-resistant agent in the panel is the oil content of the

paraffin. Although this aspect has been dealt with from the manufacturing (Carll, 1996)

approach, there is scarcely any literature that relates the oil content in paraffin to chipboard

panel waterproofing or to the stability of the emulsion. In this article the influence that oil

content exerts on waterproofing capacity is determined using the ADSA technique by

studying the water-vapor-solid interface in a wood substrate coated in paraffin with a drop

of water placed on top. Thus, the water-resistant capacity of a chipboard panel is related to

the paraffin oil content in the emulsion. Furthermore, in this article, paraffin oil content is

also related to the emulsion stability through its rheological behavior in both the fluid and

dynamic patterns.

Keywords Wax emulsions, paraffins, wetting, rheology, emulsion stability

INTRODUCTION

In the chipboard panel manufacturing sector, paraffin oil content is one of the main quality parameters. However, its role in the stability of the emulsion and in its water-resistant capacity has not been entirely ascertained. High oil content is usually associated with stable emulsions but with a poor water- proofing capacity, whereas low oil content usually associated with less stable emulsions but with a high water-resistant capacity. In any case, there is no limit on the oil content that might clarify these types of behavior. Not known either are the actual water-resistant capacity or its behavior mechanism in the chipboard panel manufacturing process. In this article, the oil’s actual water-resistant capacity and the influence it exerts on the paraffin’s water-resistant

Received 24 March 2005; Accepted 8 May 2005.

Address correspondence to R. Hidalgo-A ´ lvarez, Departamento de

Fı´sica Aplicada, Facultad de Ciencias, Universidad de Granada,

Granada E-18071, Spain. E-mail: rhidalgo@ugr.es

capacity is determined by means of a study of surface phenom- ena in the interface “vapor-water-wood coated with paraffin” using the axisymmetric drop shop analysis (ADSA) technique to establish the contact angle. On the other hand, the combi- nation of the rheological behavior in paraffin emulsions with differing oil content and the surface tension of these emulsions subjected to shearing allows the stabilizing mechanism of the oil in paraffin emulsions to be established to a certain extent.

MATERIALS AND METHODS Materials

The type of paraffin and oil used in this article comes from direct cuts carried out at a refinery vacuum distillation unit. Ten emulsions were elaborated from semi-refined paraffin with an L-cut and oil content of 2.6%. Different amounts of oil from the same distillation cut were added to paraffin. The surfactant system is the same for all the emulsions; consequently, the only variable is the paraffin oil content. Table 1 shows the prepared emulsions.

155

156

M. A. RODRI ´

GUEZ-VALVERDE ET AL.

TABLE 1 Emulsions GR-19 to GR-28 prepared with differing amounts of oil

 

GR

GR

GR

GR

GR

GR

GR

GR

GR

GR

Emulsions (%)

19

20

21

22

23

24

25

26

27

28

Paraffin L-cut (2.6% oil)

57.4

55.9

53.8

50.7

46.6

43.5

38.4

33.3

28.1

0.0

Oil

0.0

1.5

3.6

6.7

10.8

13.9

19

24.1

29.3

57.4

Surfactant

2.6

2.6

2.6

2.6

2.6

2.6

2.6

2.6

2.6

2.6

Water

40

40

40

40

40

40

40

40

40

40

Total oil in emulsion

1.5

3

5

8

12

15

20

25

30

57.4

Total oil in paraffin

2.6

5.2

8.7

13.9

20.9

26.1

34.8

43.6

52.3

100.0

Measurement of Waterproofing Capacity

Contact angle is related to numerous interface phenomena, such as free surface energy (Gindl et al., 2001; Meijer et al., 2000), wetting and absorption mechanism (Modaressi and Garnier, 2002; Shi and Gardner, 2000) specifically in wood substrates (Stehr et al., 2001; Shi et al., 2000) and paraffin- coated surfaces (Kamusewitz et al., 1999). Contact angle is defined as the angle formed by the tangent to the liquid and the horizontal in the contact zone (Rodrı´guez-Valverde, 2002). The waterproofing capacity of the substrate is defined as the resistance that this substrate exhibits when subjected to wetting. The wetting process is intimately related to spread- ing of a liquid on the substrate and is defined as the extension coefficient (Rosen, 1988):

S ¼ DG/a

in which DG is the variation of Gibbs free energy of the process and “a” is the wet area produced by the spreading liquid. The higher the extension coefficient S is, the more extensive the wetting of the solid substrate will be by the liquid placed on it. S can be determined using indirect variables according to the equation:

in which l ¼ distance traveled by the liquid in time t, R c ¼ effective interstitial pore radius, g lv ¼ surface tension of the liquid, cos u ¼ cosine of the angle formed at the interface vapor-liquid-solid, and h ¼ viscosity of liquid. However, so that absorption takes place, an initial wetting phase has to be accomplished in which the contact angle u attains a pseudo-balancing state at which the volume of the drop is kept constant. Once this pseudo-balancing situation has been attained, a second stage begins in which absorption takes place, and the contact angle u and the drop volume v fall until a new balance situation is reached. Thus, the water- proofing capacity can be determined from the angle of contact at this first stage of pseudo-balance, without taking water absorption phenomena into account and considering the water surface tension g lv to be constant throughout the process. Determination of the contact angle is carried out by the ADSA technique. The ADSA technique computes the contact angle u and the surface tension g lv using a microscope attached to a CCD camera. This optical system acquires drop images, which are subsequently digitalized by a frame grabber and analyzed by a PC that captures the actual drop shape, digitalizing it and determining the geometric buckling curve, providing the best

S ¼ g lv ðcos u 1Þ ½1 possible fit to the drop shape using an algorithm and, starting from that, the purely geometric parameters. The ADSA tech-

nique has two fundamental algorithms:

. ADSA P: It uses the drop profile shape and is applied in well-defined drops with axial symmetry. It can be carried out starting from a sessile drop (drop on solid substrate; Figure 1) on a totally homogeneous substrate with no rough patches (the ideal substrate) or starting from a drop hanging from a capillary. It provides values of surface tension g lv as well as values of the contact angle u in the case of the sessile drop. . ADSA D: It uses the shape of the drop viewed from above and is applied to sessile drops on real sub-

strates in which no type of axial symmetry can be applied. The mathematical-geometrical treatment

in which g l/ v ¼ surface tension of spreading liquid and u ¼ interface contact angle made by placing a drop of liquid on a solid substrate. According to this equation, when a drop of liquid is placed on a solid substrate, the S value can vary from S ¼ 0 (for

u ¼ 08 and cos u ¼ 1) to

S ¼ 2 2 g l/ v (for u ¼ 1808 and cos

u ¼ 2 1). The nearer the value of S is to S ¼ 0, the more exten- sive the wetting water absorption through the wood fibers is one of the main causes of deterioration in chipboard panels. The absorption mechanism is based on spontaneous pen- etration of water by capillarity in a porous medium. This process is described by the Washburn equation (Walinder et al., 1999):

l 2 ¼ t g lv R c cos u

2h

½2

INFLUENCE OF OIL CONTENT IN PARAFFINS

157

INFLUENCE OF OIL CONTENT IN PARAFFINS 157 FIG. 1. Diagrams of ADSA technique from image acquisition,

FIG. 1. Diagrams of ADSA technique from image acquisition, to processing, to the computation of interfacial quantities. ADSA-P layout (a) and ADSA-D layout (b) are separately displayed.

of the data is somewhat more complex, and there- fore it is necessary to know g lv and the volume of the drop in order to determine the contact angle u.

Although various methods of determining g lv (Gardner, 1996; Hoffmann, 2003) exist, in our case, it is obtained

applying the pendant drop method ADSA-P, and the contact angle is obtained by applying the sessile drop method ADSA-D owing to the high level of heterogeneity (high porosity and unevenness) in the wood used to make the sub- strate. In Figure 1, this technique is described in diagrammatic form.

INFLUENCE OF OIL CONTENT IN PARAFFINS 157 FIG. 1. Diagrams of ADSA technique from image acquisition,

FIG. 2. Contact angle evolution at the interface vapor-water-wood substrate coated in paraffin from emulsions GR-19 to GR-28, using a drop volume of 3 mL.

158

M. A. RODRI ´

GUEZ-VALVERDE ET AL.

The measurement of the contact angle is obtained by placing a drop of water on a reference substrate (young sandpapered pinewood) with a paraffin surface density of 0.3 g/m 2 (Mujika et al., 2005). The paraffin coating of the wood sub- strates is obtained by adding an emulsion drop to the substrate. A heat treatment (1808C) was applied to eliminate the water by evaporation. The contact angle is determined by applying the ADSA-D (sessile drop) technique and the surface tension by applying the ADSA-P technique (pendant drop).

Measurement of Emulsion Stability

The stability of the emulsion flowing through pumps and pipes is determined by means of the development of viscosity over a period of time at a constant shear rate of 100 s 2 1 and for a maximum time of one hour. The increase in viscosity over a period of time in these conditions is indicative of phase separ- ation owing to the formation of clusters from particles from the dispersed phase thus, becoming an indication of its stability (Mujika, 2005). In this way, the flow conditions are established under which the emulsion remains stable. The rheological study of emulsions in dynamic mode provides information about the dominant interactions. By analogy to Hooke’s law for elastic solids, the following equation describes the behavior of a viscoelastic solid:

t ¼ jG jg

½3

in which t is the stress, G is the complex rigidity modulus, and g is the strain. The viscoelastic modulus is defined by:

as a result of shearing to be determined, at least on a compara- tive level.

RESULTS AND DISCUSSION Influence of Oil Content on the Waterproofing Capacity

The coating of wood particles with paraffin initially produces repulsion to water, defined by the paraffin’s structural properties. However, with the passage of time, a redissolving effect of the paraffin takes place, basically depending on the molecular weight of the hydrocarbons of which the paraffin is made and that reduce the substrate’s waterproofing capacity against water. Thus, waterproofing capacity consists of two components (Mujika, 2005); intrinsic waterproofing capacity and actual waterproofing capacity or the capacity with time to construct an anti-humidity barrier. Intrinsic water- proofing capacity is the capacity to repel water in the paraffin without taking into account the effects of redissolving the water placed on the interface. It is paraffin’s waterproofing capacity at 0 time and is determined by using a drop of water of a size 3 mL in order to minimize the effect of the paraffin redissolving. The actual waterproofing capacity is determined with a 5 mL drop of water so as to take the redissolving effect into account. This would be paraffin’s waterproofing capacity at infinite time. In Figure 2, the evolution of the contact angle at the interface vapor-water-wood substrate coated in paraffin from the emulsions GR-19 to GR-28 is shown with differing contents of oil in the paraffin. As can be observed in the figure, the intrinsic waterproofing capacity

G ; G 0 þ iG 00 ½4 diminishes significantly for a reliable level of 95% as the oil content is increased.

where G 0 and G 00 are respectively the elastic (storage) and viscous (loss) moduli. The loss modulus is related to the hydro- dynamic and thermodynamic interactions, and the storage modulus is related to the surface interactions between the par- ticles in the dispersed phase or with any type of structuring in the dispersed phase.

Measurement of Emulsion Stability at Shearing

The paraffin emulsion is a dispersal of paraffin particles in water that stay in a Brownian balance thanks to the action of the surfactant system. The surfactant system coats the particles, forming a steric and electrostatic barrier preventing collisions between the paraffin particles from becoming effective. The effective collisions give rise to the formation of clusters of paraffin particles and, finally, the flocculation of the dispersed phase. The shearing gives rise to a forced surfactant desorption from the dispersed phase when dissolving is taking place that reduces the coating of the particles at the dispersed phase and facilitates flocculation. The surfactant that goes on to dis- solving brings about a reduction in the emulsion’s surface tension that allows a degree of deterioration in the emulsion

In Figure 3, the paraffin’s waterproofing capacity is shown at infinite time against the oil content using a drop volume of 5 mL. In the figure, we observe three stages: an initial stage up to 8% oil in the emulsion, in which the waterproofing capacity increases with the increase in the oil content; an inter- mediate stage from 8% oil in the emulsion up to 25%, in which the waterproofing capacity diminishes on increasing the oil content; and in excess of this value up to 57.4% (100% oil in paraffin), in which the waterproofing capacity is nil. Water- proofing capacity is considered to be nil when the angle of contact at the interface is less than 308 (value obtained with a substrate not treated with paraffin). The waterproofing capacity of the oil is nil. However, the addition of oil to paraffin improves its waterproofing capacity up to a limit, at which point the oil begins to have a clear presence on the substrate (approximately 8% in the GR-22 emulsion) and its non-waterproofing effect begins to be signifi- cant. With oil content excess of 25%, the emulsion’s water- proofing capacity is nil. The increase in oil content in paraffin diminishes the emulsion’s intrinsic waterproofing capacity and increases the actual waterproofing capacity at infinite time up to a level of 8% of oil in the emulsion (14%

INFLUENCE OF OIL CONTENT IN PARAFFINS

159

INFLUENCE OF OIL CONTENT IN PARAFFINS 159 FIG. 3. Contact angle of water on wood substrate

FIG. 3. Contact angle of water on wood substrate coated with emulsions GR-19 to GR-28 using drop volumes of 5 mL.

oil in paraffin). In excess of this value, the actual waterproofing capacity at infinite time is likewise reduced.

Emulsion Stability: Rheological Behavior

In a fluid pattern, the rheological behavior of a non- Newtonian fluid is predicted by the generalized Equation (l):

t ¼ t 0 þ h app ðg_ Þg_ n

½5

where t is the shear stress, t 0 is the yield stress, h app is the apparent viscosity, g˙ is the shear rate and n is the fluidity

index of 0.986:

h ¼

4:10 3 f 2 þ 1; 73:10 2 f þ 0; 5093 ðPa sÞ

ðr ¼ 0:926Þ

where f is the oil content in the emulsion paraffin. The fluidity rate has a value of n ¼ 0.86 + 0.20 near to unity. At very low shear rates, the emulsions being studied display a thixotropic behavior that increases when the oil content is increased, albeit to a very slight extent and of no practical

rate. This relation also includes Newtonian fluids when importance with regard to industrial application.

t 0 ¼ 0 and n ¼ 1, in which case h app is equal to the viscosity h. In Figure 4, the function h app (g˙ ) is shown in the shear rate range from 0 to 300 s 2 1 . As can be seen from this graph, paraffin emulsions exhibit a pseudo-plastic behavior up to a shear rate of approximately 100 s 2 1 . From this point, the rheo- logical behavior is Newtonian. In the newtonian range, the dependence of viscosity on oil content is described by a quadratic relation with a correlation

Stability in the fluid pattern is established by determining the emulsion’s viscosity at a shear rate of 100 s 2 1 according to the time and for a maximum time of one hour. This shear rate is equivalent to the shearing carried out in mixing, shaking, and transportation processes through pumps and pipes, typical of the chipboard panel industry. When the vis- cosity does not vary with time under these conditions, the emulsion is considered to be stable. The point at which the

INFLUENCE OF OIL CONTENT IN PARAFFINS 159 FIG. 3. Contact angle of water on wood substrate

FIG. 4. Viscosity curve against the shear rate of the GR-19 to GR-28 emulsions.

160

M. A. RODRI ´

GUEZ-VALVERDE ET AL.

160 M. A. RODRI ´ GUEZ-VALVERDE ET AL. FIG. 5. Viscosity variation in the GR-19 to

FIG. 5. Viscosity variation in the GR-19 to GR-28 emulsions in accordance with time with differing oil content in the paraffin and at a shear rate of 100 s 2 1 .

viscosity begins to fluctuate with respect to time is a compara- tive parameter of the emulsion’s stability. Figure 5 shows the viscosity obtained according to time with differing oil content in paraffin and at a shear rate of 100 s 2 1 . As can be seen, the emulsions with oil content of 8% or more (from GR-22 emulsion upwards) have a slope of 0, and they are stable throughout the entire trial time duration. The emulsion GR-19 is unstable (positive slope) from the starting point, whereas in the emulsions GR-20 and GR-21, the slope starts to be positive after approximately a half-hour. In Figures 6(a) – (f) the evolution of the moduli G , G 0 and G 00 and the emulsions GR-19 to GR-28 is shown in accordance with the oil content at temperatures of 20, 30, 40, and 508C for values of 0.1, 1 and 10 Hz. The evolution of the elastic modulus G 0 is indicative of the presence of superficial stress between the particles in the dis- persed phase, which depends on the number of intersections created and not on the intensity of these intersections (Ralston et al., 1981). High G 0 values indicate that a great number of these interactions occur. As can be observed from the graph, in every case the value of G 0 is higher than G 00 , indicating that the emulsions have a mainly elastic behavior from 0.1 to 10 Hz from temperatures of 20 to 508C. This is obvious if we take into account that these emulsions have an approximate content of 60% dis- persed phase, owing to which their elastic constituent must be great. In general, the high G 0 values are accompanied by significant differences with respect to G 00 . Significant differ- ences between the moduli indicate a predominance of surface interactions between the particles over the hydrodyn- amic and thermodynamic interactions that typify Brownian stable emulsions. According to this criterion, we can establish two zones as regards the intensity of the surface interactions between the particles measured as the intensity of the G 0 modulus: a moderate intensity zone starting from an oil content in the emulsion of 21%, emulsion GR-23, in which

the values of G 0 and G 00 are very similar and a high intensity zone for oil content in the emulsion of 21% (GR-23 emulsion) or lower content in which the G 0 value increases considerably and the interactions between the particles begin to be import- ant. This increase in the surface interactions between the par- ticles indicates a tendency to flocculation, which becomes apparent with the formation of clusters in the fluid pattern for oil content of less than 8% (see Figure 5). As we observe, the increase in oil content diminishes the tendency towards the formation of clusters, reducing the intensity of the surface interactions between the particles at the dispersed stage.

Emulsion Stability at Shearing: Variation in Surface Tension

The emulsion stability at shearing is determined by subject- ing the emulsion to the shear stress normal in the industry, con- sisting of going through a (hydraulic) blade pump for a period of 15 minutes. After this process, its surface tension is determined. In Table 2 the surface tension g lv results obtained for the emulsions GR-19 to GR-28 are compared before and after passing through the (hydraulic) blade pump for 15 minutes. In Table 2 the differences obtained in the surface tension g lv can be seen; after this process they decrease as the oil content increases. This behavior is shown in Figure 7. As can be seen in the figure, the differences decrease significantly for a reliable level of 95% (r ¼ 0.93) as the oil content increases with a slope m ¼ 2 0.161 + 0.05 mJ/m 2 . The decrease in surface tension g lv after passing through the (hydraulic) blade pump is due to the partial disintegration of the emulsion, freeing part of the surfactant to the aqueous phase. This variation in g lv decreases as the oil content increases. In the GR-28 emulsion made entirely from oil, the decrease in surface tension is 0. This indicates that the oil content in paraffin produces a stabilizing effect on the emulsion, diminishing the

INFLUENCE OF OIL CONTENT IN PARAFFINS

161

INFLUENCE OF OIL CONTENT IN PARAFFINS 161 FIG. 6. Illustration of the moduli G , G

FIG. 6. Illustration of the moduli G 0 , G 00 y G compared to the oil content in paraffin at 0.1, 1 and 10 Hz according to the temperatures for the emulsions GR-19 to Gr-28. In figures (a), (c) and (e) the moduli G 0 y G 00 are shown at 0,1, 1 and 10 Hz respectively, and in figures (b), (d) and (f) modulus G is shown at 0.1, 1 and 10 Hz respectively.

162

M. A. RODRI ´

GUEZ-VALVERDE ET AL.

TABLE 2 Surface tension g lv values in the emulsions GR-19 to GR-28 in accordance with recirculation time through the (hydraulic) blade pump

 

GR

GR

GR

GR

GR

GR

GR

GR

GR

GR

Emulsions (mJ/m 2 )

19

20

21

22

23

24

25

26

27

28

Surface tension (g l/ v )

53.4

54

54.8

53.8

51.5

51.2

51.2

50

48.6

45

Surface tension (g l/ v ) 15 0

43.3

46.2

44.8

44.4

45.4

44.4

47.1

45.2

46.8

Difference

10.1

7.8

6.4

9

7.1

5.8

6.8

2.9

3.4

0

162 M. A. RODRI ´ GUEZ-VALVERDE ET AL. TABLE 2 Surface tension g values in the

FIG. 7. Maximum decrease in surface tension of emulsions GR-19 to GR-28 owing to recirculation through a (hydraulic) blade pump according to the oil content for a period of 15 minutes.

forced desorption of the surfactant from the dispersed phase to the dissolving and reduces the formation of clusters.

CONCLUSIONS

  • 1. Oil has zero waterproofing capacity.

  • 2. Oil content gives rise to a reduction in paraffin’s intrinsic waterproofing capacity.

  • 3. Oil content gives rise to an increase in paraffin’s water- proofing capacity in infinite time up to a limit (approxi- mately 14% in paraffin), at which point this capacity begins to decrease.

  • 4. Paraffin oil content has a stabilizing effect in paraffin emul- sions, reducing the surface interactions between the par- ticles at the dispersed phase.

  • 5. Paraffin oil content has a stabilizing effect when the emul- sions are sheared, reducing the forced desorption of the sur- factant from the dispersed phase to the dissolving.

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