Nonthermal Plasmas for Materials Processing E-Book

Jörg Florian Friedrich

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 1119

Veröffentlichungsjahr: 2022

Beschreibung

NONTHERMAL PLASMAS FOR MATERIALS PROCESSING This unique book covers the physical and chemical aspects of plasma chemistry with polymers and gives new insights into the interaction of physics and chemistry of nonthermal plasmas and their applications in materials science for physicists and chemists. The properties and characteristics of plasmas, elementary (collision) processes in the gas phase, plasma surface interactions, gas discharge plasmas and technical plasma sources, atmospheric plasmas, plasma diagnostics, polymers and plasmas, plasma polymerization, post-plasma processes, plasma, and wet-chemical processing, plasma-induced generation of functional groups, and the chemical reactions on these groups along with a few exemplary applications are discussed in this comprehensive but condensed state-of-the-art book on plasma chemistry and its dependence on plasma physics. While plasma physics, plasma chemistry, and polymer science are often handled separately, the aim of the authors is to harmoniously join the physics and chemistry of low-pressure and atmospheric-pressure plasmas with polymer surface chemistry and polymerization and to compare such chemistry with classic chemistry. Readers will find in these chapters * Interaction of plasma physics and chemistry in plasmas and at the surface of polymers; * Explanation and interpretation of physical and chemical mechanisms on plasma polymerization and polymer surface modification; * Introduction of modern techniques in plasma diagnostics, surface analysis of solids, and special behavior of polymers on exposure to plasmas; * Discussion of the conflict of energy-rich plasma species with permanent energy supply and the much lower binding energies in polymers and alternatives to avoid random polymer decomposition * Technical applications such as adhesion, cleaning, wettability, textile modification, coatings, films, etc. New perspectives are explained about how to use selective and mild processes to allow post-plasma chemistry on non-degraded polymer surfaces. Audience Physicists, polymer chemists, materials scientists, industrial engineers in biomedicine, coatings, printing, etc.

Leseprobe

Table of Contents

Cover

Title Page

Copyright

Preface

1 Introduction

2 Basic Principles of the Plasma State of Matter

2.1 Characteristics and Physical Properties of Plasmas

2.2 Elementary Processes and Collision Cross Section

2.3 Interaction of Non-Thermal Plasmas with Condensed Matter

2.4 Non-Thermal Plasmas of Electric Gas Discharges

3 Plasma Diagnostics

3.1 Introduction

3.2 Overview of Diagnostic Methods Used for the Characterization of Non-Thermal Plasmas

3.3 Analysis of Charged and Neutral Plasma Particles in Non-Thermal Plasmas

3.4 Microwave Interferometry

3.5 Mass Spectrometry

3.6 Plasma and Laser-Induced Optical Emission Spectroscopy

3.7 IR Broadband and IR Laser Absorption Spectroscopy

4 Methods of Polymer and Polymer Surface Analysis

4.1 Introductory Remarks

4.2 Photoelectron Spectroscopy (XPS) or Electron Spectroscopy for Chemical Analysis (ESCA)

4.3 Secondary Ion Mass Spectrometry

4.4 NEXAFS – Use of Synchrotron Radiation

4.5 Infrared Reflection Absorption Spectroscopy (IRRAS)

4.6 Size-Exclusion Chromatography (SEC)/Gel Permeation Chromatography (GPC) and Field-Flow-Fractionation (FFF)

4.7 Matrix-Assisted Laser/Desorption Ionization Time-of-Flight Mass Spectrometry (MALDI-ToF-MS)

4.8 Electrospray Ionization Time-of-Flight Mass Spectrometry (ESI-ToF-MS)

4.9 Overview of Methods

5 Chemical Interactions Between Polymer and Plasma

5.1 Introduction

5.2 General Conflict Between High Plasma Energies and Low Dissociation Energies of Bonds in Polymers

5.3 Chemical Bonds and Functional Groups in Polymers

5.4 Response of Different Types of Polymers to Plasma Exposure

6 Polymer Surface Functionalization

6.1 Important Properties of Polymers

6.2 Why Pretreatment?

6.3 Chemical and Structural Problems of Polymers Provoked by Plasma Pretreatment

6.4 Inevitability of Simultaneous Functionalization and Polymer Degradation

6.5 Physical and Chemical Attacks of the Plasma to Polyolefin Surfaces

6.6 Chemical Grafting onto Plasma-Exposed Polymer Surfaces

6.7 Oxidation of Polymers by Exposure to the Oxygen Low-Pressure Plasma

7 Sensitivity of Polymer Units and Functional Groups Towards Exposure to Oxygen Plasma

7.1 Introductory Remarks

7.2 Behavior of Polymer Structure Upon Exposure to Oxygen Plasma

7.3 Etching Behavior of Polymers Upon Exposure to Oxygen Plasma

7.4 Classification of Polymers with Similar Degradation Behavior on Exposure to Oxygen Plasma

7.5 Stability of Surface Functionalization and Superposition with Post-Plasma Effects Upon Exposure to Air

7.6 Surface Oxidation of Polyolefins Using Atmospheric-Pressure Plasmas (DBD, APGD or Corona Discharge, Spark Jet, etc.)

7.7 Oxidation of Carbon Nanomaterials

7.8 Generation of Monosort O-Functional Groups at Polyolefin Surfaces as Anchor Points for Grafting of Molecules

7.9 Post-Plasma Chemical Grafting of Molecules, Oligomers or Polymers Onto OH-Groups

7.10 Course of Oxidation from Virgin Polymer to Oxidized Polymer and Finally to CO

2

8 Ammonia and Bromine Plasmas

8.1 Generation of Monosort NH

2

Groups

8.2 Bromine Plasma

9 Noble Gas Plasmas

9.1 Characterization of Noble Gas Plasmas

9.2 Polymer Crosslinking Caused by Noble Gas Plasmas

9.3 Vacuum-Ultra Violet Radiation Emitted by Noble Gas Plasmas

10 Plasma Polymerization

10.1 Introduction

10.2 Milestones in History

10.3 General Features of Plasma Polymers

10.4 Mechanisms of Plasma Polymerization

10.5 Special Aspects of Plasma Polymerization

10.6 Locus of Plasma Polymerization

10.7 Plasma Polymers with Monosort Functional Groups

10.8 Attempts to Increase the Yield of Functional Group

10.9 Plasma Copolymerization

10.10 Grafting Onto Plasma Polymers as Special Case of ‘Graft-Copolymerization’

10.11 Significant Side Reactions

10.12 Plasma Polymers Deposited by Atmospheric-Pressure Plasmas

11 Technical Applications

11.1 Introduction

11.2 Adhesion Promotion

11.3 Cleaning

11.4 Wettability

11.5 Etching of Polymers

11.6 Barrier Layers or Barrier Formation

11.7 Anti-Fouling Layers

11.8 Sterilization

11.9 Water Purification and Desalination

11.10 Flame Protection

11.11 Textile Modification

11.12 Modification of Carbon Fibers and Nanotubes

11.13 Silent Discharge and Excimer Radiation

11.14 Conducting Films

11.15 Scratch-Resistant Coatings

11.16 Underwater Plasma

Index

Wiley End User License Agreement

List of Tables

Chapter 2

Table 2.1 Diffusion lengths Λ for different geometries of the diffusion problem ...

Table 2.2 Phase and group velocity for different electric field frequencies ω in...

Table 2.3 Examples of equilibrium reactions in plasmas at CTE.

Table 2.4 Selected atomic transition in helium, argon, hydrogen and oxygen, take...

Table 2.5 Examples of metastable excited states of rare gas atoms and molecules.

Table 2.6 Ionization energy and electron affinity of selected atoms and molecule...

Table 2.7 Classification of elementary collision processes in plasma volume. (*:...

Table 2.8 Polarizability of selected atoms and molecules: averaged polarizabilit...

Table 2.9 Important similarity parameters in gas discharge physics.

Chapter 3

Table 3.1 Overview of diagnostic methods and techniques for low temperature plas...

Table 3.2 Spectroscopic data for the plasma processing of the gases hydrogen, ox...

Table 3.3 Overview of the vibration type of important molecular groups and the c...

Chapter 4

Table 4.1 Methods of polymer analysis.

Table 4.2 Overview of methods and areas of application*.

Chapter 5

Table 5.1 A rough comparison of appraised energies occurring as binding energies...

Table 5.2 Functional groups in polymers and their possible degradation products ...

Chapter 6

Table 6.1 Some important properties of polymers.

Table 6.2 Interactivity of several groups of polymers.

Table 6.3 Zip-lengths for polymer depolymerization [32, 34].

Table 6.4 List of important binding energies of substituents on carbon in the C1...

Table 6.5 Densities of species in the plasma discharges [81].

Table 6.6 Crystallinity of technical polymers [96].

Table 6.7 Ionization energies and energies of excited and metastable states in e...

Table 6.8 Etching efficiency of different plasmas on low-density polyethylene (L...

Table 6.9 Etch rates of polymers at mg/cm² min x 103 upon exposure to helium pla...

Table 6.10 Quantum yield for the scission of the main chain.

Table 6.11 Reactions during oxygen plasma exposure of PET surfaces and their pro...

Table 6.12 Thermal properties of plasma treated branched and linear polyethylene...

Chapter 7

Table 7.1 Efficiency of different processes.

Table 7.2 Some important advantages and disadvantages of polymers in comparison ...

Table 7.3 Advantages and disadvantages of polymer surface modification.

Table 7.4 Principal comparison of chemical reduction processes of O-functional g...

Table 7.5 Examples of processes for producing monotype functional groups.

Table 7.6 A few representative examples for O/C and C1s fitted results.

Table 7.7 List of important binding energies of substituents on carbon in the C1...

Chapter 8

Table 8.1 Standard dissociation energies [1, 10, 19].

Table 8.2 Positive low mass secondary fragment ions in ToF-SIMS and their propos...

Table 8.3 Reaction enthalpy of the halogenation of polyolefins.

Table 8.4 Ionization potentials of halogen-containing plasma gases (and methane)...

Table 8.5 Spacer grafting onto OH and B groups at polypropylene surfaces.

Chapter 10

Table 10.1 Types of starting materials for plasma polymerization with examples.

Table 10.2 Standard dissociation energies (SDE) of aliphatic compounds.

Table 10.3 Deposition rate of monomers and precursors as polymer layer upon expo...

Table 10.4 NMR results of different plasma polymers.

Table 10.5 Relative concentration of unsaturations.

Table 10.6 13C-NMR measured C-H groups in plasma polymers from ethane, ethylene ...

Table 10.7 13C-NMR measurement of the H/C ratio of different plasma polymers [54...

Table 10.8 Types of precursors which can polymerize on exposure to low-pressure ...

Table 10.9 Interactions of molecules and oligomers with polymer surfaces.

Table 10.10 Monomers and precursors for deposition of plasma polymers containing...

Table 10.11 Results of addition of gases to the monomer/precursor during plasma ...

Table 10.12 Yield of primary amino groups.

Table 10.13 Overview of bands located around the wavenumber of ν≈2200 cm-1. [M. ...

Chapter 11

Table 11.1 Overview of the selectivity of gas plasmas related to the desired fun...

List of Illustrations

Introduction

Figure 0.1 Walhalla near Regensburg; (left) general view, (right) inner arrangem...

Figure 0.2 (From left to right) Fredrick K. McTaggart and his book on plasma che...

Figure 0.3 Stanley L. Miller.

Figure 0.4 Drost’s book Plasmachemie (Plasma Chemistry).

Figure 0.5 (Left to Right) Buddy Ratner; Alexander Fridman and Gary Friedman’s b...

Figure 0.6 (From left to right) Inagaki’s book; Jose Martin Martinez; Hynek Bied...

Figure 0.7 (From left to right) Michael Wertheimer, Christian Oehr, Ricardo d’Ag...

Chapter 1

Figure 1.1 Excitation and ionization in gas plasmas.

Figure 1.2 Ionizing avalanche in plasma.

Figure 1.3 Energy distribution to collision and radiation processes during plasm...

Figure 1.4 Jablonski scheme of emission of radiation of organic molecules after ...

Figure 1.5 Overview of processes used for pretreatment of polymer surfaces.

Figure 1.6 Possible O functional groups at polymer surfaces after exposure to ox...

Figure 1.7 Processes at the surface and in the bulk of polymers when exposed to ...

Figure 1.8 Factors influencing the quality and characteristics of plasma.

Figure 1.9 Influence of plasma on structure and composition of polymer samples.

Figure 1.10 Factors affecting the structure of plasma polymers and the resulting...

Figure 1.11 Plasma diagnostics.

Figure 1.12 Important methods used for surface analysis and characterization.

Figure 1.13 Analytical methods for characterization of bulk properties of polyme...

Chapter 2

Figure 2.1 Temperature-density plot of the plasma matter. In this book the plasm...

Figure 2.2 Debye shielding potential φ(r) (2.7) with z=1 and four selected elect...

Figure 2.3 Formation of ambipolar electric field Ea in inhomogeneous plasma (L>>...

Figure 2.4 Real part of the dispersion function (2.42) for electromagnetic wave ...

Figure 2.5 Electron cyclotron motion in magnetic field Bz=0.0875 Tesla with para...

Figure 2.6 Electron transport due to the

Figure 2.7 Schematic of the binary collision process between particles Ak and Bl...

Figure 2.8 Scheme of the three-particle collision process due to simultaneous co...

Figure 2.9 Example of consecutive chemical reactions of first order. Shown is th...

Figure 2.10 Schematic of elementary collision processes between particles in the...

Figure 2.11 Schematic of elementary collision processes on the surface. A+/m: io...

Figure 2.12 Combined partial energy levels – Grotrian diagram for the hydrogen a...

Figure 2.13 Energy level diagram of the hydrogen molecule (H2), taken from Sharp...

Figure 2.14 Principle of direct electron impact ionization of a diatomic molecul...

Figure 2.15 Scheme of the hard sphere collision cross section and examples of ga...

Figure 2.16 Polarization interaction between the charged particle (point charge ...

Figure 2.17 Illustration of the differential scattering of charged particles (q1...

Figure 2.18 CF3-F potential energy and dissociative electron attachment in CF4 a...

Figure 2.19 Negative ion production F- (maximum at 6.7 eV) and CF3- (maximum at ...

Figure 2.20 Electron excitation cross section of ground state atomic oxygen O(3P...

Figure 2.21 Optical emission excitation cross section for atomic oxygen multiple...

Figure 2.22 Partial and total electron impact ionization cross section of CF4 fr...

Figure 2.23 Complex interaction between non-thermal plasma and condensed matter.

Figure 2.24 Qualitative behaviour of the electrical potential in the transition ...

Figure 2.25 High-voltage rf sheath: charged particle density and moving electron...

Figure 2.26 Electric potentials (idealized) for asymmetric capacitively coupled ...

Figure 2.27 (a) Ion energy distribution function (Ar+) at the rf electrode in as...

Figure 2.28 Overview and classification of important electric gas discharge plas...

Figure 2.29 Analytical calculation of the pressure reduced first Townsend coeffi...

Figure 2.30 Breakdown voltage in dependence on p∙dE (Paschen curve) calculated w...

Figure 2.31 Schematic of the DC glow discharge at low pressure with the separate...

Figure 2.32 (a) Double plate cathode configuration. (b) Cylindrical cathode conf...

Figure 2.33 Universal graph from equation (2.264) for the estimation of the elec...

Figure 2.34 Ions and electrons reaching the electrode from the discharge center ...

Figure 2.35 Absorbed electric power per volume unit for electric field frequency...

Figure 2.36 Power absorption of electrons per volume unit at 2.45 GHz microwave ...

Figure 2.37 Discharge configurations for CCP and ICP with RF power supply and th...

Figure 2.38 (a) Negative corona discharge around a thin wire with negative ions ...

Chapter 3

Figure 3.1 (a) Principle of single electric probe measurement (current-voltage c...

Figure 3.2 Generated current-voltage characteristics of a stationary argon plasm...

Figure 3.3 The plots show the first derivative (left) of current-voltage charact...

Figure 3.4 Probe current Ip (left) including the ion saturation current I+,sat (...

Figure 3.5 Determination of the electron temperature from the linear slope in th...

Figure 3.6 (a) Generated current-voltage characteristics of a symmetric double p...

Figure 3.7 Passive RF compensation for 1356 MHz with additional electrode, capac...

Figure 3.8 (a) Schematic of the discharge setup for local probe measurement and ...

Figure 3.9 (a) Second derivative of the retarding electron current. (b) Electron...

Figure 3.10 Spatial distribution of the normalized positive ion saturation curre...

Figure 3.11 (a) Propagation of microwaves in plasmas for ωMW >wpe. (b) Refractiv...

Figure 3.12 Schematic of the microwave interferometer to measure the phase shift Δ𝜑 and to determine the line-integrated electron density.

Figure 3.13 Principle of the 160 GHz heterodyne microwave interferometer includi...

Figure 3.14 (a) Experimental setup for low-pressure plasma diagnostics using 160...

Figure 3.15 (a) Side view of the Gaussian beam above the powered RF electrode (C...

Figure 3.16 (a) Averaged electron density in argon and oxygen CCP, and the negat...

Figure 3.17 (a) Fluctuation of the electron density in oxygen CCP at 100 Pa and ...

Figure 3.18 (a) Electron density in argon ICP vs. coil voltage with the step-lik...

Figure 3.19 (a) Pulsed oxygen ICP (10 Hz, 50% duty cycle) with additional electr...

Figure 3.20 Comparison of the electronegativity from electron density peak in th...

Figure 3.21 Schematic of mass spectrometry for extracted neutral or charged plas...

Figure 3.22 Schematic of the ideal Paul trap with hyperbolic quadrupole potentia...

Figure 3.23 (a) The mass m2 is transmitted in the quadrupole with the applied pa...

Figure 3.24 (a) Double-stage quadrupole mass spectrometer (EPIC 1000, Hiden Anal...

Figure 3.25 Mass spectrum after 20 s (left) and 170 s (right) plasma process tim...

Figure 3.26 Temporal conversion of ethylenediamine (EDA) in gaseous reaction pro...

Figure 3.27 Threshold mass spectrometry for N+ (left) and CF3+ (right) ions in N...

Figure 3.28 Dissociative electron attachment with the attachment cross section t...

Figure 3.29 Dissociative electron attachment with different attachment cross sec...

Figure 3.30 Principle of data acquisition in pulsed RF plasma using a multi-chan...

Figure 3.31 CF2 density in pulsed RF plasma (1 Hz, with 50% duty cycle) in CF4 a...

Figure 3.32 C2F4 density in pulsed RF plasma (1 Hz, 50% duty cycle) in CF4 and C...

Figure 3.33 (top) Potential behavior and self-bias in asymmetric CCP at 13.56 MH...

Figure 3.34 Multi-peak structure of the ion energy distribution of positive ions...

Figure 3.35 Ion energy distributions (shifted) of single-charged argon ions at t...

Figure 3.36 Molecular (O2+) and atomic (O+) oxygen ion energy distribution (shif...

Figure 3.37 Schematic configuration for measurement of the energy distribution o...

Figure 3.38 Energy distribution of fast negative oxygen ions (O-) at the grounde...

Figure 3.39 Scheme of the Czerny-Turner spectrograph and detection of spectrally...

Figure 3.40 Adjustment of the plasma radiation to the spectrograph.

Figure 3.41 VUV-UV radiation of H2 CCP at 13.56 MHz (250 W, 150 Pa).

Figure 3.42 UV-vis-NIR radiation of H2 CCP at 13.56 MHz (200 W, 150 Pa).

Figure 3.43 Atomic oxygen lines at 777.4 nm and 844.6 nm from oxygen RF plasma (...

Figure 3.44 Atmospheric O2 A band centered at 762 nm from oxygen RF plasma (CCP,...

Figure 3.45 Emission intensity of atomic oxygen ions from oxygen RF plasma (CCP,...

Figure 3.46 Emission intensity of molecular oxygen ions from oxygen RF plasma (C...

Figure 3.47 Emission spectrum of the atmospheric O2 A band b1Σg+(ν’=0) → X3∑g- (...

Figure 3.48 Schematic of the atmospheric O2 A band (b1∑g+ → X3∑g-) at 762 nm and...

Figure 3.49 The emission intensity of the pP and pQ branch from the atmospheric ...

Figure 3.50 Cross section of cylindrical plasma with the radius R. The measureme...

Figure 3.51 Schematic of the phase resolved optical emission spectroscopy for an...

Figure 3.52 Comparison between the spatio-temporal pattern for the normalized em...

Figure 3.53 Normalized excitation rate from atomic oxygen emission over the RF c...

Figure 3.54 Normalized intensity from argon atom emission at 750 nm and atomic o...

Figure 3.55 Schematic setup of two-photon absorption laser-induced fluorescence ...

Figure 3.56 Two-photon absorption for atomic oxygen and xenon as well as the mea...

Figure 3.57 The axial distribution of the fluorescence signal for atomic oxygen ...

Figure 3.58 The quantified number density shows a non-linear increase of atomic ...

Figure 3.59 The 3D plot provides the axial distribution (r=0) as well as the rad...

Figure 3.60 The 3D plots showing the normalized positive ion saturation current ...

Figure 3.61 Schematic of the FTIR spectrometer with Michelson interferometer.

Figure 3.62 (a) Spectral line with the sinc function (3.50). (b) Spectral line w...

Figure 3.63 Exponential decrease of the intensity due to absorption from molecul...

Figure 3.64 FTIR absorbance spectra of the gas phase showing the consumption of ...

Figure 3.65 Gas phase kinetics of stable molecules from FTIR absorption spectros...

Figure 3.66 Increasing total pressure from 60 Pa to 85 Pa in RF plasma without g...

Figure 3.67 Kinetics of the EDA, NH3, HCN and CH4 in plasma reactor with gas flo...

Figure 3.68 Optical emission intensity of the EDA-Ar plasma and the temporal dev...

Figure 3.69 Schematic of IR-TDLAS setup for analysis of infrared active gas mole...

Figure 3.70 Temporal CF density in pulsed RF plasma (CCP, 13.56 MHz, P=100 W, p=...

Figure 3.71 Spectral absorption range in wavenumber for different fluorocarbons ...

Figure 3.72 Kinetics of CF, CF2 and C2F4 in RF plasma at different RF power (CCP...

Figure 3.73 Kinetics of CF, CF2 and C2F4 with increasing H2 admixture added to t...

Chapter 4

Figure 4.1 Overview of analyzed regions in polymers by different analytical meth...

Figure 4.2 Principle processes at solid surfaces upon exposure to X-rays.

Figure 4.3 Effects of photoionization upon exposure to X-rays.

Figure 4.4 Schematic of a SIMS crater and general chance to detect greater or ev...

Figure 4.5 Schematic of IRRAS.

Figure 4.6 Principle of size exclusion in SEC/GPC.

Figure 4.7 Principle of thermal field-flow fractionation.

Figure 4.8 Schematic showing the MALDI-ToF principle.

Figure 4.9 Principle and photograph of electrospray ionization technique.

Figure 4.10 Evaporation techniques for macromolecules.

Chapter 5

Figure 5.1 Energy distribution of electrons, gas atoms or molecules and ions in ...

Figure 5.2 Reactions coordinate for plasma polymerization.

Figure 5.3 Correlation between surface energy and oxygen concentration of oxygen...

Figure 5.4 C1s peak of octadecyltrichlorosilane monolayers (self-assembled monol...

Figure 5.5 NEXAFS CK edge spectrum of octadecyltrichlorosilane monolayers (self-...

Figure 5.6 Etch rate, orientation and O introduction into octadecyltrichlorosila...

Figure 5.7 Schematic of surface modification of aliphatic structures upon exposu...

Figure 5.8 Oxygen uptake of different polymers upon exposure to the oxygen low-p...

Figure 5.9 XPS and NEXAFS results of the survival of original carbonyl and aroma...

Figure 5.10 Structural and compositional changes of polymers upon exposure to lo...

Chapter 6

Figure 6.1 Exemplified comparison of polyolefin interactions with solids in depe...

Figure 6.2 Bond dissociation energies in polyethylene and general possibilities ...

Figure 6.3 Dependence of mechanical strength of polymers on their molecular weig...

Figure 6.4 XPS-C1s peaks of polyethylene and poly(acrylic acid).

Figure 6.5 Principle and example of the application of angle-resolved X-ray phot...

Figure 6.6 XPS O1s peak of poly(ethylene terephthalate) before and after exposur...

Figure 6.7 N1s peak of pulsed plasma polymerized (duty cycle 0.1) allylamine con...

Figure 6.8 C1s peak of a commercial spin-coated polystyrene film.

Figure 6.9 Valence band spectra of polypropylene and polyethylene and the contin...

Figure 6.10 XPS survey spectrum of polystyrene.

Figure 6.11 Matching of C1s peaks of untreated polyethylene and polyethylene exp...

Figure 6.12 Self-assembled monolayer of octadecyltrichlorosilane before and afte...

Figure 6.13 SEIRA spectra of a Langmuir-Blodgett monolayer of behenic acid befor...

Figure 6.14 Reaction scheme of reduction of O-functional groups to OH groups and...

Figure 6.15 XPS survey scans of polypylene surfaces, after exposure to oxygen pl...

Figure 6.16 Comparison of the gas and electron temperatures for different atmosp...

Figure 6.17 Plasma equipment as used by Favia et al. [86].

Figure 6.18 Progression of polymer oxidation upon exposure to the oxygen plasma.

Figure 6.19 Mass spectrometric tracking of formed molecular species by exposure ...

Figure 6.20 Schematic overview of possible molecular structures in partially cry...

Figure 6.21 Presumptive primary oxidation of polyethylene upon exposure to the o...

Figure 6.22 Scheme of molecular and supermolecular orientation in polyethylene a...

Figure 6.23 Dependence of etching rate on degree of crystallinity.

Figure 6.24 Crystallinity of LDPE vs. time of exposure to the oxygen plasma [139...

Figure 6.25 Schematic of the two different processes during the etching of parti...

Figure 6.26 Oxygen introduction by exposure to different types of discharges in ...

Figure 6.27 Waterfall presentation of XPS survey scans of O2, Ar plasmas and UV ...

Figure 6.28 Model of plasma modification of polymer surfaces by particle bombard...

Figure 6.29 Original, degraded and crosslinked polymer structures as schematics.

Figure 6.30 Differences in polymer surface modification after exposure to noble ...

Figure 6.31 Polypropylene glycol-methylenediisocyanate-polyurethan after 1 h exp...

Figure 6.32 Schematic plot of changes in molecular weight of polystyrene (110,00...

Figure 6.33 Concentration of the crosslinked fraction in polystyrene in dependen...

Figure 6.34 Set of ThFFF fractograms of polystyrene films (230 nm) exposed at di...

Figure 6.35 Dependence of crosslinked fraction in polystyrene on layer thickness...

Figure 6.36 Vacuum-UV absorption of polymers.

Figure 6.37 Gel-permeation chromatograms of oxygen plasma modified polymers.

Figure 6.38 Exponential increase of oxygen introduced onto polyethylene surfaces...

Figure 6.39 C1s signals of self-assembled monolayers of octadecyltrichlorosilane...

Figure 6.40 C1s peak of polyethylene after O2 plasma treatment (15 s).

Figure 6.41 Oxygen introduction and fitted C1s on polyethylene surfaces in depen...

Figure 6.42 C1s peak of polystyrene standard (in grey) and after exposure to the...

Figure 6.43 Oxygen introduction into polystyrene if exposed to the oxygen plasma...

Figure 6.44 Shake-up intensity of polystyrene versus time of exposure to the oxy...

Figure 6.45 C K-edge, PS treated with direct-current oxygen plasma (6 Pa).

Figure 6.46 Photoelectron yield of O K-edge of NEXAFS spectra, PS with direct cu...

Figure 6.47 C1s peak of polycarbonate standard (in grey) and after exposure to t...

Figure 6.48 Normalized photoelectron yield (PEY) of NEXAFS OK and CK edge spectr...

Figure 6.49 Changes in C1s and O1s signals of poly(ethylene terephthalate) after...

Figure 6.50 Difference of the C1s signals of poly(ethylene terephthalate) before...

Figure 6.51 XPS measurements of the introduction of oxygen onto PET surfaces usi...

Figure 6.52 CK-and OK edges in the NEXAFS spectra of poly(ethyleneterephthalate)...

Figure 6.53 Dependence of relative concentration of structural elements in poly(...

Figure 6.54 Possible reactions of poly(ethylene terephthalate) exposed to the ox...

Figure 6.55 MALDI-ToF mass spectra of linear PET exposed for 180 s to the oxygen...

Figure 6.56 Polar contribution of surface energy vs. oxygen concentration at pol...

Figure 6.57 Peel strength of 150 nm evaporated Al layers onto oxygen plasma expo...

Figure 6.58 Principal course of adhesion onto oxygen plasma-modified polyolefins...

Figure 6.59 Dependence of O and OH incorporation into polyethylene surfaces with...

Figure 6.60 NEXAFS determined orientation factor (20-90° difference spectra) and...

Figure 6.61 Scanning force microscopic pictures of untreated biaxially stretched...

Figure 6.62 Branched, linear and copolymer polyethylenes in the virgin state.

Figure 6.63 Topology of 15 s in O2 plasma etched polyethylenes.

Figure 6.64 Topology of 15 s in O2 plasma etched polyethylenes followed by washi...

Figure 6.65 Enthalpies of O2 and Ar plasma-treated polyethylenes in dependence o...

Figure 6.66 C1s and O1s→π*ring related order parameter of poly(ethylene terephth...

Figure 6.67 Change in molar mass distribution of poly(ethylene terephthalate) ex...

Chapter 7

Figure 7.1 Changes in structural elements of polymers during the exposure to the...

Figure 7.2 Concentration of important structural elements of several polymers at...

Figure 7.3 Loss in molecular weight (MN) of polystyrene with time of exposure to...

Figure 7.4 Process parameter in plasma and in polymer or at polymer surface whic...

Figure 7.5 Near edge X-ray absorption fine structure (NEXAFS) spectra of oxygen ...

Figure 7.6 Principal course of etching rate of polyolefins upon exposure to oxyg...

Figure 7.7 Bond increments contributing to photoresist etching upon its exposure...

Figure 7.8 Classes of polymer degradation upon exposure to oxygen plasma.

Figure 7.9 MALDI-TOF MS spectra of a linear macrocycle-free PET 1,700 before and...

Figure 7.10 Shift of molecular weight distribution of PMMA caused by depolymeriz...

Figure 7.11 Crosslinking of poly(methyl methacrylate) upon exposure to oxygen or...

Figure 7.12 MALDI spectra of PEG 4,800 exposed to low-pressure oxygen plasma for...

Figure 7.13 Thermal field-flow fractionation (ThFFF) of polystyrene films with d...

Figure 7.14 Proposed mechanism of radical formation in polyethylene upon exposur...

Figure 7.15 Schematic of radical formation, its saturation with molecular oxygen...

Figure 7.16 Post-plasma introduction of oxygen after exposure to the argon plasm...

Figure 7.17 Post-plasma introduction of oxygen into polyethylene after different...

Figure 7.18 Post-plasma introduction of oxygen after exposure to the argon plasm...

Figure 7.19 Radical quenching by gassing with Br2 or NO.

Figure 7.20 UV-vis spectra of polyethylene exposed to argon plasma followed by i...

Figure 7.21 Post-plasma introduction of oxygen (XPS) into polyethylene after its...

Figure 7.22 Survey of newly introduced methods for modification of polyolefin an...

Figure 7.23 Comparison of oxygen introduction into polypropylene in dependence o...

Figure 7.24 Tensile shear strengths of PU-PP specimen as a function of oxygen co...

Figure 7.25 Dependence of the O/C ratio on energy density of the atmospheric die...

Figure 7.26 Surface energy of polyethylene as a function of oxygen concentration...

Figure 7.27 Schematic comparison of plasma polymerization and electrospray of po...

Figure 7.28 Proposed chemical structure of deposited polymer films.

Figure 7.29 Efficiency of different aerosol plasma treatments in the oxidation o...

Figure 7.30 O and OH introduction into polyolefins using the deposition of PEG-g...

Figure 7.31 Shift and loss in intensity of molecular weight of PMMA 1900 in MALD...

Figure 7.32 ESI spraying of a PMMA solution under conditions with additional exp...

Figure 7.33 Proposed molecular structure of chemically oxidized graphene (graphe...

Figure 7.34 Oxygen plasma-induced epoxidation of naphthalene as a model for grap...

Figure 7.35 Schematic of modification of carbon fiber surfaces and subsequent ch...

Figure 7.36 Wetting of polyethylene with water before and after equipment with O...

Figure 7.37 Processes for generation of monosort functionalized polyolefin surfa...

Figure 7.38 Efficiency of different wet-chemical processes in reduction to OH gr...

Figure 7.39 Oxygen plasma treatment of polyolefins and subsequent wet-chemical r...

Figure 7.40 XPS survey scans of polypylene surfaces after exposure to oxygen pla...

Figure 7.41 IR spectra of polypropylene surfaces after exposure to oxygen plasma...

Figure 7.42 Proposed mechanism of COOH formation on polyolefin surfaces [121].

Figure 7.43 Possible reactions of poly(acrylic acid) upon exposure to oxygen or ...

Figure 7.44 Graft reactions of amino groups to polyolefin surfaces, transesterif...

Figure 7.45 Ways to produce aldehyde groups and their chemical reaction.

Figure 7.46 Proposed scheme of plasma-assisted fluorination and oxyfluorination.

Figure 7.47 FTIT --->FTIR spectra of untreated, chemically and plasma-chemically...

Figure 7.48 Chemical and plasmachemical fluorination of polypropylene as well as...

Figure 7.49 Changes in surface composition of polytetrafluoroethylene upon expos...

Figure 7.50 PTFE surface defluorination by an H2 plasma and secondary oxygen int...

Figure 7.51 Model after Prachar and Friedrich.

Figure 7.52 Scheme of amino acid sequences grafted onto the surface of PP.

Figure 7.53 Mechanism of paraffin thermal oxidation as found in refs. [14, 20–24...

Figure 7.54 Scheme of ethane thermal oxidation.

Figure 7.55 Gaseous products emitted from polyolefins on exposure to low-pressur...

Figure 7.56 List of O-functional groups which indicate chain scissions.

Figure 7.57 Scheme of LMWOM formation (•=radical).

Figure 7.58 MALDI-ToF mass spectrum of hexatriacontane exposed to the low-pressu...

Figure 7.59 Relative contribution to the measured XPS signals for different phot...

Figure 7.60 Representation of establishment of a steady state between continuous...

Figure 7.61 Presumed O/C course at the surface of polyolefins in contact with ga...

Figure 7.62 Scheme of evaporation of small LMWOM clusters and subsequent oxidati...

Chapter 8

Figure 8.1 Examples of chemical compounds with amino groups.

Figure 8.2 Schematic view of methods for introduction of NH2 groups to the surfa...

Figure 8.3 Amino group formation at polypropylene surface during the ammonia pla...

Figure 8.4 Reaction of aminated carbon fibers with bisphenol-A-based epoxy resin...

Figure 8.5 Amino group formation at carbon surface during the ammonia plasma exp...

Figure 8.6 N1s peak at carbon fiber surface after ammonia plasma exposure for 15...

Figure 8.7 C1s peak of carbon fibers after 1800 s exposure to the ammonia rf pla...

Figure 8.8 Changes in the C1s peak of polytetrafluoroethylene after exposure to ...

Figure 8.9 Changes in the C1s signal of HOPG exposed to the cw-rf low-pressure a...

Figure 8.10 C1s peaks of N2, NH, and NH3+3 H2 plasma-treated polypropylene (cw-r...

Figure 8.11 Dependence of NH2 and Ntotal yield on mixing ratio of N2 and H2 in t...

Figure 8.12 Dependence of NH2/Ntotal quotient on mixing ratio of N2 and H2 in th...

Figure 8.13 NH3, N2 and NH3+H2 cw-rf plasma exposure of polypropylene surfaces a...

Figure 8.14 NH3, N2 and NH3+H2 pulsed-rf plasma exposure of polypropylene surfac...

Figure 8.15 (a) LB Monolayer of stearic acid exposed to the ammonia plasma (cw-r...

Figure 8.16 Hexatriacontane (h-HTC) exposed to NH3 and ND3 plasma (FTIR-ATR).

Figure 8.17 Deuterated hexatriacontane (d-HTC) exposed to NH3 or ND3 plasma.

Figure 8.18 Comparison of the 13C direct excitation spectrum of d-HTC (upper spe...

Figure 8.19 2H solid-echo (top) and corresponding 2H MAS line shape for d-HTC sh...

Figure 8.20 NH3, N2 and NH3+H2 pulsed-rf plasma exposure of polyethylene surface...

Figure 8.21 Polypropylene exposed to the ammonia plasma (cw-rf plasma, 10 W, 8 P...

Figure 8.22 N1s peak of HTC treated in ammonia plasma (cw-rf, power=15W, pressur...

Figure 8.23 C1s peaks of plasma-polymerized allylamine with derivatized amino gr...

Figure 8.24 Schematic of NH3 and ND3 plasma treatment of aliphatic chains hydrog...

Figure 8.25 Comparison of unspecific and monosort surface functionalization.

Figure 8.26 Differences in reactivity of hydrogen bonds in branched aliphatic ch...

Figure 8.27 Bromination of polyolefin surfaces by exposure to bromine, bromoform...

Figure 8.28 Time dependence on bromine introduction into polyolefin by exposure ...

Figure 8.29 Removal of loosely bonded brominated (CHBr3 plasma) polypropylene la...

Figure 8.30 Influence of the polarity of solvent used for removal of loosely bon...

Figure 8.31 Different types of plasma bromination.

Figure 8.32 Proposed model of plasma-polymerized allyl bromide.

Figure 8.33 Bromine introduction onto the surface layer of polypropylene upon ex...

Figure 8.34 Time-dependence of different bromination processes and their yield i...

Figure 8.35 Inductively and capacitively coupled plasma and afterglow (inductive...

Figure 8.36 Influence of the folding of ions (Faraday cage, 10 W) or UV radiatio...

Figure 8.37 C1s peak of polyethylene after exposure to the chloroform plasma.

Figure 8.38 Comparison of different methods of plasma treatment for incorporatio...

Figure 8.39 Gas phase fluorination and oxyfluorination as well as plasma fluorin...

Figure 8.40 Bromination of poly(ethylene terephthalate) upon exposure to bromofo...

Figure 8.41 Introduction of bromine into COC surfaces in dependence on time of e...

Figure 8.42 Overview of possible conversions of C-Br groups into other monosort ...

Figure 8.43 Maximal yield in grafting of glycols and amines onto bromoform-modif...

Figure 8.44 Click reaction at brominated PE.

Figure 8.45 Some applications of covalently grafted molecules in adhesion, waste...

Figure 8.46 Octa(aminophenylene)-POSS (left) and calculated configurations after...

Figure 8.47 Grafting of poly(glycerol) dendrimers to brominated polypropylene su...

Figure 8.48 Dependence of grafted spacer molecules on length of spacer molecules...

Figure 8.49 Comparison of different plasma-assisted polymer surface functionaliz...

Figure 8.50 Structure of graphene and brominated (black, thick spheres) graphene...

Figure 8.51 Idealized structures of graphene and the completely hydrogenated pla...

Figure 8.52 Introduction of Br and O into HOPG in dependence on exposure to the ...

Figure 8.53 Introduction of Br into diverse carbon nanomaterials in dependence o...

Figure 8.54 Comparison of Br-introduction into diverse carbon nanomaterials in d...

Figure 8.55 Introduction of bromine into freshly cleaved HOPG surfaces exposed t...

Figure 8.56 Pressure dependence of the bromination efficiency and oxygen impurit...

Figure 8.57 Scanning electron microscopy (SEM) micrographs (1:50,000) of 0.5 and...

Figure 8.58 Surface topography of HOPG untreated and after exposure to the Kr pl...

Figure 8.59 NEXAFS spectra of HOPG before and after exposure to the krypton plas...

Figure 8.60 AFM micrographs of HOPG before and after 1 min exposure to the bromi...

Figure 8.61 Highly resolved Br 3d synchrotron XP spectra taken at 385 eV for Br2...

Figure 8.62 The C K-edge NEXAFS spectra of pristine HOPG and after treatment wit...

Figure 8.63 Integrated areas of C K-edge NEXAFS π* resonance (285.4 eV) areas vs...

Figure 8.64 The C K-edge NEXAFS spectra of pristine HOPG after treatment with Br...

Figure 8.65 Dependence of bromination efficiency of HOPG on direct exposure to B...

Figure 8.66 The C K-edge NEXAFS spectra of pristine a-C:H and after treatment wi...

Figure 8.67 Comparison of bromination percentage at standard conditions and unde...

Figure 8.68 XPS C1s peaks of HOPG, NG, MWCNT, and CF before (left) and after pla...

Figure 8.69 Addition of bromine onto aromatic double bonds in graphene following...

Figure 8.70 Schematic of bromination and post-plasma wet-chemical grafting of di...

Figure 8.71 Yield in wet-chemical post-plasma grafting of molecules with amino g...

Figure 8.72 Schematic of the structure of graphene and polyethylene (Fransen mic...

Chapter 9

Figure 9.1 Principal processes at polymer surfaces upon exposure to noble gas pl...

Figure 9.2 Electron temperature in dependence on gas pressure.

Figure 9.3 Gel particle formation in PET-Mylar foils after exposure to a MW low-...

Figure 9.4 Dependence of electron temperature and density on power input of radi...

Figure 9.5 Changes in the C1s signals of polyethylene and polypropylene after ex...

Figure 9.6 Indirect oxygen introduction into polyethylene and polypropylene afte...

Figure 9.7 Oxygen introduction in dependence on time of exposure to oxygen plasm...

Figure 9.8 Polyethylene exposed to argon low-pressure rf plasma and post-plasma ...

Figure 9.9 Polyethylene exposed to argon low-pressure rf plasma and post-plasma ...

Chapter 10

Figure 10.1 Schematic reactions of radical-initiated chain-growth polymerization...

Figure 10.2 Proposed model of plasma polymer produced from ethylene (PPE) with b...

Figure 10.3 Idealized retention of functional groups X during chain-growth polym...

Figure 10.4 Often tested applications of plasma polymers.

Figure 10.5 Step-growth mechanism of plasma polymerization proposed by Yasuda.

Figure 10.6 Schematical sketch of C6 barrier for chain-growth polymerization sta...

Figure 10.7 Strain energy of cycloalkanes.

Figure 10.8 Scheme of plasma polymerization.

Figure 10.9 Possible intermediates in the plasma of organic precursors which can...

Figure 10.10 Possible degrees of crosslinking.

Figure 10.11 Crosslinked skeleton with embedded oligomers.

Figure 10.12 Thermogravimetric properties of plasma-polymerized polystyrene in d...

Figure 10.13 Different types of plasma generation with internal electrodes or wo...

Figure 10.14 Scheme of capacitively coupled rf plasma with internal electrodes.

Figure 10.15 U=f(t,p) schemes for different plasma polymerization modes.

Figure 10.16 Increase of pressure during plasma polymerization in a closed syste...

Figure 10.17 Scheme of processes during plasma polymerization.

Figure 10.18 Variants of pulsed plasma.

Figure 10.19 Pulsed plasma and undesired side reactions that hinder the start of...

Figure 10.20 Schematics of pulsed-plasma (pp) and continuous-wave (cw) polymeriz...

Figure 10.21 Pulse-referenced deposition rates of ethylene and allyl alcohol (pu...

Figure 10.22 Deposition rate of styrene per pulse in dependence on plasma-off ti...

Figure 10.23 Electron density during a rf plasma pulse in styrene plasma.

Figure 10.24 Structural comparison of cw and pulsed plasma polymerized styrene i...

Figure 10.25 FTIR-ATR transmittance spectrum of pulsed-plasma-polymerized allyl ...

Figure 10.26 C1s signals of pulsed-plasma-polymerized allyl alcohol fitted and c...

Figure 10.27 Schematic view of the correlation between high pressure, high stick...

Figure 10.28 Single-point chain growing vs. growing in plane.

Figure 10.29 Principle of plasma and pressure pulse synchronization and measured...

Figure 10.30 From left to right: untreated, NH3 plasma-treated (continuous-wave)...

Figure 10.31 Pressure- and power-pulsed plasma (10 W). (a) allyl alcohol and eth...

Figure 10.32 XPS-C1s signals of pulsed-plasma polymerized ethylene with addition...

Figure 10.33 Comparison of mechanism and structure of polymers after classic cha...

Figure 10.34 NEXAFS CK-edge spectra of plasma-polymerized acetylene, ethylene an...

Figure 10.35 Partial disappearance of C=C double bonds in plasma polymers deposi...

Figure 10.36 Ozonation of C=C double bonds.

Figure 10.37 Comparison of C-H stretching vibrations in the IR spectra of commer...

Figure 10.38 Methyl groups in polymers.

Figure 10.39 Measured H/C elemental ratio of the plasma polymer of toluene along...

Figure 10.40 H/C and N/C elemental ratio in plasma-deposited 1:1 styrene-allyl a...

Figure 10.41 Electron temperatures in the Ar and the Ar-H2 plasmas (microwave, 4...

Figure 10.42 Principal course of electron temperature in a flow tube introducing...

Figure 10.43 Loss in aromatic rings in h8-toluene (■•) and d8-toluene (□○) plasm...

Figure 10.44 Proposed reactions of benzene in a glow discharge plasma.

Figure 10.45 CH-ratio in dc-plasma-polymerized toluene layers in dependence on t...

Figure 10.46 Tube position dependence of D↔H exchange in plasma polymers deposit...

Figure 10.47 Dielectric loss ε’’ versus temperature at frequency of 1 kHz for pu...

Figure 10.48 Energy needed for total dissociation of n-hexane molecule in compar...

Figure 10.49 Different modes of hexane “polymerization.”

Figure 10.50 Deposition rates of related hydrocarbon precursor molecules with cy...

Figure 10.51 IR spectra of polymerized precursor molecules upon exposure to low-...

Figure 10.52 Significant routes of plasma polymerization.

Figure 10.53 Dependence of etching or deposition rate on position in plasma at h...

Figure 10.54 Development of a floating potential with increasing plasma polymer ...

Figure 10.55 Toluene plasma polymerization in a tube-type reactor using low-pres...

Figure 10.56 Pattern of IR spectra in the range of wavenumbers between 2100 and ...

Figure 10.57 Size exclusion chromatograms of the soluble fraction of styrene pol...

Figure 10.58 Thermal field-flow fractionation of plasma-polymerized styrene (MAL...

Figure 10.59 Possible energy balance for plasma polymerization.

Figure 10.60 Gas phase and adsorption layer model for location of plasma polymer...

Figure 10.61 Influence of monomer pressure and flow on type of products (cf. [86...

Figure 10.62 Model of sputtering the deposited plasma polymer and re-deposition ...

Figure 10.63 Effect on plasma polymer structure of plasma-UV irradiation and mon...

Figure 10.64 Model scheme of radiation penetration through polymer films.

Figure 10.65 Differences between graft-co-polymerization and homopolymerization ...

Figure 10.66 Possible termination reactions of radical chain growth.

Figure 10.67 Comparison of XPS-C1s signals of reference, pulsed-plasma-polymeriz...

Figure 10.68 Indications of chemically-polymerized (regularly structured) sequen...

Figure 10.69 O/C ratio in pulsed-plasma-polymerized allyl alcohol in dependence ...

Figure 10.70 OH groups of pulsed-plasma-polymerized allyl alcohol in dependence ...

Figure 10.71 Dependence of IR bands of pp-AAl characteristic for OH, C=O and C-O...

Figure 10.72 NEXAFS-OK-edge spectrum of pp-AAl (mild plasma condition=1.0W/sccm)...

Figure 10.73 NEXAFS-CK-edge spectra of poly(vinylmethylketone) [PVMK], pp-AAl (m...

Figure 10.74 FTIR-ATR spectra of pp-AAl in dependence on wattage at constant dut...

Figure 10.75 Concentration of carboxylic groups versus duty cycle. The dashed li...

Figure 10.76 Infrared spectrum (grazing incidence reflectance) of pp-PAA (duty c...

Figure 10.77 FTIR absorbance spectrum of pulsed-plasma-polymerized acrylic acid ...

Figure 10.78 C1s peaks of commercial reference, electrospray-ionization-deposite...

Figure 10.79 Mechanism of thermal paraffin oxidation as found by Langenbeck, Pri...

Figure 10.80 XPS survey scan and C1s peak of pulsed-plasma-polymerized pp-AAm.

Figure 10.81 Derivatization reactions of fluorine labels with primary and second...

Figure 10.82 Proposed chain scission interpretation of the ToF-SSIMS results.

Figure 10.83 FTIR-ATR spectra of plasma-polymerized allylamine with NH-/NH2-spec...

Figure 10.84 Possible reactions of allylamine in the gas phase or after plasma p...

Figure 10.85 Schematics of direct and indirect oxidation of polymer upon exposur...

Figure 10.86 XPS-measured elemental composition of plasma polymers of allylamine...

Figure 10.87 Percentages of primary amino groups in total number of nitrogen spe...

Figure 10.88 FTIR-ATR spectra of plasma-polymerized allylamine with NH-/NH2-spec...

Figure 10.89 Yields in NH2 and N incorporations, selectivity of NH2/N vs. power ...

Figure 10.90 Yield in NH2 groups for plasma-initiated copolymerization of allyla...

Figure 10.91 XPS-survey spectra of plasma-polymerized pure allylamine and its 1:...

Figure 10.92 C1s and N1s peaks of plasma polymer layers from allylamine + ammoni...

Figure 10.93 C1s peaks of pulsed-plasma-polymerized allylamine (a, 50 W) and all...

Figure 10.94 N1s peaks of pulsed-plasma-polymerized allylamine (a, 50 W) and all...

Figure 10.95 Superposition of different N1s peaks produced by pulsed plasma prod...

Figure 10.96 Fitted C1s peak of grafted glutaraldehyde onto primary amino groups...

Figure 10.97 FTIR-ATR spectra of ppPAAm and ppPAAm + NH3 deposited as thin and t...

Figure 10.98 NH deformation and C=O stretching region in the range of 1550 to 17...

Figure 10.99 Roughly estimated overview of elemental composition of allylamine m...

Figure 10.100 Introduction of amino groups to carbon fiber and poyl(ethylene ter...

Figure 10.101 Idealized structures of allyl-amine homo- and copolymers and cross...

Figure 10.102 Dependence on copolymer deposition rates in dependence on types of...

Figure 10.103 Series of FTIR spectra of pulsed-plasma-induced copolymerization p...

Figure 10.104 Copolymerization of allyl alcohol with ethylene, butadiene and sty...

Figure 10.105 IR-measured OH absorbances in dependence on composition of the com...

Figure 10.106 Extraction of differently composed allyl alcohol-ethylene copolyme...

Figure 10.107 Correlation of polar component of surface energy and concentration...

Figure 10.108 NEXAFS OK-edge spectra of plasma-polymerized allyl alcohol-ethylen...

Figure 10.109 NEXAFS CK-edge spectra of pp-AAl (mild plasma condition=1.0W/sccm)...

Figure 10.110 Dielectric loss ε″ versus temperature at a frequency of 1000 Hz fo...

Figure 10.111 ThFFF fractograms of plasma-polymerized poly(allyl alcohol)-poly(s...

Figure 10.112 Differential molar mass distribution of plasma polymerized (at dif...

Figure 10.113 Deposition rates of copolymers from acrylic acid and styrene (duty...

Figure 10.114 Yield in COOH groups for different kinds of acrylic acid copolymer...

Figure 10.115 Dependence of polar contribution to surface energy of COOH and OH ...

Figure 10.116 Dielectric loss vs. temperature at a fixed frequency of 1 kHz of t...

Figure 10.117 Deposition rates of comonomer mixtures of allylamine vs. precursor...

Figure 10.118 Yield in N/C elemental ratio for different kinds of allylamine cop...

Figure 10.119 Influence of different plasma conditions on the respective IR spec...

Figure 10.120 Schematic of interfacial spacer bonding in metal-polymer composite...

Figure 10.121 Variants of interactions between coatings and modified or unmodifi...

Figure 10.122 FTIR-ATR spectra of plasma-polymerized allylamine with NH-/NH2-spe...

Figure 10.123 Poly(allylamine) and poly(acrylonitrile) polymerized in the rf pla...

Figure 10.124 Proposed generation of imine and cyclic structures of allylamine p...

Figure 10.125 XPS data of polymerized allylamine using different exposure to amb...

Figure 10.126 DSC measurements of pulsed-plasma-polymerized allylamine without a...

Figure 10.127 Post-plasma oxidation of plasma-polymerized n-hexane upon exposure...

Figure 10.128 XPS-C1s peaks of pulsed-plasma-polymerized allylamine referenced t...

Figure 10.129 Aging behavior of pulsed-plasma-polymerized allylamine in comparis...

Figure 10.130 Comparison of post-plasma incorporation of allyl alcohol and allyl...

Figure 10.131 Aging (change in O/C ratio and C1s peak fitting) of pp-AAl films u...

Figure 10.132 Schematic of exposure of the polyolefin surface to plasma and air ...

Figure 10.133 N, NH2 and O concentrations of washed (tetrahydrofuran) and unwash...

Figure 10.134 Post-plasma oxygen incorporation of plasma polymers upon exposure ...

Chapter 11

Figure 11.1 Overview of a few important technical applications of plasma process...

Figure 11.2 Reactions on C radical sites introduced by plasma exposure or irradi...

Figure 11.3 Lap shear strength of polyurethane and steel in dependence on cleani...

Figure 11.4 Dependence of measured lap shear strength on C1s/Fe2p peak ratio pro...

Figure 11.5 Vectorial model of sessile drop on solid surface after Young’s idea.

Figure 11.6 Different wetting behavior.

Figure 11.7 Secondary amorphization of crystalline structures in polymers by par...

Figure 11.8 Schematic principle of plasma polymer deposition in the inner surfac...

Figure 11.9 Overview of applications of bioactive plasma polymer layers.

Figure 11.10 Schematic of a scratch-resistant coated polycarbonate using the PEC...

Figure 11.11 Types of underwater treatmant, (a) capillary mode, (b) corona mode,...

Figure 11.12 Swollen polymer gel formed by underwater plasma-initiated copolymer...

Guide

Cover

Table of Contents

Title Page

Copyright

Preface

Begin Reading

Index

End User License Agreement

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Scrivener Publishing

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Nonthermal Plasmas for Materials Processing

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Jürgen Meichsner

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ISBN 978-1-119-36358-3

Cover image: Pixabay.Com

Cover design by Russell Richardson

Set in size of 11pt and Minion Pro by Manila Typesetting Company, Makati, Philippines

Printed in the USA

10 9 8 7 6 5 4 3 2 1

Preface

The noteworthy application of plasma to polymers began in the 1950s. Ever since the first attempts of industrial activities, the need for a scientific explanation of plasma-polymer interactions has been indispensable. The first scientific papers published were on the subject of plasma etching, ashing and surface modification of polymers. Simultaneously, plasma synthesis of organic compounds and amino acids followed. The highlight was plasma polymerization. This process forms polymers from nearly all gaseous, inorganic or organic precursors in an exotic way that to date is not fully understood. In the past, all these plasma processes were used in many fields of industry, especially for improving the adhesivity of polyolefins. Then, the focus was directed towards books on plasma medicine, biochemistry, and biology. Very early on, the actual state of knowledge was summarized in these oftenread books.

The broad avenue populated by famous plasma scientists leads directly to the “Hall of Fame” known in Bavaria as Walhalla on the banks of the Danube River east of Regensburg (Figure 0.1) or as the Panthéon in Paris.

Figure 0.1 Walhalla near Regensburg; (left) general view, (right) inner arrangement of very prominent persons.

It is very difficult to decide who has incurred enough merit to be included in such a hall of fame. And although this is a difficult decision, it is not the most important consideration. Rather, the goal is to show a straightforward line in the development of plasma technology and research. Therefore, the purpose of this book is to act as a preliminary anchor point for plasma processing and polymers.

Figure 0.2 (From left to right) Fredrick K. McTaggart and his book on plasma chemistry; Hirotsugu K. Yasuda; David Briggs; and Kashmiri. L. Mittal.

Temporarily standing at the end of a very long line in the development of the plasma technique and its scientific explanation was Frederick K. McTaggart [1] with his famous book published in 1967 entitled Plasma Chemistry in Electrical Discharges (Figure 0.2).

Next, the most important plasma chemist was Hirotsugu K. Yasuda (Figure 0.2