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Langmuir 1991, 7 ,2492-2497

Reduction and Oxidation of Cellulose Surfaces by Means of Cold Plasma

C.M.Gilbert Carlsson' and G6ran StrBm
Institute for Surface Chemistry, Box 5607, S-114 86 Stockholm, Sweden Received August 6, 1990. In Final Form: December 5, 1990
Hydrogen and oxygen plasma treatment of two cellulose materials, a filter paper of pure celluloee and a greaseproof paper with a fairly high surface content of wood resin, has been studied with ESCA as well as by contact angle or water absorption. The hydrogen plasma treatment reducea the hydroxyl groups on the cellulose and creates low molecular weight materials. Due to the lower polarity, water absorption is reduced. The oxygen plasma treatment of the pure cellulose both oxidizes and reduces the surface. The resin-rich paper, which has a hydrophobic nature, shows improved water wettability after both hydrogen and oxygen plasma treatments. Introduction Surface modification of synthetic and natural polymers is of considerable importance in a wide range of industrial applications. It has been shown that cold plasma treatment is a powerful technique to obtain tailor-made surface properties while retaining the bulk properties of different materials.1J A cold plasma arises when a low-pressure gas at room temperature is subjected to an electric discharge, e.g., a radio frequency or a microwave field.3 As a whole the plasma is neutral. It consists mainly of neutral species as well as small fractions of free electrons, ions, radicals, excited molecules, and photons. The activated species interact with the surface in different ways. The final result depends on the gas used, treatment time, and parameters associated with the equipment, such as gas flow, energy input, and g e ~ m e t r y . ~ , ~ Plasma treatment of synthetic polymers has been used extensively to improve wettability,z6adhesion,z6and other material properties.' Studies on cellulose materials have also been reported. Westerlind et reported improved adhesion between a resin-rich paper and polyethylene after oxygen and ammonia plasma treatment. Benerito et found improved water and oil wettabilityof cotton cellulose after treatment with argon, nitrogen, or air plasma. Improved water wettability of cellulose strips after different plasma treatments has been reported by Chang Tang and Bosisio.lo Although a number of publications have shown the effects of plasma treatments, the chemistry involved is still poorly understood. The aim of this work is to carefully study the effect of oxygen and hydrogen plasma on the chemical composition and wettability of two cellulose materials. The first is a filter paper, made from a very pure cotton cellulose. The second is a greaseproof paper
(1) Kinloch, A. J. Adhesion and Adhesiues; Chapman and Hall: London, 1987; Chapter 4.

containing fairly high amounts of wood resins made from sulfite pulp. In a subsequent paper we will discuse the effect of these plasma treatments on the adhesion to polyethylene. Experimental Section Materials. The filter paper used was a Munktell filter paper made from pure cotton. The greaaeprcmf paper was made of bleached sullite pulp without any additives. It contains0.5% extractives,i.e, reaidual wood resin, as determined by extraction with dichloromethane using the SCAN-C 7:62 standard method. Plarma Treatment. For hydrogen plasma treatment a P h maprep 100 reactor from Nanotech Inc. was used. It operates at 1 3 . 5 2 MHz. The gas flow was 10 mL/min (STP) and the power 100 W. The preaaure was approximately 100 Pa. The oxygen plasma treatment was carried out in a reactor built at the Institute for Surface Chemistry. It operates in the kilohertz range. The p b m a treatment was performed under two different conditions. When 5 Wand 20 mL/min (STP) were . 7 Pa and the generator was operating at used the pressure was 8 350 kHz, while at 20 W and 5 mL/min (STP) the p m u r e was 4 . 4 Pa and the frequency 275 kHz. ESCA. The ESCA measurement8 were made with a byboldHeraeus LH 2000 electron spectrometerequipped with an Al K a X-ray source. The analyzed area was 1 X 10 m m and the exit angle from the sample to the detector was 90. Peak intensities were determinedby integrating the area under the peaksand the sensitivityfactors used were 0 . 2 1 for C 1s and 0.64 for 0ls.1* The curve fitting to the C 1s peaks was done with a Gaussian curvefitting program. Contact Angle Measurementr and Absorption Studies. The contact angles were measured on 10-pL dropleta placed on the samples. The liquids used were deionized and distilled water and diiodomethane. The absorption times were measured by placing a 0.10-mL droplet on the sample and observing the time required for total absorption. Results a n d Discussion ESCA Spectrum of Pure Cellulose. Figure l a shows the C 1s signal originating from the filter paper. The resolved signal shows four peaks, which correspond to carbons in different oxidative status.13J4 The C 1 peak represents unoxidized carbons, the CZcarbons with one oxygen bond, the CBcarbons with two oxygen bonds, and the CCcarbons with three oxygen bonds. Pure cellulose
_ _ _ _
~~

(2) Wu, S. Polymer Interface and Adhesion; Marcel Dekker. New York; 1982; Chapter 9. (3) Yaeuda, H.PloamoPolymerization;AcademicPrecle: London, 1985. (4) Gerencer, L. J. Polym. Mater. Sci. Eng. 1990, 62, 125. (6) Cleich, H.; Criens, R. M.:Mosl6. H. C.: Leute. U. Znt. J. Adhes. Adhes. 1989, 9,88. (G).Weeterdahl,C: A. L.; Hall, J. R.; Schram, E. C.; Levi, D. M. J. Collord Interface Scr. 1974, 47, 610. (7) Triolo, P. M.; Andrade, J. D. J.Biomed. Mater. Res. 1983,17,129. (8) Weeterlind, B.; Larseon, A.; Rigdahl, M. Int. J.Adhes. Adhes. 1987,
CI

I , 141.

.a.

(11) Carleeon, C. M. G.; Strt)m, G. Surf. Interface A d . 1991,17,611. pQ 80-82. (13) Dorrie, G.

(9) Benerito, R. R.; Ward, T. L.;Soignet, D. M.; Hinjcea, 0. Text. Res. J. 1981,51, 224. (10) Chan Tang, T. W.; Boeieio, R. G . Tappi 1980,63,111.

(12) Herder, P. C. TheeL, Trita-FYK-8801, Stockholm, Sweden,1988,

M.; Gray, D. C. Cellul. Chem. Technol. 1978,12,9. (14) Gray, D. C. Cellul. Chem. Technol. 1978, 12,736.

0743-7463 f 91f 2407-2492$02.50 f0

0 1991 American Chemical Society

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Figure 1. Curve-resolvedESCA C 1ssignal of (a) untreated and (b) 1-min and (c) 8-min hydrogen plasma treated filter paper. The peak marked C1 consists of unoxidizedorganic carbon (CHx), the Co peak contains carbons with one bond to oxygen (C-O), the Cs peak collects carbonswith two bonds to oxygen (C-0 and 0-C-O), and the C, peak contains carbons with three bonds to oxygen (0-C=O).

801

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Figure 2. Structure of cellulose.

-.

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0-c-0

0-c=o

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1.6

is a homopolysaccharide composed of 8-D-glucopyranose units.l6 As can be seen from Figure 2, each unit contains five carbons with one bond to oxygen and one carbon with two bonds to oxygen. Thus one expects a curve-resolved ESCA C 1s signal to consist of only two peaks (CZand C3). The carbon composition, C ~ / C ~ / C ~ / C for I , the pure cellulose is expected to be 083:17:0. However, the carbon composition for the filter paper, given by the ESCA measurements, was found to be 8:72:17:3. The appearance of the two peaks C1 and C4 may be due to either contamination of the filter paper or a chemical change in the cellulose structure. If one interprets the C1 and C4 peaks as due to chemical changes, then calculations with the carbon composition of the filter paper suggest that one carbon per two glucopyranose units has been reduced to a methylene or methyl group, and that approximately one per five glucopyranose units has been oxidized to a carboxylic acid or carboxylate group. Hydrogen Plasma Treatment of Filter Paper. After exposure to a hydrogen plasma the surface composition of the filter paper changes. This can be seen in the shape of the C 1s signals shown in parts b and c of Figures 1, which correspond to 1-and 8-min exposure, respectively. The Cz carbon decreases and the C1 increases after prolonged exposure to the hydrogen plasma. Figure 3 shows the change in the O/C atomic ratio and the different carbon peaks as a function of treatment time. The different carbon peaks are given as percent of the C 1s signal. The O/C ratio decreases from 0.75 to about one-third of that value. Carbon singly bonded to oxygen decreases sharply and carbon with two bonds to oxygen decreases slightly. A high increase is observed for unoxidized carbons while a fairly moderate increase is observed for carbons with three bonds to oxygen. These data strongly suggest a dehydroxylation of the cellulose molecule, since the CZcarbons are predominantly bound to hydroxyl groups. The increase in the C4 peak can be explained by two processes. Most probably it is a result of a reaction between radicals in the surface with oxygen
(15) Sjbtr6m, E.Wood Chemktry: Fundamentals and Applications; Academic Press: New York, 1981.

Duration of treatment / min Figure 3. Hydrogen plasma treatment of filter aper. Changes in the O/C atomic ratio and in the amount of the 8fferent carbons due to time of treatment.
098

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0

0,6

i n
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0 After plasma treatment After plasma treatment and extraction

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Figure 4. Effect of hydrogen plasma treatment and extraction (ethanoland dichloromethane)on the composition of filter paper as characterized by ESCA.

when the sample is removed from the plasma reactor. Another explanation might be that oxygen removed from the cellulose becomes activated in the plasma and then reacts with the cellulose creating C4 groups. The ESCA spectra show several indications that the molecular structure of the cellulose is degraded upon prolonged exposure to a hydrogen plasma. In Figure 3 it is shown that the O/C ratio reaches a level of 0.25. This corresponds to 1.5 oxygen per glucopyranose unit, while a structure with the two ether bonds still present and all the hydroxyl groups removed would contain two oxygen atoms per unit. Figure 3 also shows that the CZpeak decreases to below 33%. This shows that the carbons with one ether bond are lost to some degree. The C3 peak decreases, indicating that some of the carbons with two ether bonds are changed to some other carbon type. Thus we conclude that neither of these decreases can take place without a ring opening or a chain scissoring. To study the degradation further, a hydrogen plasma treated filter paper was extracted with ethanol and with dichloromethane. Figure 4 shows the changes in the C 1s signal due to the extraction. The C1 peak, which increased

2494 Langmuir, Vol. 7, No. 11, 1991

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Figure 6. Curve-resolvedESCA C 1s signal of (a)untreated and (b) 2-min and (c) 8-min hydrogen plasma treated greaseproof paper.
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Duration of treatment / min Figure 5. Absorption time for 0.10-mL water droplets on hydrogen plasma treated filter papers. After 8-min plasma treatment the absorption time is >500 a.

during plasma treatment, is reduced after the extraction; and the Cz peak is increased. After the extraction, the 1 and CZin the treated paper is not totally amount of C recovered. Thus we conclude that the hydrogen plasma treatment produces low molecular weight degradation products that are less polar than the extracted surface and this surface is in turn less polar than the untreated filter paper. The adhesive strength of these treated filter papers to polyethylene was studied. A detailed report will be published.11 It was found that even though the hydrogen plasma treatment drastically reduced the adhesive strength, it was regained after extraction of the filter paper (i.e., removal of degradation products). We thus conclude that a reduced polarity of the paper surface, which correlates to a reduced surface free energy, does not decrease the adhesive strength as long as the surface does not carry low molecular weight material. If there is low molecular weight material on the surface, the adhesion drops drastically. The observed failure is in this case then presumably due to a weak boundary layer16formed by the low molecular weight degradation products. The wettability of the hydrogen plasma treated, but not extracted, filter papers was studied by measuring the absorption time for 0.10-mL water droplets. Due to the surface roughness and the fast absorption of water on an untreated filter paper it was not possible to measure contact angles on the papers treated for less than 8 min. As can be seen in Figure 5, the absorption time increases with the plasma treatment time. After an 8-min plasma treatment, the absorption was too slow to be measured accurately due to evaporation. The filter paper absorbs water slowly, and spreading occurs laterally in the paper, yet the droplet maintains a constant contact angle, over the 8-min measurement period, of -115'. This shows that the hydrogen plasma treatment gives the paper surface a hydrophobic character. ESCA Spectrum of Greaseproof Paper. The greaseproof paper contains high amounts of wood resins in the surface." The resins are detected mainly as aliphatic hydrocarbon, Le., in the C1 peak in ESCA. Hence, the ESCA C 1s signal in Figure 6a shows a different shape compared to the untreated filter paper in Figure la. Hydrogen Plasma Treatment of Greaseproof Paper. During exposure to a hydrogen plasma the greaseproof paper shows changes similar to the filter paper, C1increases and CZdecreases (Figure 6b, c). Due to the wood resins
(16) Bikerman, J. J. J. Appl. Chem. 1961, 11, 81. (17) Abereon, G. M.TAPPI Spec. Tech. Assoc. Publ. 1970, No. 8,282.

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Duration of tre8tment / min Figure 7. Hydrogen plasma treatment of filter paper. Changes in the O/C atomic ratio and the different carbons due to time of treatment.

in the greaseproof paper surface, the O/C ratio is only 0.45. Figure 7 shows that there is a weak maximum in the O/C ratio after 2-3-min treatment time corresponding to a minimum in the amount of unoxidized carbon. This is probably due to removal of wood resins from the surface caused by a slight sputtering effect of this low molecular weight material. Figure 8 shows electron micrographs of untreated, hydrogen plasma treated, and oxygen plasma treated greaseproof paper. Although it is quite difficult to interpret surface roughness from SEM pictures of paper surfaces, a comparison of the hydrogen plasma treated and untreated paper suggests that the hydrogen plasma somewhat smooths the surface. Another explanation to the O/C maximum might be that radicals formed during the plasma treatment may react with the atmospheric oxygen when the sample is moved out of the plasma chamber. After longer exposure times the effect of the hydrogen plasma on both greaseproof paper and filter paper seems to be the same. The O/C ratio and the amounts of different carbons level out at approximately the same amounts in both cases; see Figures 3 and 7. Since the greaseproof paper is very smooth, contact

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Duration of treatment / min Figure 9. Contact angles for (m) water and (A)diiodomethane
on hydrogen plasma treated greaseproof paper.

Figure 10. Curve-resolved ESCA C 1s signal of (a) untreated

filter paper and filter paper following 2-min treatment in oxygen plasma a t (b) 5 W, 20 mL/min (STP) and (c) 20 W, 5 mL/min (STP).

Figure 8. Scanning electron micrograph of (from top to bottom) (a) untreated, (b)hydrogen plasma treated, and (c) oxygen plasma treated greaseproof paper. The scale shows the dimension of 0.1 mm.

angles could be measured with both water and diiodomethane (Figure 9). The contact angle of diiodomethane remains constant, showing that the dispersion part of the surface free energy does not change. The decreasing contact angle of water with longer hydrogen plasma exposureis surprising, since the ESCA results show a decrease in the surface polarity. However, the contact angle of water is not only determined by the average polarity of the local distribution of the hydrophobic material.l8J9 If the hydrogen plasma removes hydrophobic patches of wood resin, it is not unlikely that the advancing

contact angle decreases upon hydrogen plasma treatment, although the average surface becomes less polar. Another explanation to the low contact angles might be the formation of surface-active degradation products, which reduces the surface tension of the water. These are probably formed from degradation products of the wood resins since this effect is not seen on the pure cellulose of the filter paper. When the hydrogen plasma treated greaseproof paper was laminated with polyethylene a slight, but not very pronounced decrease was observed in the adhesive strength. Oxygen Plasma Treatment of Filter Paper. Figure 10 shows the carbon peak of the filter paper after oxygen plasma exposure at two different conditions. At low power and high flow rate the changes in the surface seem to be small. But, at the higher power and lower flow rate the shape of the carbon peak changes dramatically. The amount of C1 increases to a high level and there is some formation of C4. As can be seen in Figures 11and 12, the changes occur in the first 15 s and then level out. The effect follows the changes that have been observed in synthetic polymers.20p21 Since all carbon in cellulose is bound to at least one oxygen, oxygen incorporation in most cases would cause degradation of the molecule. The tremendous increase of C1 might be due to scissoring in the cellulose. Radicals forming during the plasma treatment process might terminate, creating double bonds or cross-linking. The increase of C4 indicates that some oxygen is incorporated, forming carboxylic acid groups.
(18) Dettre, R. H.; Johnson, R. E., Jr. J . Phys. Chem. 1965,69,1507. (19) Johnson, R. E., Jr.; Dettre, R. H. J . Phys. Chem. 1964,68,1744. (20)Gerenser, L. J. J. Adhes. Sci. Technol. 1987, 1, 303. (21) Clark,D. T.; Dilks, A. J. Polym. Sci. 1979,17,957.

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Carlsson and Strom

Figure 13. Curve-resolved WCA C l a signal of (a) untreated and (b) 16-8and (c) 60-8oxygen plasma treated greaseproofpaper.

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Duration of treatment / min Figure 11. Oxygen plasma treated (5 W, 20 mL/min (STP)) filter paper. Changes in the O/C atomic ratio and the different carbons due to time of treatment.

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Duration of treatment / min Figure 12. Oxygen plasma treated (20 W, 5 mL/min (STP)) filter paper. Changes in the O/C atomic ratio and the different
carbons due to time of treatment.

Oxygen Plasma Treatment of Greaseproof Paper. Figures 13 and 14 shows the effect of oxygen plasma on the surface composition of the greaseproof paper. All changes occur during the first 15s. The treatment reduces the content of unoxidized carbons and increases the amount of carbons with two or three bonds to oxygen. The O/C ratio increases from 0.455 to -0.6.

Duration of treatment / I Figure 14. Oxygen plasma treated (20 W, 5 mL/min greaseproof paper. Changes in the O/C atomic ratio and the different carbons due to time of treatment. Figure 8 suggests that the oxygen plasma treatment has a sputtering effect on the material. The contact angles with water were very difficult to determine since the water droplets swell the oxygen plasma treated greaseproof paper. The result of this swelling is lower contact angle values and irregularly shaped droplets. Therefore, the contact angles on oxygen-treated greaseproof paper can only be roughly estimated. The values lie 0 ' and 30' for papers treated for 15 s and below between 1 1 0 ' for papers treated for 30 s or more. It is well-known that oxygen plasma treatment can produce hydroperoxide group^.^^*^ In order to identify such groups in our material, treated and untreated greaseproof papers were exposed to sulfur dioxide, which tags the group by formation of a sulfonate group. Figure 15 showsthe ESCA S 2 p signal for both untreated and treated paper. The treated paper showed a sulfur signal corresponding to approximately 3 hydroperoxide groups per 100 glucopyranose units. The oxygen plasma treated greaseproof paper showed a sharp increase in adhesive strength when laminated to
(22) Briggs, D.; Kendall, C. R. Int. J . Adhea. Adhea. 1982,2, 13. (23) Gerensar,L.J.; Elman, J. F.; Mason, M.G.; Pochan,J.M. Polymer 1985,26, 1162.

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Conclusions
The results show that chemical changes occur during cold plasma treatment of cellulose materials and that they affect the wettability and the adhesion of the material. The hydrogen plasma reduces the hydroxyl groups on the cellulose and low molecular weight materials are formed. The water wettability of a pure cellulose is reduced due to the lower polarity of the surface, but for a paper with high amounts of resins in the surface the wettability is improved. The oxygen plasma treatment both oxidizes and reduces the surface. Among the oxygen-containing groups incorporated, hydroperoxides are formed. The water wettability of the greaseproof paper is improved after the plasma treatment.

1310

1315

1320

Figure 15. ESCA S 2p signal from oxygen plasma treated and untreated greaeeproof paper, both exposed to SOZ.

polyethylene.11 This is probably due to the formation of hydroperoxides, which decompose homolytically at the temperature used during laminationa and then may form covalent bonds t o the polyethylene surface.
(24)b m n ,8. w.; shaw, R In Organic Peroxides; Swem, D., Ed.; Wdry Intancrenw: New Yorir, 1970; Vol.1, p 106.

Acknowledgment, We thank Professor Per Stenius for valuable comments on the manuscript and Pia Fildt for skilful work on the scanning electron microscope. We also thank the Swedish National Board for Technical Development and Bo Rydins Foundation for Scientific Research for financial support.
&&try NO. Ha, 1333-74-0; 0 2 , 7782-44-7; H20,7732-18-5; CH212, 75-11-6; cellulose, 9004-34-6.