Abstract
Since more than 40 years ammonia plasma exposure of polyolefins is used for introduction of primary amino groups. The selectivity of this reaction and the yield in primary amino groups was found to be low. Here, a prominent side-reactions of this process was investigated, the hydrogenation by NH3 plasma. For identification of hydrogenation ammonia (NH3) and deuterated ammonia (ND3) were exposed to polyethylene (h-PE) and fully deuterated polyethylene (d-PE) as well as hexatriacontane (h-HTC) and fully deuterated hexatriacontane (d-HTC) as low-molecular weight model for PE. H–D exchange was assumed and detected by Time-of-Flight Secondary Ion Mass Spectrometry (ToF–SIMS), X-ray Photoelectron Spectroscopy (XPS), Attenuated Total Reflectance (ATR-FTIR) and 1H and 2H Nuclear magnetic Resonance. Results show a significant H–D exchange within the sampling depth of ATR (2.5 μm). However, N- and NH2 introduction was limited to the topmost surface as shown by SIMS and XPS (a few nanometers).
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References
Hollahan JR, Stafford BB, Falb RD, Payne ST (1969) J Appl Polym Sci 13:807
Gähde J, Wittrich H, Schlosser E, Friedrich J, Kaiser G (1972) DD-patent 106:052
Lawton EL (1974) J Appl Polym Sci 18:557
Allred RE, Merrill EW, Roylance DK (1985) Polym Sci Technol 27:333
Friedrich J, Gähde J, Frommelt H, Wittrich H (1976) Faserforsch Textiltechn/Z Polymerenforsch 27:604
Friedrich J, Loeschcke I, Gähde J, Frommelt H, Wittrich H (1974) DD-patent 115:708
Friedrich J, Gähde J, Frommelt H, Wittrich H (1976) Faserforsch. Textiltechn/Z Polymerenforsch 27:599
Friedrich J, Loeschcke I, Gähde J, Richter K (1981) Acta Polym 32:337
Friedrich J (1981) Contr Plasma Phys 21:261
Klemberg-Sapieha JE, Küttel OM, Martinu L, Wertheimer MR (1991) J Vac Sci Technol A9:2975
Lub J, van Vroonhoven F, Bruninx E, Benninghoven A (1989) Polymer 30:40
Friedrich J, Ivanova-Mumeva VG, Gähde J, Andreevskaya GD, Loeschcke I (1983) Acta Polym 34:171
d′ Agostino R, Stendardo M, Favia P (1995) In: Heberlein JV, Ernie EW, Roberts JT (eds) 12th Symposium on plasma chemistry, vol I. University of Minneapolis, p 27
Meyer-Plath A, Mix R, Friedrich J (2007) In: Mittal KL (ed) Adhesion aspects of thin films, vol III. VSP, Leiden, p 177
Oehr C, Müller M (1999) Surf Coat Technol 116–119:802
Wedenew WJ, Gurwitsch LW, Kondratjew WH, Medwedew WA, Frankewitsch EL (1971) Energien chemischer Bindungen, Deutscher Verlag für Grundstoffindustrie, Leipzig
Boenig HV (1988) Fundamentals of plasma chemistry and technology. Technomic, Lancaster
Ivanova-Mumeva VG, Andreevskaya GD, Friedrich J, Gähde J (1980) Acta Polym 31:752
Geng S, Friedrich J, Gähde J, Guo L (1999) J Appl Polym Sci 71:1231
Gerenser LJ (1987) J Adhes Sci Tech 1:303
Oran U, Swaraj S, Lippitz A, Unger WES (2006) Plasma Process Polym 3:288
Truica-Marasescu F, Girard-Lauriault P-L, Lippitz A, Unger WES, Wertheimer MR (2008) Thin Solid Films 516:7406
Girard-Lauriault P-L, Desjardins P, Unger WES, Lippitz A, Wertheimer MR (2008) Plasma Process Polym 5:631
Retzko I, Friedrich JF, Lippitz A, Unger WES (2001) J Electr Spectr Rel Phenom 121:111
Tibbitt JM, Bell AT, Shen M (1976) J Macromol Sci Chem A10:513
Friedrich J, Loeschcke I, Gähde J, Richter K (1981) Acta Polym 32:337–343
Wertheimer MR, Schreiber HP (1081) J Appl Polym Sci 13:2087
Chawla AS, Sipehia R (1984) J Biomed Mater Res 18:537
Cho DL, Yasuda HK (1986) J Vac Sci Technol A4:2307
Munkholm C, Wait DR, Milanovich FP, Klainer SM (1986) Ana Chem 58:1427
Iriyama Y, Yasuda HK (1988) J Appl Polym Sci Appl Polym Symp 42:97
Nakayama Y, Takahagi T, Soeda F, Hatada K, Nagaoka S, Suzuki J, Ishitani A (1988) J Polym Sci Part A Polym Chem 26:559
Inagaki N, Tasaka S, Kawai H (1989) J Adhes Sci Technol 3:637
Chapell PJC, Brown JR, George GA, Willis HA (1991) Surf Interface Anal 17:143
Gengenbach TR, Xie X, Chatelier RC, Griesser HJ (1994) J Adhes Sci Technol 8:305
Griesser HJ, Chatelier RC, Gengenbach TR, Johnson G, Steele JC (1994) J Biomater Sci Polym Ed 5:531
Badey JP, Espuche E, Sage D, Chabert B, Jugnet Y, Batier C, Duc TM (1996) Polymer 37:1377
Schröder K, Meyer-Plath A, Keller D, Besch W, Babucke G, Ohl A (2001) Contr Plasma Phys 41:562
Yasuda HK, Marsh HC, Brandt S, Reilley CN (1977) J Polym Sci Polym Ed 15:991
Foerch R, Hunter DH (1992) J Polym Sci Part A Polym Chem 30:279
Foerch R, Beamson G, Briggs D (199) Surf Interf Anal 17:842
Liston EM, Martinu L, Wertheimer MR (1993) J Adhes Sci Technol 7:1091
Friedrich J, Wittrich H, Gähde J (1978) Faserforsch Textiltechn/Z Polymerenforsch 29:481
Friedrich J, Reiners H-D (1980) Berlin, unpublished results
Friedrich J, Bertrand P (1989) Louvain-la-Neuve, unpublished results
Min H, Wettmarshausen S, Friedrich J, Unger WES (2011) J Anal At Spectrom. doi:10.1039/C1JA10043B
Bennett AE, Rienstra CM, Auger M, Lakshmi KV, Griffin RG (1995) J Chem Phys 103:6951
Hartmann SR, Hahn EL (1962) Phys Rev 128:2042
Cook RL, Langford CH, Yamdagni R, Preston CM (1996) Anal Chem 68:3979
Bruker Almanac (2011) Analytical tables and product overview. ISBN:13978-3-929431-25-4
Friedrich J, Unger WES, Lippitz A, Gross T, Rohrer P, Saur W, Erdmann J, Gorsler H-V (1996) In: Mittal KL (ed) Polymer surface modification: relevance to adhesion. VSP, Utrecht, pp 49–72
Friedrich J, Unger WES, Lippitz A, Koprinarov I, Kühn G, Weidner S, Vogel L (1999) Surf Coat Technol 116–119:772
Meyer-Plath A (2002) PhD thesis, Ernst-Moritz-Arndt University of Greifswald
Oran U, Swaraj S, Friedrich JF, Unger WES (2005) Surf Coat Technol 200:463
Swaraj S, Oran U, Lippitz A, Friedrich JF, Unger WES (2005) Surf Coat Technol 200:494
del Fanti NA (2008) Infrared spectroscopy of polymers. Thermo Fisher Scientific, Madison
Team of authors (1973) Strukturaufklärung-Spektroskopie und Röntgenbeugung. VEB Deutscher Verlag für Grundstoffindustrie, Leipzig
Colthup NB (1950) J Opt Soc Am 40:397
Friedrich J, Mix R, Kühn G (2004) In: d′Agostino R, Favia P, Oehr C, Wertheimer MR (eds) Plasma processing and polymers. Wiley-VCH, Weinheim, pp 3–21
Strobel JM, Strobel M, Lyons CS, Dunatov C, Perron S (1991) J Adhes Sci Technol 5:119
Behnisch J, Zimmermann H, Friedrich J (1992) Int J Mater Sci 16:139
Vasilets VN, Kuznetsov AV, Sevastianov VI (2004) J Biomed Mater Res Part A 69:428
Weidner S, Kühn G, Friedrich J, Unger WES, Lippitz A (1996) Rapid Comm Mass Spectrom 10:727
Murillo R, Poncin-Epaillard F, Segui Y (2007) Eur Phys J Appl Phys 37:299
Hudis M (1972) J Appl Polym Sci 16:2397
Friedrich J, Geng S, Unger WES, Lippitz A (1998) Surf Coat Technol 98:1132
Vickerman JC, Briggs D, Henderson A, The Static SIMS Library (1999) Manchester, Surface Spectra
Wagner D, Dikmen B, Döbele HF (1998) Plasma Sour Sci Technol 7:462
Fukumasa O, Tauchi Y, Yabuki Y, Mori S, Takeiri Y (2002) Ninth international symposium on the production and neutralization of negative ions and beams. AIP Conf Proc 639:28–34
Lyang CY, Lytton MR, Boone CJ (1960) J Polym Sci 47:139
Lyang CY (1964) IR spectra of polymers: deuteration and polarization. In: Bacon K (ed) Newer methods of polymer characterization. Interscience, New York, pp 33–102
Tasumi M, Shimonouchi T (1966) J Polym Sci A1:1011–1021
Jelinski J (1986) Deuterium NMR of solid polymers. In: Komoroski RA (ed) High resolution NMR spectroscopy of synthetic polymers in bulk. VCH Publishers, Deerfield Beach
Lyman T (1906) Astrophys J 23:181
Holländer A, Klemberg-Sapieha JE, Wertheimer MR (1994) Macromolecules 27:2893
Painter LR, Arakawa ET, Williams MW, Ashley JC (1980) Radiat Res 83:1
Truica-Marasescu F-E, Wertheimer MR (2005) Macromol Chem Phys 206:744
Nakayama M, Shibahara M, Maruyama K, Kamat K (1993) J Mater Sci Lett 12:1380
Skurat V (2003) Nucl Instrum Methods Phys Res B 208:27
Fanghänel E (2004) Organikum, 22nd edn. Wiley-VCH, Weinheim
Hergenröther PM, Levine HH (1967) J Polym Sci A 1:1453
Noren CJ, Wang J, Perler FB (2000) Angew Chem Intern Ed 39:450
Holländer A, Wilken R, Behnisch J (1999) Surf Coat Technol 116–119:788
Finke B, Schröder K, Ohl A (2008) Plasma Proc Polym 5:386
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Wettmarshausen, S., Min, H., Unger, W. et al. Significance of Hydrogen–Deuterium Exchange at Polyolefin Surfaces on Exposure to Ammonia Low-Pressure Plasma. Plasma Chem Plasma Process 31, 551–572 (2011). https://doi.org/10.1007/s11090-011-9304-5
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DOI: https://doi.org/10.1007/s11090-011-9304-5