ACCU DYNE TEST ™ Bibliography
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3014. Kusano, Y., and R. Kusano, “Critical assessment of the correlation between surface tension components and Hansen solubility parameters,” Colloids and Surfaces A: Physicochemical and Engineering Aspects, 677, Part B, (Nov 2023).
Surface or interfacial phenomena, including wetting, adsorption, adhesion, and dissolution, are of significant interest for daily life as well as for industrial and engineering applications. Surface tension and the Hansen solubility parameter (HSP) both represent similar physical characteristics related to these phenomena. It is therefore interesting to study the relation between them, and in the present work, reported empirical relations between surface tension and HSP are critically investigated. There exists an approximately proportional relation between total surface tension and HSP, although the coefficient obtained in the present work is much smaller than the commonly reported ones. The result is supported by an estimation of the coefficient using a simple physical model. On the other hand, finding correlations between the partial components of surface tension and HSP appears to be difficult as they are measured differently. The uses of databases from which measurements are taken must also be taken into question. As an example, the surface tension components of diiodomethane are investigated, and the validity of the reported values are called into question.
204. Kutsch, W.P., “Hot stamping applications and critical surface tension in the plastic industry,” in SPE Decorating Div. RETEC 1993, Society of Plastics Engineers, Oct 1993.
205. Kuusipalo, J., and A. Savolainen, “Ozone, generated at corona treater, as an adhesion promoter in extrusion coating,” in 1994 Polymers, Laminations and Coatings Conference Proceedings, 325-333, TAPPI Press, Aug 1994 (also in TAPPI J., Vol. 77, p.162-166 (Dec 1994)).
The trials documented in this paper were run on a pilot coextrusion coating line at the Tampere University of Technology's Institute of Paper Converting in Finland. The study was conducted to test the ozonization system that was installed in our pilot line to treat the polymer melt in extrusion coating. The effect of the ozone, generated at the corona treater, on adhesion was studied. Ozone was first captured and transported to the nip with separate pipes. It was then led to an air knife near the air gap and blown against the polymer melt. The measured adhesion showed the usefulness of this technique. The following parameters were varied to determine the effectiveness of the ozone: substrate, line speed, coating weight, and melt temperature. Results indicated that thicker coating weights and higher melt temperatures improved adhesion values. The corona-generated ozone clearly improved adhesion compared to corona-treated or untreated samples.
1868. Kuusipalo, J., and A. Savolainen, “Adhesion phenomena in (co) extrusion coating of paper and paperboard,” J. Adhesion Science and Technology, 11, 1119-1135, (1997).
In extrusion coating, the inadequate adhesion between the polymer coating and the fiber-based paper substrate (paper and paperboard) is both a common and a constant problem. The lack of adhesion between the printing ink, or glue, and the polymer coating is another area where adhesion improvement is needed. The common means of improving adhesion are flame, corona, and ozone treatments. A modem extrusion coating line is equipped with both a pretreatment and a post-treatment unit. From the work presented here, the following observations were made. The higher the applied corona power and the thicker the coating, the higher the surface energy and polarity of the low density polyethylene (PE-LD) surface. When a high corona power was applied to the coating, only the polar component of the surface energy was increased. The surface energy decreased sharply as a function of aging, but remained more or less constant after about 2 weeks' storage time. The contact angles of water on paper correlated well with the oxygen contents (determined by ESCA) and with the applied corona power. The polarities of both paper and paperboard increased as a function of the applied corona power. Corona pretreatment of paper and paperboard improved their adhesion to PE-LD remarkably. The adhesion of the polypropylene (PP) homopolymer is based more on mechanical interlocking than on interfacial bonding. On the other hand, the oxidizing pretreatments of the paper substrates significantly promoted the adhesion of the PP copolymer.
2754. Kuusipalo, J., and A. Savolainen, “Adhesion in extrusion coating with polypropylene,” in 1993 Polymers, Coatings and Laminations Conference Proceedings, 469-478, TAPPI Press, Aug 1993.
716. Kuusipalo, J.T., and A.V. Savolainen, “Adhesion phenomena in (co)extrusion coating of paper and paperboard,” Presented at First International Congress on Adhesion Science and Technology, Oct 1995.
206. Kuznetsov, A.Y., V.A. Bagryansky, and A.K. Petrov, “Adhesion properties of glow-discharge plasma treated polyethylene surfaces,” J. Applied Polymer Science, 47, 1175-1184, (1993).
A geometric method proposed by Kaelble and Moacanin for analyzing energetic characteristics of solid surfaces is discussed. It is shown that a number of characteristics can be presented in a visual geometric form. The method is applied to the analysis of adhesion in a three-component system. Results of the analysis, concerned with the problem of creation of biocompatible materials, support the Andrade hypothesis that materials with zero interfacial tension of their water–solid interface show maximum biocompatibility. Data are obtained on wetting of polyethylene by different liquids before and after glow discharge plasma treatment. The analysis of these data in terms of geometric method shows the plasma treatment increased the polar component of the polymer surface energy to change the surface adhesiveness toward probable enhancement of polymer biocompatibility. That is consistent with available data on glow-discharge-treatment enhancement of biocompatibility for a number of polymers. © 1993 John Wiley & Sons, Inc.
https://onlinelibrary.wiley.com/doi/abs/10.1002/app.1993.070470705
548. Kuznetsov, A.Y., V.A. Bagryansky, and A.K. Petrov, “Adhesion properties of glow-discharge-plasma-treated polyethylene surface,” J. Applied Polymer Science, 47, 1175-1184, (Feb 1993).
1018. Kuzuya, M., S. Kondo, M. Sugito, and T. Yamashiro, “Peroxy radical formation from plasma-induced surface radicals of polyethylene as studied by electron spin resonance,” Macromolecules, 31, 3230-3234, (May 1998).
The nature of peroxy radical formation from plasma-induced surface radicals of polyethylene (PE), both low-density polyethylene (LDPE) and high-density polyethylene (HDPE), was studied by electron spin resonance with the aid of systematic computer simulations. It was found that peroxy radical formation varies with the structure of component radicals of plasma-irradiated PE, both LDPE and HDPE: Among three plasma-induced radicals of PE, dangling bond sites (DBS) undergo an instant conversion into the corresponding peroxy radicals in contact with oxygen, while the midchain alkyl radical is of very low reactivity with oxygen in both LDPE and HDPE. Computer simulations disclosed that ESR spectra of peroxy radicals are similar to each other in LDPE and HDPE, both being composed of two types of spectra, a partial >em>g-averaging anisotropic spectrum and a nearly isotropic single line spectrum due to different molecular motional freedom at the trapping sites of peroxy radicals.
1019. Kuzuya, M., T. Yamashiro, S. Kondo, M. Sugito, and M. Mouri, “Plasma-induced surface radicals of low-density polyethylene studied by electron spin resonance,” Macromolecules, 31, 3225-3229, (May 1998).
Plasma-induced low-density polyethylene (LDPE) radicals were studied in detail by electron spin resonance (ESR) by its comparison with ESR of high-density polyethylene (HDPE). The observed ESR spectra of plasma-irradiated LDPE are largely different in pattern from those of HDPE. The systematic computer simulation disclosed that such observed spectra consist of three kinds of radicals, midchain alkyl radical (1), allylic radical (2) as discrete radical species, and a large amount of dangling bond sites (DBS) (3) at an intra- and intersegmental cross-linked region. All these component radicals are essentially identical to those of HDPE. One of the most special features unique to plasma-irradiated LDPE, however, is the fact that thermally stable DBS (3) is a major component radical instead of a midchain alkyl radical in HDPE. This can be ascribed to the difference in polymer morphology between LDPE and HDPE: branched structure with a large amount of amorphous region for LDPE and linear structure with a large amount of crystalline region for HDPE. Since one of the characteristics of plasma irradiation is the fact that it is surface-limited, LDPE would undergo the radical formation preferentially on the surface-branched structural moiety followed by facile cross-link reactions resulting in the formation of DBS. Thus, the nature of radical formation of PE was found to be affected by the polymer morphology in a very sensitive manner.
1698. Kwok, D.Y., “The usefulness of the Lifshitz-van der Waals/acid-base approach for surface tension components and interfacial tensions,” Colloids and Surfaces A: Physicochemical and Engineering Aspects, 156, 191-200, (1999).
The Lifshitz–van der Waals/acid-base approach proposed by van Oss et al. is found to yield inconsistent solid surface tensions and components from contact angles, for fluorocarbon, polystyrene, and poly(methyl methacrylate) solid surfaces. It is also shown that the approach cannot predict the correct interfacial tensions of all liquid–liquid pairs in question: the predicted interfacial tensions range from 34% lower to 112% higher than the experimental values. Thus, the usefulness of the approach for surface tension components and interfacial tensions is open to question. The liquid surface tension components postulated since 1986 are also summarized.
1316. Kwok, D.Y., A. Leung, A. Li, C.N.C. Lam, R. Wu, and A.W. Neumann, “Low-rate dynamic contact angles on poly(n-butyl methacrylate) and the determination of solid surface tensions,” Colloid and Polymer Science, 276, 459-469, (1998).
Low-rate dynamic contact angles of 22 liquids on a poly(n-butyl methacrylate) (PnBMA) polymer are measured by an automated axisymmetric drop shape analysis-profile (ADSA-P). It is found that 16 liquids yielded non-constant contact angles, and/or dissolved the polymer on contact. From the experimental contact angles of the remaining 6 liquids, it is found that the liquid–vapor surface tension times cosine of the contact angle changes smoothly with the liquid–vapor surface tension, i.e. γlv cos θ depends only on γlv for a given solid surface (or solid surface tension). This contact angle pattern is in harmony with those from other inert and non-inert (polar and non-polar) surfaces [34–37, 45–47]. The solid–vapor surface tension calculated from the equation-of-state approach for solid-liquid interfacial tensions [14] is found to be 28.8 mJ/m2, with a 95% confidence limit of ±0.5 mJ/m2, from the experimental contact angles of the 6 liquids.
1314. Kwok, D.Y., A. Leung, C.N.C. Lam, A. Li, R. Wu, and A.W. Neumann, “Low-rate dynamic contact angles on poly(methyl methacrylate) and the determination of solid surface tensions,” J. Colloid and Interface Science, 206, 44-51, (1998).
Low-rate dynamic contact angles of nine liquids on a poly(methyl methacrylate) (PMMA) polymer are measured by an automated axisymmetric drop shape analysis—profile (ADSA-P). It is found that two liquids dissolved the polymer on contact. From the experimental contact angles of the other seven polar and nonpolar liquids, it is found that the liquid–vapor surface tension times cosine of the contact angle changes smoothly with the liquid–vapor surface tension (i.e., γlνcos θ depends only on γlνfor a given solid surface). The dependence of γlνcos θ on γsνis explicitly illustrated by replacing the solid surface from the PMMA to other methacrylate polymers: such a procedure shifts the curves in a very regular manner. Thus, because of Young's equation, γsldepends only on γlνand γsν. This contact angle pattern is in harmony with those from other inert and noninert (polar and nonpolar) surfaces. The solid–vapor surface tension of PMMA calculated from the equation of state approach for solid–liquid interfacial tensions is found to be 38.5 mJ/m2, with a 95% confidence limit of ±0.5 mJ/m2from the experimental contact angles of the seven liquids.
1320. Kwok, D.Y., A. Li, and A.W. Neumann, “Low-rate dynamic contact angles on poly(methyl methacrylate/ethyl methacrylate, 30/70) and the determination of solid surface tensions,” J. Polymer Science Part B: Polymer Physics, 37, 2039-2051, (1999).
Low-rate dynamic contact angles of 12 liquids on a poly(methyl methacrylate/ethyl methacrylate, 30/70) P(MMA/EMA, 30/70) copolymer were measured by an automated axisymmetric drop shape analysis-profile (ADSA-P). It was found that five liquids yield nonconstant contact angles, and/or dissolve the polymer on contact. From the experimental contact angles of the remaining seven liquids, it is found that the liquid–vapor surface tension times cosine of the contact angle changes smoothly with the liquid–vapor surface tension (i.e., γl|Kv cos θ depends only on γl|Kv for a given solid surface or solid surface tension). This contact angle pattern is in harmony with those from other methacrylate polymer surfaces previously studied.45,50 The solid–vapor surface tension calculated from the equation-of-state approach for solid–liquid interfacial tensions14 is found to be 35.1 mJ/m2, with a 95% confidence limit of ± 0.3 mJ/m2, from the experimental contact angles of the seven liquids. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2039–2051, 1999
https://onlinelibrary.wiley.com/doi/abs/10.1002/(SICI)1099-0488(19990815)37:16%3C2039::AID-POLB8%3E3.0.CO;2-O
1806. Kwok, D.Y., C.J. Budziak, and A.W. Neumann, “Measurement of static and low rate dynamic contact angles by means of an automated capillary rise technique,” J. Colloid and Interface Science, 173, 143-150, (Jul 1995).
Six solid surfaces were compared with respect to their surface quality, by measuring advancing contact angles along the solid surfaces (in the vertical and horizontal directions) at constant immersion rate. It was found that surfaces of mica, dip coated in FC-721, Teflon (FEP) heat pressed against mica, and siliconized glass yield essentially constant advancing contact angles at different locations of the solid surfaces and, thus, are well suited to dynamic contact angle measurements. Static and low rate dynamic contact angles of a number of pure liquids were therefore measured on these solid surfaces. Low rate dynamic contact angles were found to be identical with the static contact angles and independent of the velocity of the three-phase contact line (up to 0.5 mm/min).
1294. Kwok, D.Y., C.N.C. Lam, A. Li, A. Leung, R. Wu, E. Mok, and A.W. Neumann, “Measuring and interpreting contact angles: A complex issue,” Colloids and Surfaces A: Physicochemical and Engineering Aspects, 142, 219-235, (1998).
Low-rate dynamic contact angles of 30 liquids on a FC-725-coated wafer surface were measured by an automated axisymmetric drop shape analysis-profile (ADSA-P). Surprisingly, results indicate that FC-725 behaves differently in some respects from what one would expect for non-polar surfaces: only nine liquids yield essentially constant contact angles whereas the others show slip/stick contact angle behaviour. In the worst case, the contact angle increases from ca 50 to 160° at essentially constant three-phase contact radius. These angles should be disregarded for the interpretation in terms of surface energetics since there is no guarantee that Young's equation is applicable. If one employs a conventional goniometer-sessile drop technique, such contact angle behaviour cannot be easily seen in all cases. These results indicate that the claim from van Oss et al. [Langmuir 4 (1988) 884] that liquids with the same contact angles do not have the same surface tensions is misleading. If the meaningful contact angles are plotted as the liquid–vapour surface tension times cosine of the contact angle versus the liquid–vapour surface tension, that is, γlv cos θ versus γlv, a smooth curve emerges. Thus, intermolecular forces (or surface tension components) do not have an additional and independent effect on the contact angles, in good agreement with the results from other studies on non-polar and polar polymers.
1315. Kwok, D.Y., C.N.C. Lam, A. Li, K. Zhu, R. Wu, and A.W. Neumann, “Low-rate dynamic contact angles on polystyrene and the determination of solid surface tensions,” Polymer Engineering and Science, 38, 1675-1684, (1998).
Low-rate dynamic contact angles of 13 liquids on a polystyrene polymer are measured by an automated axisymmetric drop shape analysis – profile (ADSA-P). It is found that 7 liquids yielded non-constant contact angles, and/or dissolved the polymer on contact. From the experimental contact angles of the other 6 liquids, it is found that the liquid-vapor surface tension times cosine of the contact angle changes smoothly with the liquid-vapor surface tension, i.e. γlvcosθ depends only on γlv for a given solid surface (or solid surface tension). This contact angle pattern is in harmony with those from other inert and non-inert (polar and non-polar) surfaces (7–13, 24–26). The solid-vapor surface tension calculated from the equation-of-state approach for solid-liquid interfacial tensions (33) is found to be 29.8 mJ/m2, with a 95% confidence limit of ±0.5 mJ/m2 from the experimental contact angles of 6 liquids.
1317. Kwok, D.Y., C.N.C. Lam, A. Li, and A.W. Neumann, “Low-rate dynamic contact angles on poly(methyl methacrylate/n-butyl methacrylate) and the determination of solid surface tensions,” J. Adhesion, 68, 229-255, (1998).
Low-rate dynamic contact angles of 12 liquids on a poly(methyl methacrylate/n-butyl methacrylate) P(MMA/nBMA) copolymer are measured by an automated axisymmetric drop shape analysis-profile (ADSA-P). It is found that 6 liquids yield non-constant contact angles, and/or dissolve the polymer on contact. From the experimental contact angles of the remaining 6 liquids, it is found that the liquid- vapour surface tension times the cosine of the contact angle changes smoothly with the liquid-vapour surface tension, i.e., γiv cos θ depends only on γiv for a given solid surface (or solid surface tension). This contact angle pattern is in harmony with those from other inert and noninert (polar and non-polar) surfaces [34-42, 51 -53]. The solid-vapour surface tension calculated from the equation-of-state approach for solid -liquid interfacial tensions [14] is found to be 34.4 mJ/m2, with a 95% confidence limit of \pm 0.8mJ/m2, from the experimental contact angles of the 6 liquids.
723. Kwok, D.Y., D. Li, and A.W. Neumann, “Capillary rise at a vertical plate as a contact angle technique,” in Applied Surface Thermodynamics, Neumann, A.W., and J.K. Spelt, eds., 413-440, Marcel Dekker, Jun 1996.
In the vast majority of contact angle studies in the literature, the method used is direct measurement of sessile drops. Recent developments in image analysis and processing have increased the accuracy and reduced the subjectivity considerably (see Chapter 10). Nevertheless, there are certain limitations which leave room for other techniques. One of the limitations of the classical sessile-drop method is that the camera or imaging device will be focused on the largest meridian section, and hence reflect only the contact angles at the point in which the meridian plane intersects the three-phase line. Surface heterogeneity and/or roughness could well cause variations of the contact angle along the three-phase line. An alternate approach is to infer the contact angle from the drop contact diameter (see Chapter 10). But even on very good solid surfaces, on which such effects are absent, there is a systematic problem with this method: contact angles will change as a function of drop size for drops up to approximately 1 cm diameter. While this dependence can indeed be used to determine line tension (see Chapter 4), this and other similar effects interfere with the interpretation of contact angles in terms of surface energetics (see Chapter 3).
1305. Kwok, D.Y., D. Li, and A.W. Neumann, “Fowkes' surface tension components approach revisited,” Colloids and Surfaces A: Physicochemical and Engineering Aspects, 89, 181-191, (1994).
By comparing the number of degrees of freedom obtained from the phase rule for capillary systems, the Fowkes surface tension component approach for interfacial tensions is shown to require more degrees of freedom than are available for a two-component solid—liquid—vapour system. Only in a special case has the Fowkes approach two degrees of freedom: a dispersive liquid on a dispersive solid, suggesting that there are no surface tension components. Experimental results suggest that the Fowkes component approach does not describe physical reality; only the liquid and solid surface tensions, γ1v and γsv, are operative in the two-component solid—liquid—vapour system. Generalization of the Fowkes component approach, of course, will increase the number of independent variables and hence definitely require more degrees of freedom than are available.
The number of degrees of freedom of the equation of state for interfacial tensions is shown to agree with that predicted from the phase rule for capillary systems as well as with experimental results. By using the empirical form of the equation of state, essentially constant solid tensions, γsv, are obtained from a variety of dispersive and non-dispersive liquids for three solid surfaces: fluorocarbon (FC721), Teflon (FEP) and poly(ethylene terephthalate) (PET).
1306. Kwok, D.Y., D. Li, and A.W. Neumann, “Evaluation of the Lifshitz-van der Waals/acid-base approach to determine interfacial tensions,” Langmuir, 10, 1323-1328, (1994).
1312. Kwok, D.Y., L.K. Cheung, C.B. Park, and A.W. Neumann, “Study on the surface tensions of polymer melts using axisymmetric drop shape analysis,” Polymer Engineering and Science, 38, 757-764, (1998).
It is shown that Axisymmetric Drop Shape Analysis (ADSA) is well-suited for the study of polymer melt surface tensions. The technique is not restricted to equilibrium surface (interfacial) tensions; it is also suitable for measuring the time dependence (or kinetics) of surface tension of polymer melts. Results for three polymers, polypropylene, polyethylene, and polystyrene, at temperatures above 170°C are reported. Contrary to the well-known decrease of surface tension in low molecular weight surfactant solutions as a result of equilibration, an increase in the melt surface tension is observed under isothermal conditions.
779. Kwok, D.Y., and A.W. Neumann, “Contact angle measurements and contact angle interpretation: Relevance to the thermodynamics of adhesion,” in Acid-Base Interactions: Relevance to Adhesion Science and Technology, Vol. 2, K.L. Mittal, ed., 91-166, VSP, Dec 2000.
883. Kwok, D.Y., and A.W. Neumann, “Contact angle techniques and measurements,” in Surface Characterization Methods: Principles, Techniques, and Applications, Milling, A.J., ed., 37-86, Marcel Dekker, Aug 1999.
1095. Kwok, D.Y., and A.W. Neumann, “Contact angle measurements and criteria for surface energetic interpretation,” in Contact Angle, Wettability and Adhesion, Vol. 3, Mittal, K.L., ed., 117-160, VSP, Nov 2003.
1226. Kwok, D.Y., and A.W. Neumann, “Contact angle measurements and interpretation: Wetting behavior and solid surface tension for poly(alkyl methacrylate) polymers,” J. Adhesion Science and Technology, 14, 719-743, (2000).
Low-rate dynamic contact angles of a large number of liquids were measured on a poly(ethyl methacrylate) (PEMA) polymer using an automated axisymmetric drop shape analysis profile (ADSA-P). The results suggested that not all experimental contact angles can be used for the interpretation in terms of solid surface tensions: eight liquids yielded non-constant contact angles and/or dissolved the polymer on contact. From the experimental contact angles of the remaining four liquids, we found that the liquid-vapor surface tension times the cosine of the contact angle changes smoothly with the liquid-vapor surface tension, i.e. γlv cos ζ depends only on γlv for a given solid surface (or solid surface tension). This contact angle pattern is again in harmony with those from other methacrylate polymer surfaces of different compositions and side-chains. The solid-vapor surface tension of PEMA calculated from the equation-of-state approach for solid-liquid interfacial tensions was found to be 33.6 ± 0.5 mJ/m2 from the experimental contact angles of the four liquids. The experimental results also suggested that surface tension component approaches do not reflect physical reality. In particular, experimental contact angles of polar and nonpolar liquids on polar methacrylate polymers were employed to determine solid surface tension and solid surface tension components. Contrary to the results obtained from the equation-of-state approach, we obtained inconsistent values from the Lifshitz-van der Waals/acid-base (van Oss and Good) approach using the same sets of experimental contact angles.
1311. Kwok, D.Y., and A.W. Neumann, “A simple experimental test of the Lifshitz-van der Waals/acid-bsae approach to determine interfacial tensions,” Canadian J. Chemical Engineering, 74, 551-553, (1996).
A study was conducted which showed that the Lifshitz-van der Waals / acid-base approach yielded liquid-liquid interfacial tensions which were incompatible with experimental results. The approach allowed correct prediction of interfacial tensions for only four completely miscible liquid/liquid pairs. This result calls into question traditionally held interfacial tension theories, and points up the need for caution in the application to solid/liquid contact angle systems if an approach should fail the liquid/liquid test.
1319. Kwok, D.Y., and A.W. Neumann, “Contact angle measurement and contact angle interpretation,” Advances in Colloid and Interface Science, 81, 167-249, (1999).
Recent progress in the correlation of contact angles with solid surface tensions are summarized. The measurements of meaningful contact angles in terms of surface energetics are also discussed. It is shown that the controversy with respect to measurement and interpretation of contact angles are due to the fact that some (or all) of the assumptions made in all energetic approaches are violated when contact angles are measured and processed. For a large number of polar and non-polar liquids on different solid surfaces, the liquid–vapor surface tension times cosine of the contact angle, γlvcosθ, is shown to depend only on the liquid–vapor surface tension γlv, and the solid–vapor surface tension γsv when the appropriate experimental techniques and procedures are used. Equations which follow these experimental patterns and which allow the determination of solid surface tensions from contact angles are discussed. Universality of these experimental contact angle patterns is illustrated; other reasons which may cause data to deviate from the patterns slightly are discussed. It is found that surface tension component approaches do not reflect physical reality. Assuming the fact that solid surface tension is constant for one and the same solid surface, experimental contact angle patterns are employed to deduce a functional relationship to be used in conjunction with Young's equation for determining solid surface tensions. The explicit form of such a relation is obtained by modifying Berthelot's rule together with experimental data; essentially constant solid surface tension values are obtained, independent of liquid surface tension and molecular structure. A new combining rule is also derived based on an expression similar to one used in molecular theory; such a combining rule should allow a better understanding of the molecular interactions between unlike solid–liquid pairs from like pairs. Existing static contact angles for 34 different types of solid surfaces from Zisman et al. are evaluated in terms of their solid surface tensions using experimental contact angle patterns. A FORTRAN computer program has been implemented to automate these procedures. It is found that literature contact angles do not have to be discarded completely; they can be used to determine solid surface tensions, with caution. The surface tensions for the 34 solid surfaces from Zisman et al. are also reported.
1325. Kwok, D.Y., and A.W. Neumann, “Contact angle interpretation in terms of solid surface tension,” Colloids and Surfaces A: Physicochemical and Engineering Aspects, 161, 31-48, (2000).
Recent experimental (low-rate) dynamic contact angles for 14 solid surfaces are interpreted in terms of their solid surface tensions. Universality of these experimental contact angle patterns is illustrated; other reasons that can cause data to deviate from the patterns are discussed. It is found that surface tension component approaches do not reflect physical reality. Assuming solid surface tension is constant for one and the same solid surface, experimental contact angle patterns are employed to deduce a functional relationship to be used in conjunction with the Young equation to determine solid surface tensions. The explicit form of such a relation is obtained by modifying Berthelot’s rule together with experimental data; essentially constant solid surface tension values are obtained, independent of liquid surface tension and molecular structure. A new combining rule is also derived based on an expression similar to one used in molecular theory; such a combining rule should allow a better understanding of the molecular interactions between unlike solid–liquid pairs.
1331. Kwok, D.Y., and A.W. Neumann, “Contact angles and surface energetics,” Progress in Colloid and Polymer Science, 109, 170-184, (1998).
Recent progress in the correlation of contact angles with solid surface tensions are summarized. The measurements of meaningful contact angles in terms of surface energetics are also discussed. It is shown that the apparent controversy with respect to measurement and interpretation of contact angles are due to the fact that some (or all) of the assumptions made in all energetic approaches [7–14] are violated when contact angles are measured and processed. For a large number of polar and non-polar liquids on different solid surfaces, the values of γ 1v cos θ are shown to depend only on γ 1v and γsv when the appropriate experimental techniques and procedures are used. An equation which follows these experimental patterns and which allows the determination of solid surface tensions from contact angles is discussed.
2547. Kwon, O.-J., S. Tang, S.-W. Myung, N. Lu, and H.-S. Choi, “Surface characteristics of polypropylene film treated by an atmospheric pressure plasma,” Surface and Coatings Technology, 192, 1-10, (Mar 2005).
After the atmospheric pressure plasma treatment of polypropylene (PP) film surface, we measured the contact angle of the surface by using polar solvent (water) and nonpolar solvent (diiodomethane). We also calculated the surface free energy of PP film by using the measured values of contact angles. And then we analyzed the change of the contact angle and surface free energy with respect to the conditions of atmospheric pressure plasma treatment. Upon each condition of atmospheric pressure plasma treatment, the contact angle and surface free energy showed optimum value or leveled off. Through AFM analysis, we also observed the change of surface morphology and roughness before and after plasma treatment. The surface roughness of PP film showed the highest value when the plasma treatment time was 90 s. Finally, we analyzed the change of chemical compositions on the PP film surface through XPS. As the result of analysis, we observed that polar functional groups, such as –CO, –C=O, and –COO were introduced on the PP film surface after atmospheric pressure plasma treatment.
2450. Kwon, O.-J., S.-W. Myung, C.-S. Lee, and H.-S. Choi, “Comparison of the surface characteristics of polypropylene films treated by Ar and mixed gas (Ar/O2) atmospheric pressure plasma,” J. Colloid and Interface Science, 295, 409-416, (Mar 2006).
In an attempt to modify the hydrophobic surface properties of polypropylene (PP) films, this study examined the optimum process parameters of atmospheric pressure plasma (APP) using Ar gas. Under optimized conditions, the effects of a mixed gas (Ar/O2) plasma treatment on the surface-free energy of a PP film were investigated as a function of the O2 content. The polar contribution of the surface-free energy of the PP film increased with increasing O2 content in the gas mixture. However, slightly more oxygen-containing polar functional groups such as CO, CO, and COO were introduced on the PP film surface by the Ar gas only rather than by the Ar/O2 gas mixture. In addition, AFM analysis showed that the Ar plasma treatment of the PP film produced the smoothest surface as a result of the relatively homogeneous etching process.
2778. LaPorte, R.J., Hydrophilic Polymer Coatings for Medical Devices, CRC Press, 1997.
207. Ladizeski, N.H., and I.M. Ward, “The adhesion behavior of high modulus polyethylene fibers following plasma and chemical treatment,” J. Materials Science, 24, 3763-3773, (1989).
Previously published pull-out adhesion results have been substantiated by more extensive studies of chemical and plasma treatment. Particular attention has been paid to the affect of geometrical variables on the values of adhesion obtained. The effect of strain rate has also been examined. Most of the results can be understood on a semi-quantitative basis by a simple extension of lap joint theory.
724. Lahooti, S., O.I. del Rio, P. Cheng, and A.W. Neumann, “Axisymmetric drop shape analysis (ADSA),” in Applied Surface Thermodynamics, Neumann, A.W., and J.K. Spelt, eds., 441-508, Marcel Dekker, Jun 1996.
Numerous methodologies have been developed for the measurement of contact angles and surface tensions as outlined in Chapter 8 and Refs. 1-4. Liquid surface tension measurements commonly involve the determination of the height of a meniscus in a capillary, or on a fiber or a plate. Contact angles are most commonly measured by aligning a tangent with the profile of a sessile drop at the point of contact with the solid surface. Other notable methods are the Wilhelmy slide (Chapter 8) and the capillary rise technique (Chapter 9). An overview of such techniques reveals that in most instances a balance must be struck between the simplicity, the accuracy, and the flexibility of the methodology.
2581. Lahti, J., “Dry toner-based electrophotographic printing on extrusion coated paperboard (PhD thesis),” Tampere University of Technology, 2005.
2756. Lahti, J., “The role of surface properties in digital printing on extrusion coated paperboard,” in Proceedings of the 9th TAPPI Advanced Coating Fundamentals Symposium, TAPPI Press, 2006.
2758. Lahti, J., “The effects of corona and flame treatment II: PE-HD and PP coated papers,” in 12th TAPPI European PLACE Conference Proceedings, 278-314, TAPPI Press, May 2009.
The most important function of a packaging material is to shield the product inside the package. Extrusion coated papers and paperboards are generally used in various consumer packages like food, medical and cosmetic packages. Extrusion coatings give a barrier against water, water vapour, aroma, grease, oxygen, etc. In addition to barrier properties, heat sealability and printability are important properties in packaging applications. From the point of view of printing, the dense and impervious structure of extrusion coatings is challenging: printing inks and toners do not penetrate into the coatings. The durability of the printed image is significant, because the image must withstand various converting operations when the package is constructed. The most common method for obtaining good ink or toner adhesion is to oxidise the surface. Surface treatments are used to change the chemical composition, increase surface energy, modify surface morphology and topography, or remove contaminants and weak boundary layers. Two widely used methods are corona discharge treatment and flame treatment. These processes generally cause physical and chemical changes in a thin surface layer without affecting the bulk properties. Treatments will increase surface energy and also provide polar molecular groups necessary for good bonds between ink/toner and polymer molecules. In addition to printability, surface treatments also affect the sealing properties, i.e. initial heat sealing temperature, initial hot tack temperature, sealing window and seal strength of extrusion coatings. Both the sealability of packaging material and the tightness of the seal are critical points in the manufacturing process of packages and of the final package. The printability must be obtained without losing the sealability properties. In the first part of this research (TAPPI European PLACE 2007), surface energy, printability and sealability of low density polyethylene (PE-LD) coated paperboard after flame and corona treatments were studied. In this second part of the study, the research is extended to other polyolefins, i.e. high-density polyethylene (PE-HD) and polypropylene (PP). The surface chemistry is evaluated with contact angle measurements and X-ray photoelectron spectroscopy (XPS) measurements. Scanning electron microscopy (SEM) and optical profilometry are used to study the topographical and morphological changes on the surfaces. Furthermore, the heat sealing and hot tack properties, and water vapour barrier properties of the extrusion coatings are evaluated. The aim of this study is also to evaluate the printability of the extrusion coatings and to map out the role of surface modification in print quality formation. This study has concentrated on digital printing, particularly on the dry toner-based electrophotographic printing process. Flame treatment decreases the contact angle of water on PE-LD, PE-HD and PP coated papers more than corona treatment, but the lowest contact angle is obtained when the treatments are used simultaneously (i.e. co-effect of the treatments). Flame treatment deteriorates the sealability properties of PE-LD coated paper, whereas corona treatment improves sealability for example by decreasing the minimum heat sealing temperature. The sealability properties of PE-HD and PP coated papers are improved not only by corona treatment, but also by flame treatment. Flame treatment significantly improves the water vapour barrier of PEs. Where printability is concerned, it can be noticed that all the treatments improve rub-off resistance with PEs. With PE-LD flame is the most effective, and with PE-HD corona. With PP, the co-treatment gives the best result. Morphological changes in micro- and nano- scale were most observed on the flame treated PE-LD surface, whereas the electret phenomenon was observed on PE-LD, PE-HD and PP surfaces only after corona treatment.
1468. Lahti, J. A. Savolainen, J.P. Rasanen, T. Suominen, and H. Huhtinen, “The role of surface modification in digital printing on polymer-coated packaging board,” Polymer Engineering and Science, 44, 2052-2060, (Nov 2004).
Digital printing is increasingly being used for package printing. One of the major techniques of digital printing is dry-toner electrophotography. This paper evaluates the printability of three different extrusion coatings used for packaging boards: low-density polyethylene (PE-LD), ethylene methyl acrylate (E/MA) and polyethylene terephthalate (PET). Extrusion coatings in general have an impervious, chemically inert, nonporous surface with low surface energies that cause them to be non-receptive to bonding with toners. The most common methods used in improving the adhesion properties of polymer coatings are different surface treatments. These increase the surface energy and also provide the polar molecular groups necessary for good bonds between the toner and polymer molecules. The polymer coatings have been modified with electrical corona discharge treatment. The effects of corona on polymer surfaces and the correlation between surface modification and print quality have been evaluated. Results show that sufficiently high surface energy and surface-charge uniformity are necessary for even print quality and toner adhesion. E/MA and PET have the required surface-energy level without the corona treatment, but PE-LD needs surface modification in order to succeed in the electrophotographic process. E/MA also has exceptional surface-charge properties compared with PET and PE-LD. Polym. Eng. Sci. 44:2052–2060, 2004. © 2004 Society of Plastics Engineers.
2336. Lahti, J., K. Eiroma, T.-M. Tenhunen, M. Pykonen, M. Toivakka, and M. Tuominen, “Atmospheric plasma treatment of plastic packaging film: Effects on surface properties and UV inkjet printability,” Presented at 13th TAPPI European PLACE Conference, 2011.
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