Journal of Materials Science and Engineering A 3 (9) (2013) 591-600

DA VID

PUBLISHING

Solvent Interactions with Polymeric Heat Transfer Surfaces

Christian Dreiser and Hans-Jrg Bart
Chair of Separation Science and Technology, University of Kaiserslautern, Kaiserslautern D-67653, Germany

Received: June 27, 2013 / Accepted: July 29, 2013 / Published: September 10, 2013. Abstract: Polymers offer many advantages (price, corrosion resistance, etc.) as construction materials for efficient heat exchangers. A disadvantage is a lacking permeation barrier in regard to heat transfer media. The transient swelling properties of the thermoplastic polymers polyetheretherketone (PEEK), polypropylene (PP) and polysulfone (PSU) are studied in different modifications and various solvents. The solubility parameter theory can be applied to the observed equilibrium swelling ratios, which makes it promising for future process specific material pre-selection. The amount of increasing hydrophobic surface character, even for small equilibrium swelling ratios, was found to be related to the increase in polar part of surface free energy. This wetting enhancement can be compared to the amount achieved with common treatment technologies (plasma, corona) and is of interest in heat exchanger processes. Key words: Polymers, swelling, wettability, surface modification, solubility parameter.

1. Introduction
In apparatus design in corrosive environments polymers become a serious alternative to metallic materials or high-performance alloys. Special advantages like corrosion resistance, low specific costs, mechanical and price stability are very important for a potential use as heat transfer surfaces in thermal seawater desalination plants, galvanic industry or other less corrosive applications (swimming pools, fishing breeding ponds etc.). Polymers are economically attractive and applied as thin films they give a basis for high heat transfer coefficients (> 3,500 Wm-2K-1) [1, 2]. In contrast to metallic construction materials, polymers interact with (heat exchanger) media, and allow permeation and swelling [3-6]. The dissolubility of chemical compounds affects mechanical properties,

Corresponding author: Hans-Jrg Bart, Prof. Dipl.-Ing., Dr. techn., research fields: heat transfer, two phase flow, extraction and chromatography. E-mail: bart@mv.uni-kl.de.

thermal conductivity or surface wettability, where the latter is of ultimate importance to guarantee a stable falling film heat transfer. As been reported, the polymer-fluid interaction changes the wettability or more basically the surface free energy [7]. A skillful manipulation of the wetting behavior is an important issue in interfacial engineering affecting adhesion phenomena as are scaling deposits in industrial heat transfer processes [8, 9]. The transient swelling and the solubility of various liquids is studied for different polypropylene, polysulfone and polyetheretherketone films for different level of crystallinity and polymer film thickness. Surface property characterization with regard to wettability is carried out to quantify surface energetic changes after solvent interaction and compared to common film treatment techniques. The solubility parameter theory is tested to evaluate its applicability in polymer heat exchanger materials pre-selection.

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Solvent Interactions with Polymeric Heat Transfer Surfaces

Table 1 material

Thermal and mechanical properties of selected polymers and stainless steel 1.4571.

density ultimate tensile strength Youngs modulus coefficient of thermal maximum operating (kgm-3) (MPa) (MPa) expansion (10-6K-1) temperature air (C) d d d 1.4571 8,000 580 200,000 17.5d 870-925d PP 910b 150-280b 1,400d 170d 70d c c c d PSU 1,240 73.3 2,690 56 149d a a a a PEEK Aptiv 1000 1,300 130 3,000 47 230-315d a a a a PEEK Aptiv 2000 1,260 130 1,800 60 PEEK Aptiv 1103 1,540a 100a 5,000a 35a 249d a Datasheet for 25 m films Victrex Europa GmbH, b Datasheet Ptz GmbH + Co. Folien KG, c Datasheet Dr. D. Mller GmbH d literature [10, 11].

2. Experiments
2.1 Materials and Preparation All thermoplastic polymers were used as films of 25 m thickness. PEEK films were provided by Victrex Europa GmbH, PSU purchased from Dr. D. Mller GmbH and PP from Ptz GmbH + Co. Folien KG. Decisive mechanical and thermal properties of the used polymers compared to stainless steel 1.4571 are given in Table 1. The thermal conductivity and the mechanical properties are attributed to the structure or modifications of the polymers (predominantly amorphous: PSU, PP, PEEK Aptiv 2000 and partially crystalline: PEEK Aptiv 1000 and PEEK Aptiv 1103 including 30% mineral filler). It should be mentioned that the mechanical properties and the maximum operating temperature are drastically influenced by the operating media as discussed elsewhere [12, 13]. In respect to this, commercial available modified films of PEEK are also provided as plasma treated versions by Victrex Europa GmbH (atmospheric in-line helium/oxygen-plasma) and of PSU from Dr. D. Mller GmbH as a corona treated film. An improvement of the wetting behavior should be the aim of these modifications. To ensure both reproducibility of the results and comparability of different materials a common cleaning strategy before initial surface characterization is carried out. For that reason the cleaning with pure water is followed by drying with

pressurized air. On the one hand preliminary tests showed strong surface interactions when additionally cleaning with organic liquids. On the other hand this approach is very similar to the condition of a technical used surface. For example prior usage in seawater desalination the polymer films are recommended to be conditioned in a water bath. According to DIN EN ISO 62 the uptake of water is tested at standard conditions (23 C, 50%). In respect to the permanent contact of the polymer films with the heat transfer media the recommended (DIN EN ISO) storing procedure of the polymer samples is modified and the samples are totally immersed in the liquid. The samples are kept in darkness to avoid any impact of UV irradiation. Drying of the samples after storage is again done with pressurized air. 2.2 Polymer Characterization A detailed investigation of the surface characteristics and its changes is achieved by a combination of analytical methods. The qualitative impression of the surface topology detected with an optical microscope is added by a quantitative roughness and contour measurement (Hommel-Etamic T 8000 by Jenoptik AG) with the tactile scanning method according to DIN EN ISO 4287. Besides topology also the wetting characteristics of the surfaces are determined by the measurement of contact angles and calculation of surface free energies and its polar/non-polar components. The contact angle between the wetting liquid and

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593

the solid surface at the triple point is an essential value in wetting characterization and results from the static equilibrium at the interface of solid, liquid and surrounding gas-phase and is [14, 15]:
cos = SG SL LG

(1)

The surface tension of the liquid LG can be measured by using the pendant drop method. The surface free energy SG is the value of interest and can only be calculated by substituting the interfacial energy SL. The most recommended models for this substitution applicable for polymer surfaces are the OWRK-method (Eq. (2)) developed by Owens and Wendt [16], Rabel [17] and Kaelble [18] as well as the WU-method (Eq. (3)) [19]. These models allow a quantification of the polar (p) and disperse (d) parts of the surface free energy and differ only by the calculation of the mean value. Geometrical mean:

polar surface energy components the van Oss model [20, 21] can be used. For polymer surfaces this model was allocated as very sensitive but allows a qualitative description of the molecular surface character [2]. Swelling after immersion is detected using a microbalance (Sartorius ME36S, repeatability 2 g). The transient swelling ratio is defined as follows: wt w0 Swelling ratio (%) = 100 (4) w0 Here wt and w0 are the weights of the swollen samples at a certain time and of the dry samples. Additional wetting analysis should give evidence for molecular rearrangements or incorporation of solvents.

3. Results and Discussion

3.1 Wetting in Heat Transfer Processes The stability of a falling film is a central criterion in efficient heat transfer processes and is directly connected to the wettability of the surface. Heat transfer processes handling aqueous solutions (desalination, paper industry) require hydrophilic

(1 + cos )
(1 + cos )

LG

p p + d d = 2 SG LG SG LG
p p d d SG LG SG LG + = 4 p d d p SG + LG SG + LG

(2)

Harmonic mean:
LG

(3)

surfaces for acceptable wetting characteristics. Fig. 1 compares the wettability of different polymers and an electro-polished stainless steel surface as benchmark. The static contact angle of water as a polar liquid is directly connected to the polar part of the surfaces free energy. The wettability is quite competitive for all polymers except the nonpolar polypropylene. The polarity of a surface is influenced by the chemical structure as well as the level of crystallinity, which affects also the molecular structure and topology. Fig. 2

To solve these equations contact angle measurements with minimal two liquids with known polar and disperse parts have to be carried out. The static contact angle measurements based on the sessile drop technique are done with an OCA 15 EC setup (Dataphysics). The surface energy components of the used liquids are determined by measurements against reference liquids or solids (Table 2). To describe Lewis acid and base components of
Table 2 Liquid Water DMSO Ethylene glycol Formamide n-octane

Experimental surface energies and components of the used liquids.

LG (mNm-1)
d LG (mNm-1) p LG (mNm-1)

73.2 0.1 42.7 0.5 48.1 0.1 58.5 0.2 21.8 0.1

23.1 0.2 33.9 0.6 32.3 0.1 32.7 0.3 21.8 0.1

50.1 0.2 8.8 0.8 15.8 0.2 25.8 0.3 0.0 0.0

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Solvent Interactions with Polymeric Heat Transfer Surfaces

50 45

disperse part polar part contact angle with water

100

35 30 25

90

80 20 15 10 5 0
1.4571 PEEK PEEK PEEK PSU ep Aptiv Aptiv Aptiv 1000 2000 1103 PP

70

60

Fig. 1 Contact angle with water and corresponding surface free energy and its components for the studied surfaces (calculated with Eq. (3)).

contact angle with water /

40

shows representative microscopic pictures of the surface topology of the two PEEK films differing by their level of crystallinity. The higher level of crystallinity of the PEEK film Aptiv 1000 (30% to 35% compared to 9% to 12% for PEEK Aptiv 2000, according to Victrex Europa GmbH) results in a more unruffled surface. The arithmetic mean roughness of the Aptiv 2000 film is 0.56 m compared to 0.03 m of the Aptiv 1000 film. With the higher level of crystallinity and the lower arithmetic roughness the contact angle with water is also smaller for the Aptiv 1000 film (76.8 0.1 compared to 82.5 0.2). To enhance the wettability besides surface roughness manipulation physical and chemical surface treatments can be applied. Plasma and corona treatments for example are well-known techniques in activating polymer surfaces [22-24]. They can easily be integrated in-line to polymer foil production processes, which make it a very cost-efficient finishing procedure. Fig. 3 illustrates how the surface free energy changes with different commercial available treated materials compared to their untreated version.
45 + 30 %

surface free energy SG / mNm-1

surface free energy SG, treated / mNm-1

ct pt pt

40 pt 35 ep 30 PSU PEEK Aptiv 1103 PEEK Aptiv 1000 PEEK Aptiv 2000 1.4571 25 30 35 40 45 surface free energy SG, untreated / mNm-1

25

Fig. 2 Impact of level of crystallinity on PEEK Aptiv surface topology.

Fig. 3 Parity plot of surface free energy for treated vs. untreated surfaces (ep: electropolished, ct: corona treated, pt: plasma treated) calculated with Wu-method (Eq. (3)).

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The relative surface free energy increase due to the different treatment techniques can reach almost up to 30%. The PEEK film Aptiv 1103, which contains mineral filler, is less influenced by such a treatment. The limits of the plasma intensity are given by the energy input which can result in topological changes or crosslinking of the polymer [25]. Optimal process parameters, respectively the influence of the plasma treatment time, have already been studied [25, 26]. The used films show a long-term stability of surface free energy of minimum two years (at 23 C and 50% rel. humidity) and the relevant mechanic properties stay unaffected due to the low depth of the physical treatment [2]. In that respect the long-term stability of the wettability is of major interest in falling film processes to ensure an effective heat transfer at low liquid loads. However, also adhesion properties (affecting scaling/fouling deposits) will change when optimizing wetting properties [27]. 3.2 Swelling Characteristics Polymers are permeable and allow interactions with surrounding media, which result into swelling, shrinking of the foil or migration/re-orientation of
9 PEEK Aptiv 8 7

molecular groups on its surface, which affects the wetting and adhesion properties as well as the mechanical behavior [12, 13, 28]. The immersion of a polymer in the media of interest gives evidence about its chemical resistance and its swelling characteristics easily measured by its relative mass change. Fig. 4 shows swelling ratios of PEEK Aptiv 1000 immersed in acetone and ethanol as a function of time and the thickness of the polymer films. Acetone, as a polar ketone, shows considerably stronger interactions with PEEK compared to the uptake of ethanol, as alcohol, based on their functional similarity (like dissolves like). Besides of the higher uptake quantity (at equilibrium) also the kinetics of the swelling is faster for acetone. As expected, the uptake velocity of the organic liquids is also related to the thickness of the studied polymer films. For the thicker film (50 m) the process is slower, but also limited to the same maximum values (Fig. 4 dependent on the liquid: acetone (a) after 4 weeks and ethanol (b) after 8 weeks). The difference in the level of crystallinity of the two PEEK films Aptiv 1000 and 2000 (as discussed above) impacts also the mass related uptake of organic solvents (Fig. 5).
3.5 PEEK Aptiv 3.0 2.5

1000 in acetone

1000 in ethanol

Swelling ratio/%

Swelling ratio/%
Thickness of foil 25 m 50 m

6 5 4 3 2 1 0 0 5 Time of immersion t (weeks) 10

2.0 1.5 1.0 0.5 0.0 0 5 Time of immersion t (weeks) 10 Thickness of foil 25 m 50 m

(a) (b) Fig. 4 Relative mass changes of polymers stored in (a) acetone and in (b) ethanol as a function of the time of storage and the thickness of the polymer foil.

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Solvent Interactions with Polymeric Heat Transfer Surfaces

Fig. 5 Relative mass changes after 8 weeks of storage in various liquids as a parity plot of PEEK films with different level of crystallinity.

A higher level of crystallinity in the case of the Aptiv 1000 film causes a decrease in swelling quantity. This can be explained by the decrease of the chain flexibility, a lower amount of solvent molecules is able to dissolve or permeate into the polymer. Solubility parameter theory has been applied on swelling and physical property characterization of polymers, hydrogels and membranes, as can be found elsewhere [29-31]. The principle of like dissolves like can be explained by solubility parameter theory and the interaction can be expressed by the solubility parameter difference between solvent and polymer. A small solubility parameter difference indicates dissolution or strong interaction/swelling. Table 3 represents solubility parameters for the solvents of immersion taken from literature as well as the
Table 3

solubility parameter difference = solvent polymer. The solubility parameters of the polymers were also calculated as average values from literature. Polypropylene has the lowest solubility parameter of 8.65 0.27 (calcm-3)1/2 followed by 9.31 0.08 (calcm-3)1/2 for polyetheretherketone and 10.71 0.49 (calcm-3)1/2 for polysulfone. Since the solubility parameter can also be expressed by the square root of the cohesive energy density the order of solubility parameters is reasonable with regard to the functional groups of the monomer units. Fig. 6 shows the general relation between the calculated solubility parameter difference and the equilibrium swelling ratio for amorphous polymers after immersion at room temperature (296 2 K) in the studied liquids (values from Table 3). Polypropylene shows very low interaction with the studied solvents (open rectangles). The theoretical correlation of stronger polymer swelling with smaller solubility parameter differences is observed for polyetheretherketone and polysulfone. The observed swelling maximum of those polymers is around 2 = 0 calcm-3 and the relation is of logarithmic proportionality (trend line). The level of crystallinity impacts the equilibrium swelling ratio (as discussed above), but the influence on the polymers solubility parameter is not clarified. Though a calculation with values from literature and comparison to experimental swelling data shows good accordance to solubility parameter theory, a time-efficient polymer pre-selection can be arranged in early stage apparatus design. Solubility parameter differences near zero should be avoided to prevent

Solubility parameters of pure solvents and solubility parameter differences with amorphous polymers. lit a (calcm-3)1/2 23.31 0.09 9.90 0.05 11.57 0.08 12.79 0.07 PEEK b (calcm-3)1/2 14.00 0.12 0.59 0.09 2.26 0.11 3.48 0.11 PSU b (calcm-3)1/2 12.60 0.50 -0.81 0.50 c 0.86 0.50 2.08 0.50 PP b (calcm-3)1/2 14.66 0.29 1.25 0.28 2.92 0.28 4.14 0.28

liquid water acetone isopropanol ethanol

Average values and standard errors calculated from literature a [31-34] and b [33, 35-38]. c destruction observed in immersion.

Solvent Interactions with Polymeric Heat Transfer Surfaces

597

Fig. 6 Equilibrium swelling ratio of studied polymers vs. solubility parameter difference between solvent of immersion and polymer.

strong interaction or destruction (observed for polysulfone in acetone with 2 = 0.66 calcm-3). The influence of swelling on mechanical properties should not be discussed in the present work. 3.2 Swelling-Property Relation In comparison to the organic solvents, the observed uptake of water for all studied polymers was very low (< 1% in relative mass change over time), but the wettability with water itself increases significantly after immersion. Fig. 7 presents the major changes in wetting behavior as a function of storage time. The changes in wettability are significant and reach up to a contact angle difference of about 20. For the three different materials presented in Fig. 7 these changes happen in the first three days of storage and reach nearly steady state (also the range of error bars). The low molecular weight of water and the ability to build strong hydrogen bonds with the functional polymeric groups contribute to this effect. The hydrophilization of the surface can be explained by irreversible reorientation of hydrophobic groups or polymer chains also discussed in literature [23, 39].

The predominantly amorphous PEEK Aptiv 2000 experiences a contact angle decrease of around 17 in the first three days of storage (Fig. 7). The measured contact angle change of the partially crystalline film of PEEK Aptiv 1000 is about 9 (from 82 to 73 in the first three days). This fact can be related to the lower molecular flexibility due to the higher level of crystallinity (as discussed regarding swelling ratio), which retards possible reorientation of the polymeric structure. The surface free energy and its components (polar and disperse) at swelling equilibrium (water and isopropanol) is determined to allow a fluid-independent interpretation of changes in molecular orientation. Regarding to Fig. 8a the amount of surface free energy increase due to solvent immersion is comparable to results of common surface treatment techniques discussed above (Fig. 3). In particular the changes for PEEK and PP in interaction with water are large, since polymer swelling with hydrophobic organic solvents was very low.

100

PP PEEK Aptiv 2000 PSU

Contact angle /
/

90

80

70

60

50 0 10 20 30 Time of storage ts/d Fig. 7 Static contact angle of water on conditioned amorphous polymer films as a function of the storage time.

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Solvent Interactions with Polymeric Heat Transfer Surfaces

(a) (b) Fig. 8 (a) Parity plot of surface free energy change at equilibrium swelling ratio after storage in water and isopropanol and (b) relative changes in polar part of different polymers calculated with Wu-method (Eq. (3)).

Most of the changes in surface free energy occur due to an increase of the polar part (Fig. 8b). For that reason the surfaces hydrophilic character is increased which enhances the wettability with water (compare to Fig. 7). The latter is of great interest in polymer heat exchanger design when processing aqueous solutions. The impact on adhesion properties to potential scaling deposits (e.g., desalination) and mechanical properties has to be studied for an overall understanding of polymer swelling consequences in heat transfer processes.

4. Conclusions
Polymer swelling processes affecting heat transfer were studied with special regards to wettability of the surfaces. The transient polymer solvent interaction was investigated for different polypropylene, polysulfone and polyetheretherketone films and various solvents. The equilibrium swelling ratio was found to be dependent on level of crystallinity of PEEK and three organic solvents. The application of solubility parameter theory correlated well with the observed experimental results, which makes it a

predictive method in early stage of polymer heat exchanger material selection. Low equilibrium swelling ratios for an immersion in water and isopropanol but a significant change in wettability were observed for the studied polymers. The increase in hydrophobic character of the polymers is comparable to surface finishing with common treatment techniques (plasma, corona) and attributed to the increase in polar parts of surface free energy. Besides mechanical investigations, the knowledge of surface energetic effects contributes to existing polymer heat exchanger design criteria.

Acknowledgments
The authors would like to thank the Deutsche Forschungsgemeinschaft (DFG) for the financial support and the Institute for Measurement and Sensor-Technology (MTS) of the Department of Mechanical and Process Engineering at TU Kaiserslautern for providing experimental equipment (contour measurement). The authors are also thankful to Victrex Europa GmbH for providing PEEK samples.

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