20 Surface Modification of Plastics: Kenth S. Johansson

20 Surface Modification of Plastics
Kenth S. Johansson
SP, Technical Research Institute of Sweden, Stockholm, Sweden
20.1 Introduction: Surface contaminant with another. Solvent surface treat-

ment could be beneficial in cases where swelling
Modification of Plastics: of the polymer substrate can improve adhesion of
For What Reasons? coatings without adversely affecting the mechanical
properties of the substrate. The major drawbacks of
Modification of surface properties is based on this technology are the environmental and process
the principle of formation of physical, chemical and hazards associated with the use of large quantities of
multilayer surface structures of various complexities, chemicals. Any savings in equipment cost is usually
including deposition of amorphous films. Plastics are offset by the increased cost of environmental con-
inherently hydrophobic, low surface energy materi- trols. Acid etching is more effective than solvent-
als and thus do not adhere well to other materials based methods but it can easily result in overtreated
brought in contact. Generally, surface modification and damaged parts, in addition to serious hazard and
is used to introduce functional groups with high- disposal problems. For example, other than plasma
bonding ability on the plastic’s surface in order to treatment (Section 20.3.1), the most effective meth-
create interactions and bonds with other functional od for improving the bonding to fluoropolymers has
groups; to increase the surface energy; to introduce been to etch the surface with a material commonly
surface crosslinking; to modify surface morphol- referred to as sodium etch. The process consists of
ogy by increasing or decreasing surface crystallinity brief immersion of the fluoropolymer component
or roughness; and to remove contaminants or weak to be bonded in a solution of sodium naphthalene
boundary layers from the plastic surface. Improv- in tetrahydrofuran or another suitable solvent [2].
ing their adhesional properties is probably the most Although sodium etch is quite effective in treating
common reason for modifying the surface of plastics, fluoropolymers, concerns with operator safety and
but targeted variations of surface characteristics also problems of disposal have caused many users to
include wettability, water- and chemical resistance, seek alternatives. Each of the methods mentioned
nonfouling properties, tribological behavior, flame earlier has limitations, thus providing a strong driv-
resistance, and oxygen and water vapor transmission; ing force for the development of alternative surface
all while retaining the bulk properties of the original preparation methods.
plastic substrate. It has been estimated that 70% of Today, there are many different techniques avail-
the total production of plastic materials must be sur- able (ranging from vacuum to atmospheric pressure,
face treated prior to processing [1]. wet to dry, simple to sophisticated, and inexpensive
to very costly) to obtain the required functional char-
acteristics of plastics. Most methods used today are
20.2 Overview of Surface dry and thus environmentally sound. The methods
Modification Techniques presented later are roughly divided in surface activa-
tion and surface-coating techniques.
Historically, surface engineering methods have
included mechanical abrasion, solvent wiping to re-
move surface contaminants, solvent swelling, wet
chemical etching, and the application of specialized 20.3 Surface Modification
coatings. Abrasion only increases the surface area (Activation) Techniques
of the part prior to adhesive bonding and is thus of
limited use. Solvent cleaning is useful for remov- The purpose of surface treatment of polymer-
ing gross contamination. However, in ultraclean based materials is to increase surface wettabil
applications solvent cleaning merely replaces one ity through electrical discharge. The low surface
Applied Plastics Engineering Handbook. http://dx.doi.org/10.1016/B978-0-323-39040-8.00020-1

Copyright © 2017 Elsevier Inc. All rights reserved. 443
444 Applied Plastics Engineering Handbook
energy of polymer-based substrates often leads to weakly ionized plasma [6–9]. Plasmas can be di-
poor adhesion of inks, glues, and coatings. To ob- vided into equilibrium- and nonequilibrium plasmas,
tain optimum adhesion, it is necessary to increase or they can be categorized by electron temperatures
the surface energy of the substrate to just above that and electron densities [6]. Plasmas used for surface
of the material to be applied. The surface activation modification and deposition of organic coatings are
techniques presented here include plasma treatment, referred to as nonequilibrium plasmas. In such plas-
corona treatment, flame treatment, and UV-excimer mas, the electron temperature often significantly ex-
laser treatment. Corona and flame treatment can also ceeds the temperature of heavy particles. Ionization
be defined as plasmas, but in this chapter they are and chemical processes in nonequilibrium plasmas
considered to be different surface modification tech- are directly determined by the electron temperature.
niques. All surface treatments presented here result Nonequilibrium plasmas are usually called nonther-
in improved surface-adhesion properties. mal, glow discharge, or low-temperature plasmas.
Such plasmas are able to produce very high concen-
trations of chemically active species (electron tem-
20.3.1 Plasma Treatment perature >10,000 K), and still keep the bulk (ion)
temperature as low as room temperature [6–8]. In
Low-temperature plasma processing is a versa- contrast to thermal equilibrium plasmas, a glow dis-
tile technique that is increasingly used in surface charge plasma is generally characterized by a rather
and interface engineering of plastics [3–5]. Plasma low degree of ionization (10−5–10−6). A low-temper-
treatment has several significant benefits compared ature plasma is most commonly created by applying
to traditional wet chemistry techniques. Only a thin energy into a gas in order to produce excited species
surface layer is modified by the plasma treatment. and ions. The energy can be thermal or induced by
Thus, desired surface properties of various materi- an electric current or electromagnetic radiation. In
als are achieved without altering their bulk material electrically created plasmas, electrons receive energy
characteristics. It allows the achievement of a higher from the electric field; and during the following col-
quality of surface characteristics than would other- lisions with heavy particles the energy is transferred
wise be possible, as well as treatment of materials from the electrons to the heavy particles. The mecha-
that are beyond the reach of traditional wet chem- nisms of ionization, that is, the conversion of neu-
istry processing. In addition, plasma processing is a tral atoms or molecules into electrons and positive
dry and environmentally friendly technique that does ions, can vary between different plasma–chemical
not require a vast supply of water, heating, or drying, systems. Elementary plasma–chemical processes can
only minute amounts of chemicals to produce the de- be described by several collision parameters but they
sired functionality. are generally subdivided into elastic and nonelastic
ones. Elastic collisions do not change the internal en-
ergy of neutral species but slightly increase their ki-
20.3.1.1 Fundamentals and Effects of netic energy. If the electronic energy is high enough,
Plasma Treatment nonelastic collisions modify the electronic structure
Plasma is an ionized gas and can be considered of neutral species, which leads to the creation of ex-
as the fourth state of matter after solid, liquid, and cited species or ions if the collisions are energetic
gas. Ionized gas is usually called plasma when it is enough [6–8]. Nonthermal atmospheric plasmas can
electrically neutral and contains a significant number be created and excited by different kinds of electric
of the electrically charged particles, such as, elec- discharges. Tendero et al. [9] and Napartovich [10]
trons, ions, atoms, radicals, excited states, and dif- have made extensive reviews of atmospheric plasma
ferent wavelength photons. Plasmas can be found in sources and their application, especially in the field
nature and in industrial applications. Lightning and of surface modification.
the aurora borealis are excellent examples of plas- The plasma–solid interactions at the surfaces can
ma present in nature, while industrial applications be classified in several ways, for example, surface
for plasma include lasers, fluorescent lamps, and cleaning and etching, crosslinking and chain scis-
plasma screens. The ionization level of particle spe- sion, and chemical modification. All of the inter-
cies in the plasma can vary. A plasma is called com- actions contribute to the plasma process usually to
pletely ionized when the ionization level of particle some degree, but the substrate, plasma gas, equip-
species is close to unity, but if the ionization degree ment design, and operating parameters define which
of the particles is low, the plasma is referred to as of the interactions dominates in the plasma process
20: Surface Modification of Plastics 445
[11–13]. In addition, plasmas are also utilized in which promotes heat resistance and bond strength,
polymerization for deposition of thin coatings onto and limits the migration of polymer additives to the
the surfaces (Section 20.4.3). Surface cleaning, that surface. Plasma treatment using noble gases can also
is removal of organic contaminations and additives be used for surface cleaning because it removes low-
(e.g., antioxidants, oligomers, antiblock agents, molecular-weight compounds or converts them to
and solvents) from the surfaces, is one of the main high-molecular-weight compounds by crosslinking
reasons for enhanced coatability and bondability [3,11,12,16].
of plasma-treated surfaces. Etching or ablation dif-
fers from cleaning only in the amount of material
that is removed from the surface. Plasma etching
is used for the cleaning of badly contaminated sur-
20.3.1.2 Plasma Treatment at Low
faces, removal of weak boundary layers, and for the Pressure
treatment of filled or semicrystalline materials. The Low-pressure plasma treatment of polymer sur-
etching mechanisms depend on the surface proper- faces has been extensively reported over the past
ties of polymers (morphology) and plasma process three decades [3–5]. Low-pressure plasma discharg-
(treatment gas and exposure time) because an amor- es are widely used in materials processing because
phous polymer is removed many times faster than they have a number of distinct advantages com-
a crystalline material or inorganic filler material pared with atmospheric pressure plasma discharges:
[11–13]. Chemical modification can be defined as an (1) low-breakdown voltages; (2) a stable operating
alteration of the surface region with new chemical window between spark ignition and arcing; (3) an
functionalities. Different plasma gases are producing electron temperature capable of dissociating mol-
various functional groups on the surface, for exam- ecules (1–5 eV), but a low neutral temperature;
ple, ether, hydroxyl, carbonyl, carboxyl, hydroper- (4) relatively high concentrations of ions and radicals
oxyl, and amino groups. Generally, these functional to drive etching and deposition reactions; and (5) a
groups are able to increase the surface energy and uniform glow over a large gas volume [17].
establish covalent bonds on the surface and thus in- Plasma glows are easily generated at low pressure
crease bonding strength, stability or permanency and and brought into direct contact with the surface of
resistance to environmental degradation [11,12,14]. the treated plastic material. The active species in the
Oxygen- and oxygen-containing plasmas are used plasma attack the polymer surface and create active
for surface cleaning, etching, and chemical modifica- sites, such as free radicals, which then react readily
tion. Several reactions are occurring simultaneously with nearly any coating material. Thus, all the de-
in oxygen plasma but the dominating reaction de- sirable properties of the polymer are preserved, such
pends on the operating parameters and substrate. The as, low cost, ease of fabrication, molding into de-
main function of oxygen- and oxygen-containing sirable shapes, low density, and flexibility. The use
plasmas is to increase the surface energy and bond- of low-pressure plasmas for polymer surface modi-
ability by introducing oxidized functional groups on fication up to 1994 has been critically reviewed by
the surface [11,12]. Liston et al. [12]. Several industrial applications of
Nitrogen and nitrogen containing plasmas are plasma treatment use low-pressure systems [4]. For
used to produce nitrogen functionalities, such as, instance, low-pressure glow discharge plasma is the
amino groups onto surfaces, which enhance the backbone of the global plasma industry and work-
wettability, dyeability, and printability of surfaces horse of a dozen major industries, in particular the
[11,12,15]. Plasma treatment of polymer surfaces us- omnipresent microelectronics industry, which would
ing noble gases, such as, helium or argon, is known not exist without the glow discharge plasma. Adhe-
as crosslinking via activated species of inert gases sion promotion is probably the single most common
(CASING). Helium and argon plasmas are effective application of plasma treatment as it is generally well
in the creation of free radicals but they do not add suited for this task, but also cleaning and etching are
new chemical functionalities to the surface. The ions important applications. Carboxylic, amine, hydroxyl,
and UV photons present in the plasma are able to epoxy, and so on, are possible functional groups that
break C─C or C─H bonds, which leads to the pro- are most suited to interact with polymers, inorganics,
duction of carbon radicals. These formed radicals can and metals [4,18].
react with radicals in the near polymer chains, result- Another interesting industrial application is plas-
ing in the formation of a stable crosslinked polymer ma-assisted sterilization. Hydrogen peroxide (H2O2)
surface. Crosslinking forms a very cohesive surface, gas plasma (HPGP), also called low-temperature
Figure 20.1 One of Sterrad 100NX sterilization cycles. Pressure unit: mtorr; Time unit: minutes (Reproduced with
permission from Johnson and Johnson).
hydrogen peroxide gas plasma sterilization (LTH- The main drawback of low-pressure plasma treat-
PGP) and marked under the trade name Sterrad ments is the need to operate in vacuum. This greatly
(Advanced Sterilization Products, ASP, Johnson limits the size of objects, which could be convenient-
and Johnson, Irvine, CA). It is used as an industrial ly treated and also required the use of cumbersome
sterilization but also, and more importantly, has en- and costly vacuum chambers and supporting equip-
countered much success in healthcare centers, with ment. Hence, there is an increasing interest in the
several thousand hospitals equipped around the development of atmospheric-pressure plasma (APP)
world. This process combines an oxidative chemical treatment systems [4,18].
phase (vaporized H2O2, a strong antimicrobial agent),
followed by low-temperature plasma, as described
later. The five phases of the LTHPGP sterilization
process consist of vacuum, H2O2 injection, diffusion,
plasma, and vent as outlined in Fig. 20.1 [19]. The
H2O2 is provided in multidose cassettes containing
10 single doses of liquid (nominal) 59% H2O2, which
becomes vapor when injected under vacuum. After
vacuum and diffusion of H2O2 for a certain period of
time (which varies between the available systems),
an electromagnetic field is created in which the H2O2
vapor breaks apart, producing a low-temperature
plasma cloud. H2O2 produces reactive species, such
as, hydroxyl and atomic oxygen radicals, UV light,
which attack the cell membrane, DNA, and enzymes
[20,21].
The largest chamber (Sterrad 100NX, conceived
for operating rooms and large facilities) is shown in
Fig. 20.2. Sterrad sterilization can be used on metals,
elastomers, silicone, and most polymers [22,23].
More generally, low-pressure plasmas have been
able to kill microorganisms very rapidly [24,25,26].
It is a promising technology in that it acts rapidly,
does not leave toxic residuals on processed parts or
in the exhaust gas, and the temperature of a substrate
usually does not exceed 60°C. This field is rapidly Figure 20.2 Sterrad 100NX large chamber for the
moving forward, for sterilization, as well as, for operating room. (Reproduced with permission from
cleaning processes [26,27]. Johnson and Johnson).
20.3.1.3 Plasma Treatment at form of two opposing electrically conductive elec-

Atmospheric Pressure trodes separated by a gap containing the gas from
which the plasma is generated and connected to a
As mentioned earlier, low-pressure (vacuum)
high-voltage source. The geometry of the electrodes
plasma has been used for quite some time for poly-
is highly assymetric, examples being sharply pointed
mer-surface modification but in the past decade there
needle or thin wire electrodes opposing flat planes
has been an explosive growth of interest in APP pro-
or large diameter cylinders. These are powered with
cesses, mainly because of their technological and
high, continuous or pulsed DC or AC voltages. The
economic advantages. They require no vacuum, need
high-electric field around the singularity, that is,
no expensive equipment, are easy to handle, can be
the point of the needle or the wire, causes electrical
used in continuous mode, have a very good scalabil-
breakdown and ionization of whatever gas surrounds
ity, and can easily be integrated in existing process
the singularity, and plasma is created, resulting in a
lines. As a consequence, APP technology has been
fountain-like spray out from the point or wire. The
effectively utilized to treat plastics (polymers), pa-
mechanism of a corona discharge is schematically
per, rubber, wool, fabrics, steel, glass, and fiber-rein-
illustrated in Fig. 20.3.
forced composites. At the same time there has been
much activity in improving the existing processes, Coronas are weakly ionized with a free electron
plasma sources, and reactors. Nonthermal atmo- density of about 108 electrons/cm3, which compare
spheric plasmas can be created and excited by dif- with the particle density of a gas at atmospheric
pressure of ∼1019 particles/cm3. The corona is
ferent kinds of electric discharges. Tendero et al. [9]
strongly nonthermal with some very high-energy
and Napartovich [10] have made extensive reviews
free electrons with temperatures in excess of
of atmospheric plasma sources and their application,
100,000 K.
especially in the field of surface modification.
Examples of plasma sources operating at atmo- Coronas are widely used as chemical reactors
spheric pressure are: for surface treatment. Depending on the material
to be treated and the desired surface properties, the
optimal corona gas composition, discharge param-
• AC corona discharge,
eters, and operating procedure may be very differ-
• dielectric barrier discharge (DBD), ent. An industrially very important application is
• atmospheric-pressure glow discharge (APGD), the surface treatment of polymers, in particular to
• atmospheric-pressure plasma jet (APPJ), and increase their wettability and adhesion to facilitate
• surface barrier discharge (SBD). printing, painting, sealing, and coating. Read more
about corona discharges for surface treatment in
Section 20.2.
20.3.1.3.1 AC Corona Discharge This is achieved simply by corona discharges in
Corona discharges are plasmas that result from ambient air. Discharge products transfer their activa-
the high-electric field that surrounds an electrically tion energy to the polymer by breaking chains and
conductive spatial singularity when a voltage is ap- creating radicals. These will rapidly react with the
plied. Corona generation systems usually take the further impinging particles, with the environment,
Figure 20.3 Schematic illustration of the mechanism of a corona discharge. (Reproduced with permission from
Hephaestos82).
Figure 20.4 Basic DBD configuration [28] . (Used with permission from Springer).
and even with gas coming from the bulk material. electron density of about 1010 electrons/cm3 but the
Polar bonds and hydrogen bonds formed in this free electrons are slightly cooler at temperatures
way will increase the polymers surface energy. The of 20,000–50,000 K. This is thus a much more at-
bonds most frequently encountered are C─O, C═O, tractive candidate for surface modification of plas-
C─O─O, C─OOH [12]. tics than the pure corona [29]. The transport current
in the discharge gap between electrodes has to be
high enough to cause breakdown of the gas. The volt-
20.3.1.3.2 Dielectric Barrier Discharge age value where the ionization of the gas takes place
In contrast to the asymmetry of the corona sys- is called breakdown voltage. According to Paschen’s
tem, if a symmetrical electrode arrangement is set law, the breakdown voltage (V) depends on the type
up, comprising two parallel conductive plates placed and pressure (d) of plasma gas and gap distance (p).
in opposition, separated by a gap of ∼10 mm, and a The breakdown voltage dependence on the param-
high voltage (1–20 kV) is applied, the gas between eter pd is usually referred to as the Paschen curves.
the plates can be electrically broken down and a plas- Fig. 20.5 presents the Paschen curves for different
ma discharge generated. However, the plasma gener- atomic and molecular gases.
ally takes the form of a hot thermal plasma arc less These curves have a minimum corresponding to
than a millimeter in diameter, which jumps from one the easiest breakdown conditions. The breakdown
spot on one electrode plate to a spot on the opposing conditions, for example, pressure, treatment gas, dis-
electrode. This configuration is useless for surface charge gap, voltage, and frequency, define the oper-
treatment and would do nothing except destroying ating mode of DBD plasma [6,7,28].
the material to be treated. DBD can exist in two modes, that is, filamenta-
However, if one or both of the electrode plates is ry and homogenous mode. The latter is sometimes
covered by a dielectric, such as, ceramic or glass, the confusingly also called as APGD. In most cases,
plasma finds it much more difficult to discharge as DBD plasma operates in the filamentary mode where
an arc and is instead forced to spread itself out over the electrical conductivity is restricted to numer-
the area of the electrodes to carry the current it needs ous successions of microdischarges. The plasma is
to survive. This type of plasma is called DBD and
is large area, nonthermal, and uniform. In a typical
DBD, plasma state is generated between two metal
electrodes, from which at least one is covered with
an insulating dielectric barrier or layer, as seen in
Fig. 20.4.
The plasma is created by applying a high voltage
across the discharge gap into the gas. Typically, the
discharge gap for DBD plasma at atmospheric pres-
sure is a few millimeters, with the frequency vary-
ing from 500 Hz to 500 kHz and the voltage being
around 10 kV. The dielectric barrier materials have
low-dielectric loss and high-breakdown strength.
The discharge requires alternating voltage to oper-
ate because the dielectric barriers are insulating ma- Figure 20.5 Breakdown Paschen curves for different
terials, and thus they cannot pass DC current. The atomic and molecular gases [6]. (Reproduced with per-
DBD is denser than the corona with a typical free mission from Cambridge University Press, New York).
not homogenously ionized and the current is passed planar or curved electrodes, separated by millimeters
through streamers, that is, thin, weakly ionized plas- at high frequency or even very high frequencies (2–
ma channels formed in the discharge gap between the 60 MHz), which is much higher than the other plasma
electrodes. The microdischarges are built from un- types. The electrodes are not covered by dielectric
evenly distributed streamers, of which the channel di- but are bare metal. This feature enables significant-
ameter is 0.1–1.0 mm and specific energy input small, ly higher power densities (up to 500 W/cm3) to be
10–3 eV/mol (corresponds to heating of ∼10 K), dur- coupled into the discharge than can be achieved with
ing a short period (∼30 ns). The visible filaments in corona or DBD. The application of voltage between
DBD are microdischarges repeatedly forming at the metal plates would generally result in generation of
same spot because of the microdischarge remnant. a highly undesirable, very high-current density, and
Without the remnant, the microdischarges would hot plasma arc. However, by control of the interelec-
form in a new spot each time as the polarity changes trode gap and the frequency of the driving voltage
and the discharge would appear uniformly. Streamers and, above all, by the use of helium as ∼99 % of
develop perpendicularly to the surface of the treated the generation gas, arching is prevented and a large
substrate. As a consequence, the plasma is only in volume, nonthermal plasma is generated, which is
limited contact with the surface, resulting in rela- both dense and a rich source of the chemical species
tively long treatment times, typically in the order of needed to carry out the surface modification. A typi-
one minute. Further, as streamers tend to follow the cal APGD based on helium is shown in Fig. 20.6.
partially ionized tracks of previous microdischarge Chemical fluxes 100 times greater than those
channels over a wide range of frequencies, increas- available from DBD and 1000 times greater than co-
ing discharge power may lead to thermal damage of rona are claimed. The need to use helium, a finite
the treated polymer material, such as, the formation and increasingly expensive resource, is undoubtedly
of pinholes in a treated textile or plastic material. a commercial issue for APGD in some but not all
In any event because of the short duration and thus processes. This can be addressed by the inclusion of
the limited charge transport and energy dissipation a helium recycling subsystem in the equipment pack-
in each microdischarge, there is typically little gas age since helium is not consumed in the process. It
heating so that a large portion of the free electron en- is obvious that helium is an amazing gas with sev-
ergy is utilized for exiting atoms or molecules in the eral special properties that, in combination, make it
background gas, thus creating the precursors needed uniquely suited for generation of well-behaved, large
to initiate surface chemical reactions. This explains volume, cool plasma at atmospheric pressure. A de-
the great interest in DBDs and why it is one of the tailed description of helium’s properties can be found
most commonly used APP sources in large industrial in Ref. [29].
scale applications. Extensive research has led to sev- Commercial APGD systems are offered, for ex-
eral applications for DBD, for example, excitation of ample, by Dow Corning Plasma Solutions (Ireland)
CO2 lasers, flat plasma-display panels, and surface [34] and Enercon (USA) [35]. As a practical exam-
modification of various substrates [28]. Commercial ple, Enercon has developed an implementation of the
DBD systems are supplied, for example, by Enercon APGD technology for large scale plasma treatment
(USA), Ahlbrandt (Germany), Softal (Germany), of polypropylene (PP) film. Fig. 20.7 shows an in-
and AFS (Germany). The commercial applications dustrial APGD system for modification of polymer
of these systems are restricted to improving (in- sheet surfaces.
creasing) the surface energy and thus, for instance, A 0.40-mm thick PP sheet needed improved aque-
the printability of these plastic films and foils only. ous-based ink adhesion. PP sheets were treated in a
For thicker materials the electrode gap is usually too plasma system similar to the one shown in Fig. 20.7.
large for discharge initiation [29]. Such a machine can treat polymer sheets from 27–
60 in. The surface energy of the sheets was enhanced
substantially after atmospheric plasma treatment. Un-
20.3.1.3.3 Atmospheric-Pressure Glow
treated, corona-treated, and APGD-treated PP sheets
Discharge were printed with a water-based ink deposited by a
APGD is analogous in its mode of generation flexographic printer and then subjected to a tape-peel
and some key characteristics to low-pressure glow test to determine the adhesion of the ink. During the
discharge plasma described earlier [30–33]. The peel test, the untreated samples exhibited total ink-
APGD is generated by application of relatively low adhesion failure, with all image ink removed with the
(∼200 V) voltages across opposing symmetrical tape. The corona treated film retained approximately
Figure 20.6 Example of an APP helium glow discharge. (Reproduced with permission from Prof. Denis Dowling).
Figure 20.7 Atmospheric-plasma treater for surface modification of polymer sheet material on an industrial scale.
(Courtesy of Enercon Industries Corporation).
90% of the image ink at its surface and the APGD- treatment in enhancing the adhesion of water-based
treated samples displayed 100% ink adhesion, with inks to PP. It is also understood that APGD treatment
no residue being removed from the surface. The re- need not be restricted to PP sheet materials. Other
sults confirm the effectiveness of atmospheric-plasma materials that can be successfully treated with this
method include polypropylene fibers, polyethylene

(PE) sheets, poly(ethylene-terephthalate) (PET) fi-
ber, Tyvek, and nylon, wool [35].
20.3.1.3.4 Atmospheric-Pressure
Plasma Jets
In recent years various APPJ systems producing
plasmas at low temperatures have been developed.
The main distinctive feature of this plasma source is
the generation of the plasma at a distance from the
treated surface. Active plasma species are expelled
toward the surface through an orifice of a nozzle.
APPJs can essentially be classified by the type of
discharge used for the generation of plasma. There
are many methods of plasma generation, such as,
DBD, corona discharge, and glow discharge. How-
ever, in corona discharge, the electric current den-
sity is low and the discharge is heterogeneous, thus a
plasma jet cannot be formed. Glow discharge occurs
at low pressure, which cannot be adapted to generate
a plasma jet. [36]. The simplest method of generating
plasma is the use of DC discharge, although it re-
quires radiofrequency (RF) for ignition. This type of
APPJ has been described in several papers [37–43]. Figure 20.8 Example of an APPJ. (Reproduced with
The basic operation of APPJ technology involves permission from PlasmaTreat GmbH).
the use of a high-voltage discharge (between 5 and
15 kV in the frequency range of 10–100 kHz) to cre-
ate a pulsed electric arc in an enclosed chamber. A assembling APPJ arrays [46–48]. Scanning is simpler
process gas is then allowed to flow through the dis- but could significantly increase the time required for
charge section thereby being excited into the plasma processing. An APPJ array requires a more compli-
state. This plasma then passes through a jet head to cated design but allows for the treatment of a larger
arrive on the surface of the material to be treated. An surface at the same time. Recently, an APPJ device
example of an APPJ is shown in Fig. 20.8. with a jet array reactor consisting of five parallel
The jet head is carefully designed to determine single jet units was developed, allowing larger area
the geometry of the exiting plasma stream and is also coverage [49]. In this way, even sheet materials hav-
kept grounded to avoid uncontrolled charge buildup, ing treatment widths of several meters can be treated
which could cause instabilities in the flow. Depend- today. Two examples of this alignment configuration
ing on the power of the jet and many other parame- are shown in Fig. 20.9.
ters, the length and width of the beam can be tailored In doing so, the modification of the surface
to a large variety of applications. achieved by plasma jets is comparable to the effects
Due to their remote operation, plasma jets are par- obtained with the low-pressure plasma systems men-
ticularly suited for treatment of three-dimensional tioned earlier. However, the inherent disadvantages
(3D) structures and for selective surface modifica- of such a configuration are the use of high-gas flows
tions of specific parts. The treatment of plastics by and consumption of electricity. It is also possible to
small-sized atmospheric plasma jet sources based on use wide-angle rotary plasma jets in order to treat
RF discharges was reported in Ref. [44]. larger areas. One example is shown in the Fig. 20.10.
The main disadvantage of most APPJs is the small It was shown that APPJs can be very effective for
area that can be treated or coated, which results from materials processing and suitable for materials sensi-
the nature of the point discharge most commonly tive to thermal damage. In particular, the hydrophilic
used in APPJs. This disadvantage could be success- character of certain materials could be improved and
fully addressed by scanning the surface (substrate), the contact angle often decreases significantly after
as demonstrated in several papers [37,38,41,45] or by the plasma treatment.
Figure 20.9 Alignment of several potential-free APPJ. (Part A: Reproduced with permission from Dr. Gerstenberg
GmbH; Part B: Reproduced with permission from PlasmaTreat GmbH).
Figure 20.10 APPJ with wide-angle rotating jet head plasma jet for treatment of larger areas. (Reproduced with
permission from PlasmaTreat GmbH).
APPJ could also be successfully used for the im- perature of PS. Activations of PE, PP, and PS by the
provement of surface adhesion due to the activation air plasma were also investigated by Moritzer et al.
of the surface. Dowling et al. [50] reported results [51] and similar surface activation behaviors were
of treatment of PP, polystyrene (PS), and poly- observed. APPJ treatment of polyamide with helium
carbonate (PC) substrates with air plasma. It was (He)/CF4 plasma can significantly affect the chemi-
found that in the case of PP and PC polymers, the cal state of the APPJ treatment of polyamide with
activation energy of the surface could be increased, He/CF4 plasma can significantly affect the chemical
whereas the surface energy of PS was decreased by state of the polymer. This treatment method could be
the plasma treatment. This unexpected result could used to change the surface energy to manipulate ad-
be attributed to some decomposition of the polymer hesion and hydrophobicity [52]. APPJ treatment of
surface due to relatively low-glass transition tem- poly-e-caprolactone could significantly decrease its
hydrophobicity by incorporating oxygen-containing

groups (C─O, C═O, and O─C═O) [53]. Only
after 390 ms of the treatment, the contact angle was
decreased from 74 to 38 degree. Further increase of
the treatment time did not cause the contact angle to
change due to saturation.
Commercial APPJ systems are provided by sev-
eral companies, for example, Surfx Technologies
(USA) [54] and Enercon [55] (USA), Vito (Belgium)
[56], Plasmatreat (Germany) [57] and Tigres [58]
(Germany). The APPJ technology finds applications
in several industrial sectors, for instance, automotive, Figure 20.11 Schematics of the electrode arrange-
transportation, packaging, life science, electronics, to ments of (A) SBD and (B) CBD [60] . (Reproduced with
mention a few. Examples from the automotive sector permission from Scrivener Publishing).
include for instance Plasmatreat’s Openair Plasma
process for tightly sealed, cost-saving bonding of microdischarges obtained. Macroscopically uniform
headlights and tail lights. Modern headlights using SBDB plasma can be generated in any reactive gas
LED technology last for the lifetime of the vehicle, mixture, including electronegative gases, without the
thus eliminating the need to change bulbs. To ensure need for any rare (noble) gas admixtures or high-gas
this longevity, they must be effectively protected to flows [60].
keep all moisture out. When bonding headlights and SDBDs are discharges in which plasma genera-
tail lights made of PP and PC, the adhesive must tion is essentially limited to a thin layer adjacent to
therefore have excellent sealing properties, as well the dielectric barrier. The electrodes are set on or
as, provide reliable adhesion. Precise localized pre- completely embedded in the dielectric, as schemati-
treatment with Openair Plasma activates the nonpo- cally shown in Fig. 20.11. There are two main ge-
lar materials in all critical areas, ensuring reliable ometries of the SDBD systems. The most common
bonding and long-term sealing of the headlights [59]. geometry uses metallic strip electrodes deposited on
Other automotive applications include, treatment of alumina dielectric (Fig. 20.11A). This system is re-
EPDM door seals, and interior and exterior car parts. ferred to as SBD. An alternative electrode geometry
The use of plasma jets on industrial robots allows is known as coplanar barrier discharge (CBD). Here
highly precise, rapid, and environmentally respon- a thin layer of macroscopically uniform high-den-
sible surface pretreatment of large 3D car interior sity plasma is generated on a dielectric without any
parts prior to coating, wrapping, in-mold decoration direct contact between the plasma and the electrodes
or in-mold labeling. For pretreatment of parts, such (Fig. 20.11B) [60].
as, instrument panels, door trims, or sidewall trims,
Plasmatreat uses a number of patented wide-angle
rotary jets, making it possible to achieve rapid uni-
20.3.1.3.6 Diffuse Coplanar Surface Barrier
form surface activation even over large areas. Discharge (DCSBD)
DCSBD is a novel type and a further development
of the CBD-type of SDBD plasma source introduced
20.3.1.3.5 Surface Dielectric Barrier in the previous section. It has been developed for
Discharge (SDBD) high-speed, large-area surface plasma treatments to
SDBD offer a breakthrough with respect to dis- address various needs of the industry. DCSBD al-
charge homogeneity, power density, and operational lows a visually diffuse high-density “cold” plasma
stability, as alternatives to the aforementioned plas- to be sustained in atmospheric-pressure air at a high-
ma sources. The discharges are not glow-like, but the plasma power density exceeding 100 W/cm3 that
simultaneous and spatially well-distributed forma permits high-speed surface processing of large-area
tion of plasma microdischarges parallel to the treated webs and flat surfaces. The idea is to generate a thin
surface results in effective treatment of the polymer (of the order of 0.1 mm) layer of plasma with a high-
surface. A remarkably positive feature is the com- power density in the immediate vicinity of the treat-
paratively high-power density at which SDBDs ed surface and bring it into a close contact with the
can be operated. Moreover, the higher the power treated surface. Such a diffuse plasma layer enables
density, the more homogeneous the distribution of the use of the discharge to its full potential, including
gowns and surgical drapes [61,62]. It is hypothe-

sized that the more diffuse and highly nonequilibri-
um DCSBD air plasma is, the more efficient it is in
generating such crosslinking-stabilized wettable PP
surfaces than the filamentary plasma generated by
conventional volume DBDs. A narrow-web pilot
Figure 20.12 Cross-sectional schematics of DCSBD scale DCSBD plasma treater shown in Fig. 20.13A
electrode system arrangement. (Reproduced with per- is commercially available for a wide variety of tex-
mission from Masaryk University, Brno). tile materials for the treatment speeds up to 100 m/
min. A customized DCSBD plasma treater consist-
charged species, atomic and radical species, as well ing of numerous (up to 25) diffuse coplanar SBD
as, the UV radiation emitted by the air plasma to aid units in shown in Fig. 20.13B. Use of more than
material processing. Consequently, it is believed to one plasma unit is beneficial for improvement of
provide substantial advantages in energy consump- treatment efficiency when operating at high-speed
tion and exposure time [61]. production lines [63].
A schematic diagram of a DCSBD electrode sys- The DCSBD equipment, which can be easily in-
tem designed for ambient air plasma generation is tegrated into existing converting lines, was success-
shown in Fig. 20.12. Two systems of parallel strip- fully tested for surface activation of PP-NW fabrics
like electrodes (typically 1.8 mm wide, ∼0.1 mm in-line with a standard manufacturing machine at
thick, 230 mm long, 0.4 mm strip to strip; silver) are speed of 450 m/min and plasma exposures as short
embedded in 96% alumina using a green tape tech- as 0.14 s. This has been claimed to be “the highest
nique. The thickness of the ceramic layer between plasma treatment speed among the plasma sources
the plasma and electrodes was 0.4 mm. A sinusoi- hitherto tested for textile surface treatment applica-
dal high-frequency high-voltage ∼10–20 kHz, up to tions” [61].
15 kV peak-to-peak was applied between the elec- Besides the PP-NW treatment, the potential of
trodes. DCSBD plasma sources for textile surface activation
The DCSBD source was originally designed to has already been demonstrated in many contexts,
fulfill the specific requirements of the textile non- for example, in an improvement of polyester cords
woven industry for hydrophilization of lightweight to rubber [65] and efficient cleaning and activation
(i.e., with the thickness on the order of 0.1 mm of various materials including polymer films, paper-
only) PP-nonwoven (NW) fabrics, which are wide- board, and glass. On a laboratory scale it has been
ly used in personal care absorbent products, such tested also for the plasma activation of polymer films
as, feminine hygiene products, diapers, adult in- for various applications [66] and surface activation
continent products, and medical products, such as, of paper [67].
Figure 20.13 (A) Narrow-web pilot-scale DCSBD plasma treater. (B) A customized DCSBD plasma treater con-
sisting of numerous (up to 25) diffuse coplanar surface barrier discharge units. See also [64]. (Reproduced with
permission from Masaryk University, Brno).
20.3.2 Corona Treatment material’s surface. A typical corona treatment station

is shown in Fig. 20.14B.
Corona treatment is the most widely used surface An industrial corona treater normally operates in
treatment method in the plastic film-, extrusion-, and a frequency range between 10 and 50 kHz and out-
converting industries and has been used since the put powers over 50 kW because the width of unit
1950s. It was indeed the only nonthermal APP type can be up to 10 m with operating line speeds over
in industrial production for around half a century un- 500 m/min [28,68].
til the new millennium. For reasons to do with power The effectiveness of the corona treatment depends
sources, ease of plasma generation, and robustness, on the specific material being used. Different plastic-
the plasma industry has developed equipment config- film materials have different characteristics and
urations that run a hybrid corona/DBD plasma type different amounts of slip and additives, which will
that is universally and colloquially called “corona,” determine the effect of the corona treatment. There
with the equipment called a “corona treater,” and the are no limits with regard to the materials that can
process that it runs called “corona treatment.” In fact, be corona treated. However, the required intensity
the industrial “corona” uses elements of both its coro- of the treatment (corona dose in W/min per m2) may
na and DBD parents. It combines the corona plasma vary significantly. The treatment level can be calcu-
type’s asymmetric electrode configuration, typically lated by using the following formula:
a metal rod opposing a large diameter metal cylin-
der, and the DBD’s dielectric, generally a ceramic, Power (W) = T × S × W × M
covering the rod or the opposing cylinder or both. P = Total power (W) required
It uses a low-temperature corona discharge plasma
to impart changes in the properties of a surface. As T = Number of sides to treat (single/double sided)
described earlier, the corona discharge is generated S = Line speed (m/min)
by the application of high voltage to an electrode that W = Film width (m)
has a sharp tip. The plasma forms at the tip. A linear M = Material factor (required W/min per m2)
array of electrodes is often used to create a curtain of
corona discharges (Fig. 20.14A). Materials, such as The exact value is best determined by testing a
plastics, cloth, or paper may be passed through the sample of the actual film that is used for a specific
corona plasma curtain in order to change (increase) application.
the surface energy of the material. Surface treatment When the surface of a plastic substrate is bombard-
systems are available for virtually any surface for- ed with formed high-speed electrons, the molecule
mat including dimensional objects, sheets, and roll bonds on the surface of most plastics are broken [68].
goods that are handled in a web format. Corona The oxidants present in corona, for example, ozone,
discharge equipment consists of a high-frequency atomic oxygen, and oxygen-free radicals, are very
power generator, a high-voltage transformer, a sta- similar to those present in APPs described earlier (at
tionary electrode, and a treater-ground roll. Standard least those using air as process gas). The oxidants
utility electrical power is converted into higher fre- create oxidized groups with free radicals present on
quency power, which is then supplied to the treater the surface. The depth of oxidation on corona-treated
station. The treater station applies this power through surfaces is usually only 3–10 nm and the introduc-
ceramic or metal electrodes over an air gap onto the tion of different oxidized groups on corona-treated
Figure 20.14 (A) A linear array of electrodes to create a curtain of corona discharges. (B) Typical corona treat-
ment station. (Reprinted with permission from Vetaphone).
polyolefin surfaces have been reported by several re- As shown earlier, the most common application of
searchers [69,70]. These oxidized functional groups corona treatment is to improve the adhesion of web-
increase the surface energy and thus improve the based materials in the plastic film-, extrusion-, and
wetting and adhesional properties of the surface of converting industries. However, corona treatment
mainly polyolefins, such as, LDPE and PP [71–73]. can also be used to improve the adhesional proper-
Other adhesion-improving mechanisms include the ties of various 3D plastic parts.
crosslinking of surface regions and increasing of the Tantec, headquartered in Denmark [84], has devel-
cohesive strength of the substrate by the elimination oped several corona treaters for surface activation of
of possible low-molecular-weight oxidized materials various plastic parts. One example is the RotoTEC-
(LMWOM) from the surface, changing the surface X system, which is used for in-line corona treatment
morphology and increasing the surface microrough- of injection molded parts prior to coating, printing,
ness and charging (electret) on the surface. The effect gluing, and painting for optimization of the adhesion
of corona treatment of polyolefins has also been stud- properties of a given substrate, mostly polypropylene
ied with respect to surface roughness [15], printabil and PE (Fig. 20.16).
ity [74,75], heat sealability [76], friction [77], and This universal system developed by Tantec op-
coatability [78,79]. erates with patented rotating electrode elements re-
A range of commercial equipment suppliers offer sulting in complete and uniform treatment of parts.
standard corona treaters (based on filamentary DBD) These self-contained units can be installed within
include, Enercon (USA) [35], Ahlbrandt (Germany) existing production lines or used as an off-line treat-
[80], Softal (Germany) [81], AFS (Germany) [82], ing process. The system includes a high-frequency
and Vetaphone (Denmark) [83]. Some typical indus- generator, high-voltage transformer, rotary elec-
trial corona treaters are shown in Fig. 20.15. trodes, ozone filter, and customized stand-alone or
Figure 20.15 Examples of some industrial corona treaters. (Part A: Reproduced with courtesy of Enercon Industries
Corporation; Part B and C: From Reproduced with permission from Softal; Part D: From Reproduced with permission from
Ahlbrandt GmbH).
Figure 20.16 RotoTEC-X system with rotating electrode elements from Tantec for corona treatment of 3D plastic
parts. (Reprinted with permission from Tantec A/S).
Figure 20.17 Corona treater for surface activation of plastic parts. (Reprinted with permission from Tantec A/S).
bench-top treating station. Both standard and cus- medical industry. In extrusion coating, flame treat-
tomized RotoTEC-X stations are available for both ment can be used to enhance the adhesion between
single- and dual sided treatment. polymer- and fiber-based substrate, and to improve
Other types of plastic parts that can be treated the printing, gluing, or coating properties of extru-
include, pipes, syringes, cables, extruded profiles, sion coatings [86].
needle hubs, and containers. Fig. 20.17 shows a spot Flame treatment is a thermal plasma method
treater and treatment of a plastic container and ex- where exothermic reactions between oxygen and fuel
truded pipes before printing [84]. gas create thermally activated radical atoms and mol-
ecules, such as, O, OH, NH, NO, and CN [87,88].
The most commonly used gases in flame treatment
20.3.3 Flame Treatment are propane (C3H8), natural gas or methane (CH4) and
butane (C4H10). These gases mainly burn with atmo-
Flame treatment and corona treatment are the spheric oxygen, producing water and carbon diox-
most used methods for the surface activation of ide. The combustion is a complex process involving
polyolefin films and coatings in industrial pro- many chemical reactions, but it is well summarized
cesses today. Flame treatment is mainly used for
by, Farris et al. [85] and Strobel et al. [89]. For ex-
the surface treatment of board and thicker polyole-
ample, the combustion reaction of propane is:
fin materials, such as, automobile body parts and
blow-molded bottles [85]. Flame-plasma treatment C 3H 8 + 5 O 2 + 18.8 N 2 → 4 H 2 O + 3CO 2 + 18.8 N 2
has also become increasingly popular with intravas-
cular devices, such as, balloon catheters due to the Fig. 20.18 gives an overview of the main reactions
precision and cost-effectiveness demanded in the taking place in the flame.
Figure 20.18 Schematic overview of the combustion process [85]. (Reproduced with permission from Elsevier).
released energy is low and thus the region is negli-

gible for surface activation purposes. The main re-
action zone, also called the luminous zone, is used
for surface treatment because the temperature and
amount of oxidizing species is the highest in this
zone. Theoretically, the highest temperature of flame
(1900–2000°C) is reached when all the propane has
reacted with the air. The highest concentration of oxi-
dizing species is reached just before the postcombus-
tion zone, which is the largest of the three regions. A
flame treatment unit is usually equipped with a water-
cooled burner. The geometry of the flame is adjusted
by the size and number of ribbon slots or drilled ports
of the burner. The cooled back-up roll can be used to
ensure uniform flame treatment [86,90]. The flame
treatment parameters (equivalence ratio or air–gas
ratio, distance between flame and substrate, air–gas
mixture flow, and treatment time, that is the exposure
time between flame and substrate) are used to con-
trol the quality and level of treatment [86,85,89,90].
Figure 20.19 Main zones in a laminar flame profile The flow rate of treatment gases (air–gas mixture)
[85]. (Reproduced with permission from Elsevier). defines the physical size and amount of heat energy
of the flame (W/cm2), whereas the treatment time
is mainly determined by the line speed. The treat-
Three different zones, that is, prereaction, main ment time shortens when the line speed increases
reaction, and postcombustion zone, can be observed and thus the feed rate must be increased in order to
in the flame, as shown in Fig. 20.19. obtain the same treatment level. The preliminary task
Each zone has a different thermal gradient and of the flame is to break through the boundary layer
amount of reactive species. According to Farris et al. of air, which moves along with the moving substrate
[85], the precombustion zone is the coldest region [85]. On the other hand, excessive flame treatment
of a flame because the combustion process has not eventually damages or overoxidizes the surface
yet reached the explosion condition. The amount of of the substrate. Overoxidation can lead to a weak
boundary layer, which usually leads to adhesion fail- flame on printability and heat sealability [100,101].
ure [91,92]. The optimum distance between burner In addition to the surface oxidation, flame treatment
and substrate depends on the burner design and treat- introduces surface crosslinking and chain-scission,
ment level, since the luminous zone is used for sur- modifies surface morphology by increasing or de-
face treatment. The optimum distance between the creasing surface crystallinity and roughness, and re-
luminous zone of flame and substrate has varied from moves contaminants or weak boundary layers from
2 to 10 mm, depending on the study [85,89,90,93]. the surface of polyolefins [14,86,102].
For example, Tuominen [90] observed that the op- The depth of oxidation and the amount of oxygen
timum distance between burner and board increased on a LDPE surface is greater compared to on a PP
from 6–8 mm to 10–12 mm when the air–propane surface because of the different surface-oxidation
flow was increased from ∼500 L/min to ∼700 L/ mechanisms [85,89]. The detailed surface oxidation
min. The equivalence ratio of gas mixture is probably mechanisms of PE and PP are discussed by, for ex-
the most important parameter because it determines ample, Strobel et al. [103] and Farris et al. [85].
the temperature and oxygen radical content of flame. As indicated earlier, industrial applications of
The exact ratio of oxidizer to fuel required for com- flame treatment involve activation of both two- (e.g.,
plete combustion is called the stoichiometric ratio. polyolefin films, coatings, and paperboard) and 3D
For example, the stoichiometric ratio for propane–air surfaces, mainly to promote adhesion. A typical
mixture (m3/m3) is approximately 24:1, depending burner for treatment of web-based materials is shown
on the purity and temperature of the gases [85]. The in Fig. 20.20.
equivalence ratio (ø), is defined as the stoichiometric Flame treatment of plastic parts encompasses
oxidizer:fuel ratio divided by the actual oxidizer:fuel an infinite range of extruded or molded products in
ratio. A fuel-lean (oxidizing) flame contains more many different market sectors, including packaging,
oxidizer than stoichiometric (ø < 1) and a fuel-rich automotive, medical, bottles, containers, moldings,
flame contains more fuel gas than stoichiometric components, extruded pipes and cable covers. Flame
(ø > 1) [89]. Generally, an oxidizing flame has led treatment can be utilized to promote the adhesion
to the highest wetting and adhesion on LDPE and PP of labels or printing of caps, closures, bottles, con-
surfaces, but the optimum value has varied between tainers, cables, and many more. Different designs of
studies [89,92,94,95]. Strobel et al. [89] stated that burners, for treatment of plastic parts with different
the best performing equivalence ratio for PP is 0.93 geometries, are shown in Fig. 20.20. Flame treatment
for all combinations of flame parameters. Eventually, of mobile phone covers is another application for en-
the final performance of flame treatment is a result hanced paint adhesion (Fig. 20.21A). In automotive
of several factors, such as, substrate, gas type, appli- industry, flame treatment is used for both exterior and
cation, equipment, and parameters. The flame treat- interior parts, including car bumpers (Fig. 20.21B),
ment parameters are affecting one another and thus headlamps, wheel trims, instrument panels, air bags,
the optimum combination of parameters must be de- door covers. Some nice illustrations of flame treat-
fined in each case separately. ment of car bumpers and other plastic parts can be
The oxidizing radical species present in the flame found in Refs. [104–106] as well.
react with the plastic substrate, producing adhesion- A range of commercial equipment suppliers offer
promoting functional groups. Hydroxyl, carbonyl, different types of flame treaters, for example, Aero-
carboxyl, and amide groups have been identified on gen Ltd. [107], Enercon [35], and Arcotec GmbH
the surfaces of flame-treated PE and PP [87,92,96]. [108].
Generally, the enhanced wettability and adhesion
properties of flame-treated LDPE and PP surfaces are
attributed to the oxidation of the top surface (<10 nm) 20.3.4 Aging Phenomena in
[14,87,92,94–96]. However, the oxidation depth of Surface Oxidation of Plastics
flame-treated PP surface can be even 300–400 nm,
when the exposure times are long enough [97]. One of the main drawbacks of corona treatment,
Several studies have reported how flame treatment as well as plasma and flame treatments, is the decay
affects the surface wetting and energy, oxidation of treatment level as a function of time, also known
and roughness of polyolefin surfaces. In some stud- as the aging phenomenon or hydrophobic recovery.
ies [87,94–96,98,99], the effects of flame treatment The possible explanations include: the thermody-
on adhesion properties are discussed, whereas only namically driven reorientation (rotation) of the polar
few studies have focused on examining the effects of groups from the surface into the bulk, the migration
Figure 20.20 (A) Typical burner for flame treatment of 2D materials (B) Different geometries of burners. (Repro-
duced with permission from Arcotec GmbH).
Figure 20.21 Flame treatment of (A) mobile phone covers, and (B) car bumbers. (Reproduced with permission from
Aerogen Ltd.).
Table 20.1 Concentrations and Ratios of Some of the Important Gas-Phase Reactive Species
in a Flame and an Air Corona
Time-Averaged Concentrationsa in an Air Corona

Species Mole Fractions in a Fuel-Lean Flameb At RH = 1% At RH = 100%
OH 51.4 × l0−6 0.18 × 1014 1.34 × 1014
HO2 30.4 × 10−6 1.46 × 1014 5.00 × 1014
H2O2 18.7 × 10−6 4.98 × 1014 16.0 × 1014
H 15.9 × l0−6 0.002 × 1014 0.016 × 1014
O 0.3 × l0−6 7.57 × 1014 4.88 × 1014
O3 <10−12 4700 × 1014 1800 × 1014
O/OH 0.006 42.1 3.63
a
Concentrations in species per cm3.
b
At an equivalence ratio of 0.94.
(With permission from Springer).
of low-molecular-weight additives from the bulk of compared with corona-treated ditto have also been
the plastic to the surface, and airborne contamination observed by several researchers. For instance, in
of surfaces due to improper storage conditions, es- the study by Tuominen and Lahti [100], the effects
pecially in the case of surface-oxidized polymer sur- of corona and flame treatment on the surface prop-
faces [12,14,102]. erties of LDPE-coated board were compared as
Strobel et al [103] have compared flame treatment a function of time. The wetting of corona-treated
with corona treatment of PP film with respect to gas- surface was higher directly after the treatments but
phase chemistries, wettability, and aging. Although the decay of wetting and decrease in adhesion was
both corona- and flame treatments are surface- significantly slower on the flame-treated surface
oxidation processes, the two methods differ consid- than on the corona-treated one. Brewis and Briggs
erably in the mechanism of oxidation. Some of the [70] have also stated that the wettability of flame-
important gas-phase reactive species in a flame and an treated surface decays slower compared to corona-
air corona are presented and compared in Table 20.1. treated surfaces. Briggs et al. [87] did not observe
As shown in Table 20.1, corona discharges are any significant changes in the surface oxidation or
dominated by O-atom reactions involving, for ex- adhesion levels of flame-treated LDPE surface after
ample, atomic oxygen and ozone that lead to scission 12 months of aging.
of the PP chains and the formation of water-soluble The effects of plasma treatment on the aging-
LMWOM. The extensive chain scission associated phenomenon of various surfaces have been studied
with corona processes affects the wettability and sta- extensively as well. For example, air- [112–114],
bility of the treated-PP films. By contrast, as shown oxygen- [115–117], nitrogen- [15,74,117], helium-
in Table 20.1, flame-surface oxidations are domi- [118], and argon- [118] plasmas have been used to
nated by OH radical reactions that lead to oxida- modify LDPE [15,112,115] and PP [112,115,118].
tion without LMWOM formation. The more limited The main differences between plasma and corona
chain scission associated with flame treatment leads (filamentary mode DBD) treatments have already
to formation of more polar groups on the PP surface. been listed, but a specific comparison between co-
Due to the lack of LMWOM formation, it was con- rona and plasma treatment is difficult because of
cluded the flame-treated PP is more highly oxidized the large variety of plasma sources and gases in use.
after washing with water, more wettable, and more However, the hydrophobic recovery effect of corona
stable than corona-treated PP [103]. treatment has been compared to APPs, particularly
The relatively poor stability of corona-treated to glow-type DBD plasma [119] and DBD plasma
polyolefin surfaces has been reported by several operating in a roll-to-roll process [112]. In both stud-
investigators [15,109,110,111]. The superior ag- ies, the plasma treatment produced higher and lon-
ing properties of flame-treated polymer surfaces ger lasting wettability on the PE surfaces than did
the corona treatment. To conclude, aging is a very XPS and FTIR spectroscopies; and change of surface
complex phenomenon that is strongly affected by morphology by the introduction of uniform rough-
the treatment method, the nature of substrate, and ness as observed by SEM. It can be concluded that
the storage conditions (temperature and humidity). all four important considerations affecting adhesion
Therefore, the hydrophobic recovery is difficult to strength were met using UV-laser treatment: cleanli-
generalize or predict [12,102,120]. ness, mechanical interlocking, chemical attraction,
and wetting. The potential of using UV laser for pre-
adhesion surface treatment was confirmed for a wide
20.3.5 UV-Excimer Laser Treatment variety of substrates, each requiring its optimal laser
parameters for successful treatment. As an example,
The term laser is an acronym for “light amplifica- the light absorption of PE and PP is up to two orders
tion by the stimulated emission of radiation.” Pulsed of magnitude smaller than that of PET in the spec-
excimer lasers became commercially available in the tral range of 190–250 nm. Thus, irradiation of PE
late 1970s [121]. Excimer, a word coined by combin- and PP materials using ArF- and KrF-lasers did not
ing two words “excited” and “dimer,” is the term giv- result in any modification of the surface structure,
en to a group of molecules, usually diatomic, that are only heavy thermal damages [125]. The process is
not stable in the ground state but yet have chemically effective in air and at room temperature, and is an
stable excited states. The common diatomic mol- effective, clean, environmentally friendly, precise,
ecules (and their wavelengths) used as lasing species and safe process.
include Ar2 (126 nm), Kr2 (146 nm), F2 (157 nm), One important application of the UV-laser treat-
Xe2 (172 nm), ArCl (175 nm), ArF (193 nm), KrCl ment is the activation of polymeric fiber surfaces for
(222 nm), KrF (248 nm), XeCl (308 nm), and XeF improved fiber/resin interfacial interaction in fiber-
(351 nm). Among these excited molecules, the rare reinforced composites or “advanced composites”
gas halide lasers, such as, ArF, KrF, and XeCl, are [126–128]. As shown in Tables 20.2 and 20.3, the
favored because of their efficiencies and commercial laser treatment environment has a clear effect on the
impact [122]. The pulse durations for excimer lasers surface chemistry and acid–base characteristics, as
are in the nano- to picosecond range, thus providing well as, the resulting IFSS in the composite. It is ob-
the capacity to deliver high-peak power output at vious there is an excellent correlation between the
several UV wavelengths. This makes them attractive acid–base component of the surface energy and the
for a wide range of applications, such as, microma- IFSS [129].
chining, surface modification including surface treat- For example, recently introduced Boeing 787
ment for adhesion improvement [123]. “Dreamliner” and the Airbus 350 use significant
UV-excimer laser irradiation has been shown to amount of composites as body and structural compo-
be an effective method to modify polymeric surfaces nents to reduce their weight and increase the payload
[124]. The surface modification can be carried out in and thus are in great need for good adhesion.
a variety of ways depending on the purpose of the Another important application is ultrasonic weld-
modification (etching, ablation, deposition, evapora- ing as it is an important method for joining plas-
tion, surface functionalization, etc.), the type of laser tics. Ultrasonic welding plays an important role in
used, the ambient conditions, and the material to be processing of thermoplastics because it is easily
treated. These factors are a function of the power automated and is the most rapid way to weld ther-
density (power/unit area), pulse repetition rate (fre- moplastics at a low cost. Successful welding often
quency), and the wavelength of the pulse (energy). requires a suitable treatment of the thermoplastic’s
By subjecting the polymer surface to UV-laser surface prior to the bonding. UV-excimer laser irra-
light in atmospheric environment, some part of the diation is a relatively recent technique for improving
chemical structure in its hydrocarbon group (CHx) the self-adhesion (weld) strength of commodity (e.g.,
chain can be altered to form intensely polar groups, PP, PS) and engineering [e.g., acrylonitrile butadiene
such as, carbonyl (─C═O) and hydroxyl (─OH) styrene (ABS)] thermoplastics [123]. As an example,
groups. The general phenomena observed due to the mechanical properties of PP specimens ultrasoni-
UV-laser treatment are surface cleaning by removal cally welded using different laser treatment condi-
of contamination and weak boundary layers through tions are summarized in Table 20.4.
evaporation; modification of surface chemistry by As shown in Table 20.4, the highest weld strength
imposing polar groups, such as, oxide derivatives is obtained for PP using laser parameters of 205 mJ
and hydroxides; surface crosslinking as observed by pulse energy, 700 pulses, and 400 Hz pulse frequency.
Table 20.2 Surface Energy and its Components for XeCl Laser-Treated UHMWPE (Ultrahigh-Molecular-Weight-
PE) Fibers Determined From Measured Contact Angles of Probe Liquids [129]
Experimental Conditions Dispersiona Acid–basea Surface Energya

Environment Energy Densityb No. of Pulses γD γAB γS
Control 35.7 0.4 36.1
Air 450 500 34.6 11.7 46.3
Ammonia 450 500 30.4 15.0 45.4
Argon 450 500 33.4 2.1 35.5
Helium 450 500 34.8 1.1 35.9
a
All surface energy values are in mJ/m2.
b
Energy density or fluence in mJ/pulse·cm2.
(Reproduced with permission from Taylor and Francis).
Table 20.3 Resulting UHMWPE Fiber/Epoxy Resin Interfacial Shear Strength (IFSS) After XeCl Laser
Treatment of the Fibers Under Different Conditions [129]
Experimental Conditions
Environment Energy Densitya No. of Pulses IFSS (MPa) CV (%) Increase in IFSS (%)
Control 0.96 10.6 —
Air 450 500 3.13 4.3 326
Ammonia 450 500 3.76 31.9 392
Argon 450 500 2.38 9.6 248
Helium 450 500 2.09 5.6 218
CV, Coefficient of variation.
a
Energy density or fluence in mJ/pulse·cm2.
(Reproduced with permission from Taylor and Francis).
Table 20.4 The Effect of Laser Treatment Conditions on Polypropylene Weld Strength Obtained Using
Ultrasonic Weld Conditions of 210 N Trigger Force, 2.6 s Ultrasonic On-Time, and 60 KPa Clamping Pressure
[123]
Number of Laser Pulse Laser Pulse Weld Strength Ultimate

Laser Pulses Energy (mJ) Frequency (Hz) (MPa) Extension (%)
300 205 10 1.82 ± 0.32 0.64 ± 0.02
500 205 10 6.91 + 1.31 1.18 ± 0.17
700 150 10 2.45 ± 1.24 1.41 ± 0.21
205 10 11.74 ± 1.51 1.67 ± 0.22
100 12.60 ± 0.62 1.46 ± 0.08
400 13.35 ± 0.83 1.29 ± 0.04
250 10 11.25 ± 1.49 1.43 ± 0.12
300 10 12.58 ± 1.07 1.35 ± 0.11
330 10 11.87 ± 0.95 1.29 ± 0.09
1000 205 10 9.59 ± 2.60 1.62 ± 0.10
(Reproduced with permission from Scrivener Publishing).
This corresponds to a 191% increase in weld strength CVD, most modern processes come under two head-
as a result of the laser treatment [123]. ings separated by the CVD-operating pressure: low-
pressure CVD (LPCVD) and ultrahigh vacuum CVD
(UHVCVD). LPCVD is the CVD procedure carried
20.4 Surface-Coating Deposition out under subatmospheric pressures. This low pres-
Techniques sure helps to prevent unwanted reactions and produce
more uniform thickness of coating on the substrate.
A thin film is a layer of material ranging from UHVCVD is a process in which CVD is carried out
fractions of a nanometer (monolayer) to several mi- under extremely low-atmospheric pressures; usually
crometers in thickness. Applying a thin film to a sur- in the region of 10–6 Pa. CVD methods integrate read-
face is called thin-film deposition—any technique ily with other vacuum processes used to fabricate
for depositing a thin film of material onto a substrate patterned surfaces and devices. CVD-film growth
or onto previously deposited layers. It is a fundamen- proceeds from the substrate up, allowing for inter-
tal step in many applications and advances in thin- facial engineering, real-time monitoring, thickness
film deposition techniques during the 20th century control, and the synthesis of films with graded com-
have enabled a wide range of technological break- position. There are mainly two LPCVD polymeriza-
throughs in many industrial areas. It is, for instance, tion methods that closely translate solution chemistry
useful in the manufacture of optics (e.g., for reflec- to vapor deposition; initiated CVD (iCVD) and oxi-
tive, antireflective coatings, or self-cleaning glass), dative CVD (oCVD). iCVD closely translates free-
electronics (layers of insulators, semiconductors, radical polymerization to vapor deposition, whereas
and conductors-form integrated circuits), packag- oCVD is used to form coatings of conductive poly-
ing (e.g., barrier coatings), pharmaceuticals (e.g., via mers. Both methods benefit from high chemical con-
thin-film drug delivery), and energy generation and trol and functionality retention and are able to form
storage (e.g., thin-film solar cells and thin-film bat- conformal coatings on various substrates [131,132].
teries), just to name a few. In iCVD, an initiating species, such as, tert-butyl
Deposition techniques fall into two broad cat- peroxide and a chain-growth monomer are simulta-
egories, depending on whether the process is neously introduced through the vapor phase. Inside
primarily chemical or physical [130]. Chemical the iCVD reactor chamber (Fig. 20.22A), heated
deposition processes include for instance chemical filament wires are suspended a few centimeters
vapor deposition (CVD), Parylene-coating deposi- above the substrate. The modest temperature of the
tion and plasma-enhanced chemical vapor deposi- filaments (∼250°C) results in selective formation of
tion (PECVD) or plasma polymerization. Physical free radicals from the initiator without cracking of
deposition processes include mainly physical vapor the monomer.
deposition (PVD). Adsorption and polymerization then proceed on a
cooled substrate. In the absence of an initiator species,
film growth is negligible [134]. The iCVD method has
20.4.1 Chemical Vapor Deposition proved exceptionally versatile for chain growth poly-
mers including PTFE [135], acrylates [133], methac-
CVD is a powerful technology for surface engi- rylates [136], styrenes [137], vinylpyrrolidone [138],
neering. When combined with the richness of organic and maleic anhydride [139]. Some typical functional
chemistry, CVD enables polymeric coatings to be de- monomers are shown in Fig. 20.22B. A variation on
posited without solvents, that is, the monomer(s) are the iCVD method involves the simultaneous vapor-
delivered to the surface through the vapor phase and phase introduction of a photosensitive initiator along
then undergo simultaneous polymerization and thin- with a vinyl monomer. Upon excitation by a UV-
film formation. By eliminating the need to dissolve light source, a piCVD-polymer layer deposits [140].
macromolecules, CVD enables insoluble polymers to As in the case with other CVD depositions, the range
be coated and prevents solvent damage to the sub- of polymer structures that can be deposited by iCVD
strate. As dewetting and surface tension effects are is limited by the delivery of the precursors into the
absent, CVD coatings conform to the geometry of vacuum chamber and onto the substrate surface. The
the underlying substrate. Hence, CVD polymers can precursor molecules need to have a high enough va-
be readily applied to virtually any substrate: organic, por pressure to achieve a reasonable and steady flow
inorganic, rigid, flexible, planar, 3D, dense, or porous. rate into the reactor. This limits the use of monomers
Although there are a number of different formats of and initiators with high-molecular-weight or polarity.
Figure 20.22 (A) Schematic of a typical iCVD reactor. (B) Some functional monomers polymerized by iCVD and
piCVD. (Reprinted with permission from Ref. [133]. Copyright 2016, American Chemical Society).
Most iCVD and piCVD reactors are pancake-shaped thesized using preapplied oxidant in combination with
vacuum chambers into which monomers are evapo- vapor-phase monomers has been termed vapor-phase
rated and metered by mass-flow controllers or needle polymerization (VPP) [148,149]. As the need for a
valves [131] (Fig. 20.22A). Vertical barrel style reac- solid-state dopant typically utilized to achieve solu-
tors [141] and larger scale roll-to-roll systems [142] bility is avoided, CVD results in high-conductivity
have also been described. In all cases, reactors must layers (>1000 S/cm). Simply by changing the sub-
be designed to ensure uniform gas flow to achieve strate temperature, both the electrical conductivity
uniform film thickness. One or more monomers can and the work function of oCVD PEDOT can be sys-
be delivered to the reactor, and their delivery rates can tematically tuned [150,151]. Other conductive poly-
be varied throughout the deposition process, making mers, PPy and PTAA, have also been deposited by
it possible to form copolymers, terpolymers, and gra- oCVD [152]. oCVD precursors need to have a high
dient chemistries with simple control [143,144]. The enough volatility to be delivered into the vacuum
total pressure in the reactor, filament temperature and chamber without decomposition. This, in addition to
stage temperature can also be used to tune and op- the commercial availability of functional precursors,
timize the deposition process [145]. iCVD reactors limits the range of chemistries that can be achieved
are often equipped with viewports that allow in situ by oCVD.
monitoring of the deposition process, such as, laser
interferometry [131,146] to monitor the growth rate
or spectrometers to analyze the gas-phase composi- 20.4.2 Parylene-Coating
tion in real time. This confers great control over the Deposition
iCVD deposition process and makes it possible to de-
posit films of a wide range of thicknesses with high The Parylene-coating technology is a thin-film
precision. technique belonging to the category of CVD. It dif-
oCVD enables the step growth of electrically confers from typical CVD processes, usually used to
ductive polymers, such as, poly (ethylenedioxythio- deposit inorganic oxides, carbides, or nitrides, in
phene) (PEDOT). For oCVD, the oxidant and monomer its two principal aspects. First of all, its product is a
are delivered to the substrate through the vapor phase linear ultrahigh-molecular-weight organic polymer.
(Fig. 20.23). The second difference consists in a reversed thermal
Adsorption and spontaneous reaction proceed di- arrangement. While typical CVD processes are real-
rectly on the substrate. No additional excitation of ized under cold gas hot substrate conditions, Parylene
reactants is required. Conductive polymer layers syn- is deposited in a hot gas–cold substrate system. The
Figure 20.23 (A) Schematic of a typical oCVD reactor. (B) Chemical structures of conductive polymer deposited
by oCVD. PEDOT; PPy, polypyrrole; PTAA, poly(3-thiopheneacetic acid) [147]. (With permission from Elsevier).
Parylene-vacuum deposition process is illustrated in Parylene is the generic name for members of a
Fig. 20.24. unique polymer series. These members (or variations
The coating cycle begins with vaporization of the of Parylene) each offer their own, slightly different,
powdered raw material (dimer) at 150°C, creating a coating properties to engineers. Commercially avail-
dimeric gas. Gas molecules are subsequently cleaved able Parylene variants, along with their respective
to the monomer form in a second stage by heating to properties, include the following.
650°C. The active monomer gas is then introduced to
an evacuated coating chamber where it disperses and • Parylene N, poly(para-xylylene), the basic
polymerizes spontaneously on substrate surfaces at member of the series, is a completely linear,
room temperature to form a Parylene film. Unlike a highly crystalline material. It is a primary
curing liquid coating, this molecular stage activity dielectric, exhibiting a very low-dissipation
produces no stress or surface tension on coated sur- factor, high-dielectric strength, and a low-
faces. The monomer gas disperses evenly throughout dielectric constant invariant with frequency.
the chamber. The Parylene deposition exhibits no liq- This form has the highest penetrating power of
uid properties, such as, surface tension or meniscus, all the Parylenes (with exception for Parylene
and all sides of every surface are exposed simulta- HT, see later in this section).
neously to the polymerizing gas, including flat sur- • Parylene C, the second commercially available
faces, sharp edges, slots, and crevices. As Parylene member of the Parylene series, is produced
is applied as a gas, the coating effortlessly penetrates from the same raw material (dimer) as Parylene
crevices and tight areas on multilayer components, N, modified only by the substitution of a chlo-
providing complete and uniform encapsulation. Op- rine atom for one of the aromatic hydrogens.
timal thickness of the polymer coatings is determined Parylene C has a useful combination of elec-
based on the application and the coating properties trical and physical properties, plus a very low
desired. While Parylene coatings can range in thick- permeability to moisture and corrosive gases.
ness from hundreds of angstroms to several millime- • Parylene D, the third member of the series,
ters, a typical thickness is in the micron range. is produced from the same raw material as
Figure 20.24 Illustration of the Parylene vacuum deposition process. (Reproduced with permission from Para Tech
Scandinavia).
Parylene N, modified by the substitution of of 10–5 Torr or below, the Parylenes are formed at
chlorine atoms for two of the aromatic hydro- around 0.1 Torr. Under these conditions, the mean
gens. Parylene D is similar in properties to Pa- free path of the gas molecules in the deposition
rylene C with the added ability to withstand chamber is in the order of 0.1 cm. Therefore, un-
slightly higher-use temperatures. like vacuum metallizing, the deposition is not line of
sight, and all sides of an object to be encapsulated are
The chemical structure of the different Parylene uniformly impinged by the gaseous monomer. This
variants is shown in Fig. 20.25. is responsible for the truly conformal nature of coat-
In addition, the Parylene polymer series also in- ing. Compared with vacuum metallizing, deposition
clude Parylene HT, the newest commercially avail- rates are fast, especially for Parylene C, which is nor-
able variant of Parylene. The alpha hydrogen atoms mally deposited at about 0.2 mm/h. The deposition
of the N dimer have been replaced with fluorine. This rate of Parylene N is somewhat slower [154].
variant of Parylene is useful in high-temperature The Parylene conformal coatings are ultrathin,
applications (short term up to 450°C) and those in pinhole-free polymer coatings that provide a number
which long-term UV stability is required. Parylene of high-value surface treatment properties, such as,
HT also has the lowest coefficient of friction and di- excellent moisture, chemical and dielectric barrier
electric constant, and the highest penetrating ability properties, thermal and UV stability, and dry-film lu-
of the four variants [153]. bricity. These properties make Parylene coatings the
The Parylene polymers are deposited from the ideal choice for a number of industrial applications
vapor phase by a process that in some respects re- throughout the medical device, electronics, automo-
sembles vacuum metallizing. Unlike vacuum metal- tive, military, and aerospace industries. Some exam-
lization, however, which is conducted at pressures ples are listed [155].
Figure 20.25 Chemical structure of the most commonly used Parylene variants. (Reproduced with permission from
SCS).
• Hydrophobic coating (moisture barrier in, for costly and higher performance fluoroelastomers
example, biomedical hoses). through Parylene coating as it allows more conven-
• Barrier (e.g., for filtering, membranes, or tional rubbers to be used in demanding industrial
valves). applications. Parylene is resistant to salts, acids, sol-
• Electronics in harsh environments. vents, reagents, and gases; and the applied film has
high-dielectric strength and does not compromise
• Microwave electronics, as well as, for space, the original electrical properties of the rubber com-
avionics, and military applications. ponents it is protecting [155].
• Sensors in harsh environments (e.g., fuel/air A large industrial Parylene-coating system from
sensors in vehicles). Para Tech Scandinavia is shown in Fig. 20.26. The
• Corrosion protection on metal surfaces. large deposition chamber can be used to coat up to
• Reinforcements of microstructures. 80 lbs of substrates per cycle. The horizontal tumbler
• Abrasion protection (protection from wear). is set to rotate at a speed that provides maximum ex-
posure of surfaces to the monomer gas while avoid-
• Protection of plastics, rubber, and similar mate- ing substrate damage.
rials in harmful environments. The coating chamber is mounted on a rail mech-
• Reduce friction on, for example, catheters, acu- anism to speed the loading and unloading of the
puncture needles, and microelectromechanical tumbler. Tumble coating is a fast and cost-effective
systems. means for coating unfixtured components, such as,
• Electric insulation in very limited spaces (e.g., ferrites, elastomer parts, and other small components
as dielectric in VLSI circuits). with an even and controlled layer of Parylene [155].
As shown, the Parylene coatings can be deposited

on many different substrates, including plastics and 20.4.3 Plasma Enhanced Chemical
rubber. When coating elastomers, film elasticity, Vapor Deposition
and surface-adhesion integrity enable the coating to
accommodate elongation of the underlying elasto- PECVD causes the reactive gases to decompose
mer without fracture or loss of the film-to-substrate and enhance chemical reaction rates of the precur-
bond. In fact, Parylene has a typical elongation to sors via the electrical discharge rather than via ther-
break performance of 200%. The Parylene coat- mal heating. This allows films to deposit at lower
ing also tends to eliminate surface tact and sticki- temperatures than CVD. The lower temperatures
ness without adding stiffness. This is often called also allow for the deposition of organic coatings,
lubricity, a very useful property for items, such as, such as, plasma polymers. Usually, the operational
rubber keypads and medical products. In the case pressures in these systems are 0.1–10 Torr, the plas-
of keypads, the Parylene coating prevents dirt and ma density in PECVD discharges is 109–1011 cm–3
oils from penetrating the elastomer surface, protects and the ionization degrees are 10–7–10–4 [6]. The
printed legends (up to 400% longer), and preserves process is also often referred to as plasma polym-
keypad appearance. Parylene also adds chemical re- erization. PECVD/plasma-polymerization processes
sistance to rubber surfaces. It might even be possible are performed both at low and atmospheric pressure,
to substitute more conventional rubbers for the more as described later.
Figure 20.26 Model 2000H horizontal Parylene-coating system. (Reproduced with permission from Para Tech Scan-
dinavia).
20.4.3.1 Plasma-Deposited Coatings a variable composition; they should also be durable

at Low Pressure and resistant toward aging, oxidation, shrinking, if
possible, comparable with conventional polymers.
Plasma polymerization refers to the formation of
A second objective is to convert monomers possess-
polymeric materials under the influence of plasma
ing functional groups into polymer-like films with a
(partially ionized gas). As the most practical means
“unique” functional group. Depending on choice of
of carrying out plasma polymerization involves the
monomer (precursor), plasma polymers have found
use of an electric glow discharge in a vacuum, the
several different functions and applications.
term glow discharge polymerization has been used,
in every practical sense, synonymously with plasma
• Adhesion promoting surfaces, using for in-
polymerization, although plasma polymerization can
stance vinyl-, acrylic- or allyl-based mono-
be carried out by means other than glow discharge. In
mers containing either carboxylic (─COOH),
contrast to pure chemical chain-growth polymeriza-
amino (─NH2), hydroxyl (─OH), epoxy
tion of classic monomers containing activated double
bonds, polymerization can also be initiated by any (CH─O─CH), vinyl (─CH2═CH2─) func-
gas plasma at atmospheric- or low pressure or in liq- tionality. Proper choice of these functional
uid phase. The materials formed are vastly different groups allows them to react with both substrate
from conventional polymers [156]. Several reaction and coating with formation of covalent bonds,
mechanisms have been proposed for the formation which is important for adhesion since it is ex-
of plasma polymers, such as, monomer fragmenta- pected that covalent bonding produces more
tion followed by polyrecombination into randomly powerful and highly durable adhesion [157].
structured and crosslinked films; fragmentation, ac- • Hydrophobic and oleophobic surfaces, by using
companied by the formation of acetylene or other organosilicon-, hydrocarbon-, fluorocarbon-
film-forming intermediates and deposition of PS-like based precursors, silicone-, polyolefin-, and
material; plasma-initiation of a radical chain-growth Teflon-like coatings can be prepared. If these
polymerization; and ion-molecule reactions, as well coatings are combined with a suitable micro-/
as, ionic chain-growth polymerization. An excellent nanosurface structure, even superhydrophobic
review on this topic can be found in Ref. [157]. The and superoleophobic surfaces can be obtained
bulk structure of plasma polymers is completely ir- [158].
regular, far from that of conventional polymers. • Gas diffusion barrier coatings, oxygen- and
Generally, one of the intentions of plasma polymer- water vapor transmission rates through various
ization is to produce ultrathin, pinhole-free polymer- polymeric packaging materials, films, as well
like layers with a defined, regular structure, but with as containers, can be significantly reduced by
Figure 20.27 Overview of Sidel’s ACTIS-coating process. (Reproduced with permission from Sidel).
plasma deposition of ultrathin, glass-like SiOx than 600 mL), which are especially susceptible to gas
coatings [from a mixture of hexamethyldisilox- exchanges (ingress of oxygen, O2 and loss of carbon
ane (HMDSO) (or similar organosilicons) and dioxide, CO2) make it possible to package sensitive
oxygen] [159–161]. Similar barrier improve- drinks, such as, beer, sodas, tea, juices, carbonated
ments can also be achieved by deposition of water, and even sauces, in PET and to meet the mar-
hydrocarbon-rich coatings from acetylene or ket requirements in terms of shelf life for these prod-
methane/helium mixture [162]. ucts. An overview of the coating process is shown
• Abrasion and scratch resistant coatings, can in Fig. 20.27 and the principle of how the ACTIS
be obtained on plastic substrates by plasma coating is deposited on the inside wall of PET bottles
deposition of glass-like SiOx coatings, but sig- is outlined in Fig. 20.28.
nificantly thicker layer (approx. 5 µm) with a The barrier coating process comes in two versions,
gradient from a highly organic composition at ACTIS and ACTIS Lite, and in both cases the com-
the substrate to a highly inorganic glass-like position of the carbon layer is the same. However,
composition at the uttermost surface [163]. its thickness and slight coloration are directly related
• Corrosion-resistant coatings, can be obtained to the plasma process time: ACTIS = 2.5 s, whereas
on metal substrates by plasma deposition of hy- ACTIS Lite = 1.2 s (Fig. 20.29).
drophobic coatings (e.g., HMDSO) with a high As it is inside the bottle, the ACTIS barrier is pro-
degree of crosslinking [164]. tected from mechanical impact. The inert layer, in
direct contact with the beverage, prevents any PET-
• Biocompatible coatings, poly(ethylene oxide), related migrations (acetaldehyde). It protects the
also known as poly(ethylene glycol) (PEG), is packaged product from any gases coming from PET
the most common surface coating in the bio- (O2, etc.). Barrier-improvement factors up to 30 and
medical materials field used to render a material 7 have been reported for O2 and CO2, respectively,
resistant against protein fouling. Poly(ethylene which correspond to a 6-month shelf life (with less
glycol)-like films has been developed through than 1 ppm of O2 ingress and less than 17% of CO2
the use of plasma polymerization of monomers loss). Up to 40,000 bottles can be coated per hour
containing ethylene oxide units, typically gly- [166].
col diethers, which are also commonly known KHS Plasmax has developed a gas-barrier coat-
as the “glyme” family of monomers [165]. ing process for plastic bottles called FreshSafe-PET,
which is quite similar to the ACTIS process described
earlier [167]. The main difference is that KHS uses
20.4.3.1.1 Some Examples Of Industrial a PECVD process where an ultrathin glass-like SiOx
Applications coating is deposited from a plasma based on a HMD-
The Amorphous Carbon Treatment on Internal SO/O2 mixture on the inner wall of PET bottles. In
Surface (ACTIS) coating, developed by the French contrast to the ACTIS coating, the SiOx coating is
company Sidel, is a thin layer of hydrogen rich car- 100% transparent. Otherwise, the gas barrier proper-
bon deposited by plasma polymerization of acetylene ties are comparable. The InnoPET 20Q is designed
on the inside wall of a PET bottle. This barrier solu- for large product lines and achieves outputs of up to
tion is designed for small-size PET containers (less 40,000 PET bottles per hour processing container
Figure 20.28 Principle of how the ACTIS coating is deposited on the inside wall of PET bottles. (Reproduced with
permission from Sidel).
Figure 20.29 (A) ACTIS process time = 2.5 s. (B) ACTIS Lite process time = 1.2 s. (Reproduced with permission
from Sidel).
sizes of 100–1500 mL. The plasma coating process based on perfluorinated carbon compounds, for pro-
is also illustrated in [168,169]. tection of products across five key market sectors
P2i is a nanotechnology solutions provider who mentioned earlier. Their patented pulsed-plasma
works with manufacturers to deliver liquid repellent process takes place under low pressure within a
nanocoating protection to products across five key vacuum chamber at room temperature. A RF plasma
market sectors: electronics, lifestyle, life sciences, activates the device’s surface, ensuring water and
filtration and energy, and military, and institutional other contaminants that could disrupt the bonding
[170]. The P2i technology employs plasma polym- are removed and free-radical sites are created. The
erization, sometimes also referred to as PECVD, monomer is introduced as a vapor and pulsed RF
to apply an ultrathin liquid-repellent nanocoating plasma is used to polymerize it and bond it to the
free-radical sites on the surfaces. The low pressure in

the chamber means that the monomer can permeate
into all areas of the device so that the polymer coats
all surfaces—internally and externally. The result is
an ultrathin layer of polymer that is just a few nano-
meters thin. With P2i, the lifetime of smartphones
and other electronic devices increases dramatically.
The plasma coating provides invisible protection
against a range of liquid exposure, including splash-
es, spills and accidental immersion. Furthermore,
P2i’s technology enhances the performance and
applicability of naturally water repellent materials,
such as, PP and PTFE. By increasing the levels of
oil and alcohol repellency, filters can be used in the
most demanding environments, such as, automotive,
industrial, gas turbine, and pharmaceutical product
protection-making fabrics, such as, cotton, liquid re- Figure 20.31 Example of a lab set up for aerosol-
pellent, without changing their breathability or other assisted DBD treatment. (Reproduced with permission
properties [170]. from VITO).
20.4.3.2 Plasma-Deposited Coatings is provided in Fig. 20.31. To ensure stable plasma

at Atmospheric Pressure operation in nitrogen gas, the gap is limited to 2 mm.
Hence, this configuration is mainly used for foils,
Operating at ambient pressure allows industry to textiles, and fibers of limited thickness. The upper
move from batch to continuous processing and also stainless steel high-voltage electrode is water cooled
facilitates much simpler equipment designs with re- and can move over the grounded aluminum substrate
duced maintenance requirements due to the lack of holder at speeds up to 50 m/min. Multipassing is pos-
vacuum pumps, seals, etc. Besides activation and sible to simulate in-line treatment using more elec-
functionalization of surfaces, the APP technology trodes. Several samples, typical of A4 paper size,
also involves different coating processes. Recent can be treated at once for various analysis and ap-
advances in this technology have included the de- plication tests. The high-voltage electrode consists of
velopment of aerosol-assisted plasma deposition two separate stainless steel plates of 80 × 300 mm.
techniques. A schematic view of an aerosol-assisted Additional nitrogen-purge gas knives are installed to
DBD treatment of foils is shown in Fig. 20.30. eliminate the atmospheric oxygen in order to limit
An example of a lab setup for aerosol-assisted streamer formation. A bottle with liquid precursor
plasma treatment in direct contact with the substrate and aerosol atomizer are mounted on the moving
high-voltage electrode. Plasma discharges are gener-
ated in a frequency range of 1–100 kHz and at power
levels between 0.5 and 5 W/cm2 [171].
Switching from a traditional gas-phase PECVD
system to one based on liquid aerosol technol-
ogy opens up a range of coating options involv-
ing complex precursor formulations that cannot be
readily accessed using traditional technology. Such
formulations could include different hybrid organic–
inorganic precursors and sol–gel systems thereof (e.g.,
tetraethoxysilane, glycidoxypropyltrimethoxysilane,
methacryloxypropyltrimethoxysilane, and propyl-
trimethoxysilane) [172], fluorocarbons (e.g., hep-
Figure 20.30 Schematic view of an aerosol-based tadecafluorodecyl acrylate), organometallic (e.g.,
DBD treatment of foils. (Reproduced with permission titanium tetrachloride and titanium tetraethoxide),
from VITO). liquid silicones, silicon-based films, etc. [173–176].
The aerosol technology can be utilized in different environmental impact [178]. The APPLD process is
plasma sources, including DBD, APGD, and plasma based on APGD presented earlier.
jets. Mix et al. has for instance sprayed water and
ethanol as aerosol into the plasma zone in a DBD to
introduce polar, O-containing groups on PE and PP 20.4.3.2.1 Deposition of Coatings by
films [177]. Atmospheric-Pressure Plasma Jet
Dow Corning has developed the atmospheric- The deposition of coatings by APPJs is more com-
pressure plasma liquid deposition (APPLD) process, plicated than surface treatment. It requires supplying
which combines APP processing with liquid precur- an additional precursor as a vapor rather than in a
sors to deliver highly functional thin-film surface gaseous state. Silicon–organics, metal–organics, or
coatings. APPLD is a room temperature process that various solutions may be used as precursors. Liquid
can be applied continuously to material in flexible precursors are atomized or vaporized for transfer into
web, rigid sheet or 3D geometry. Dow Corning has, the working volume of the APPJ system. A typical
for instance, developed wide-area APP processing APPJ is shown both schematically and in operation
platforms for depositing fluorocarbon coatings on a in Fig. 20.32 [179,180].
wide range of flexible substrates (e.g.,textiles), for APPJs have been widely used for the deposition
incorporation of oil-repellent functions. Compared of various metal oxide coatings, but the majority of
with traditional fluorocarbon treatment of textiles, the scientific work found in the literature deals with
the APPLD processing eliminates the need for costly deposition of coatings on inorganic substrates. How-
multiple processing steps, significantly reducing the ever, APPJ is also used to deposit various coatings
Figure 20.32 Example of an APPJ for deposition of coatings. (A) Schematic view. (B) APPJ in operation [179,180].
(Reproduced with permission from Fraunhofer IFAM).
on plastic substrates. For instance, SiOx- and AlOx

films, using HMDSO and aluminum-containing pre-
cursors, respectively, have been deposited on plastic
substrates to enhance scratch resistance or to lower
the gas permeability [181–183]. Using an appro-
priate precursor makes it possible to deposit other
types of oxide materials on plastics. For example,
the depositions of tungsten/molybdenum oxide films
[184], electrochromic organomolybdenum [185],
and nickel–iron oxide (NiFexOyCz) thin films on PET/
indium–tin oxide (ITO) substrates to create flexible
electrochromic devices [186] have been demon-
strated. Deposition of photocatalytic TiO2 coatings
on membranes (with an 800 nm pore size) by APPJ
was reported by Fakhouri et al. The method is based
on the introduction of a liquid precursor sprayed
into an open-air APPJ. The photocatalytic activity
of the TiO2-thin films prepared by APPJ have been
compared with our best N-doped TiO2-thin films, de-
posited by reactive RF magnetron sputtering. Under
optimized conditions, the TiO2 coatings deposited by Figure 20.33 An APPJ system designed for deposi-
APPJ were characterized by a higher photocatalytic tion of coatings. (Reproduced with permission from Plas-
activity as compared to the optimized thin films de- maTreat).
posited by RF sputtering [187]. Although most ap-
plications of APPJs have involved the deposition of The plasma source and the precursor delivery system
oxides, the use of this method for preparation of a are shown in Fig. 20.34.
metal coating has also been reported. DBD APPJs Tetraethoxysilane may be combined with oxygen
were used for the direct deposition of Cu coatings plasma to deposit glass-like SiOx coatings for scratch
on polyamide substrates. Using a mixture of Ar and and corrosion resistance. As an example, the plasma
H2 avoided oxidation of the Cu and resulted in high- source has been used to synthesize hard, adhesive,
purity coatings [188]. and highly transparent bilayer organosilicate thin
Commercial APPJ systems for deposition of coat- films on large poly(methyl methacrylate) substrates
ings are provided by several companies, for exam- by atmospheric plasma, in ambient air, at room tem-
ple, Plasmatreat and Surfx Technologies. By using a perature, in a one-step process, using a single pre-
combination of Plasmatreat’s Openair plasma tech- cursor. The bottom layer is a carbon-bridged hybrid
nology and PlasmaPlus, complex 3D components silica with excellent adhesion to the poly(methyl
can be coated using APP [189]. Depending on the ap- methacrylate) substrate, and the top layer is a dense
plication, PlasmaPlus nanocoating can deposit spe- silica with a high Young’s modulus, hardness, and
cific functional coatings ranging from hydrophobic scratch resistance. The bilayer structure exhibited
water and dirt-repellent, gas-diffusion barrier coat- ∼100% transmittance in the visible wavelength
ings, electrically conductive coatings, antimicrobial range, twice the adhesion energy and three times the
photocatalytically active TiO2 coatings, adhesion- Young’s modulus of commercial polysiloxane sol–
promoting coatings [190]. Plasmatreat’s APPJ sys- gel coatings [191].
tem for deposition of coatings is shown in Fig. 20.33.
Surfx Technologies has developed a device for
PECVD [54]. A volatile precursor containing the 20.4.4 Physical Vapor Deposition
coating elements is fed separately to the source. The Processes
precursor and plasma gas mix together, react, and
deposit the desired thin film. The A-PD precursor PVD comprises a variety of vacuum deposition
delivery system includes a temperature-controlled methods, which can be used to produce a vapor
bath, gas manifold system with vent/run, and dilu- of material, which is then deposited on the object,
tion mass-flow controllers, which provide accurate which requires coating. It is an entirely dry process,
delivery of precursors and act as moisture barriers. which offers a wide range of coating materials. A
Figure 20.34 (A) Device for PECVD. (B) The A-PD precursor delivery system. (Reproduced with permission from
Surfx Technologies).
very large number of inorganic materials—metals, magnetron sputtering). Table 20.5 gives an overview
alloys, compounds, and mixtures, [e.g., titanium ni- of the typical parameters and the quantity of ionized
tride (TiN), zirconium nitride (ZrN), chromium ni- target atoms of some PVD processes [198].
tride (CrN), titanium aluminum nitride (Ti–Al–N)]
are commonly used)—as well as some organic mate-
rials, can be deposited using PVD technologies. The 20.4.4.1 PVD Coatings on Plastics
basic PVD processes fall into two general categories: PVD processes are traditionally used for the de-
sputtering and evaporation. There are several PVD position of various coatings on tools and compo-
techniques available for deposition of hard coatings. nents and other metallic or ceramic substrates, for
Among them, cathodic arc vapor (plasma or arc ion example, to improve surface hardness, wear resis-
plating) deposition [192–194], magnetron sputtering tance, and corrosion resistance. However, more and
(or sputter ion plating) [195], and combined mag- more plastic products are used today in fields where
netron and arc processes [196], are the most widely metals were previously predominant. In these cases,
used techniques. Magnetron sputtering is a plasma- the end product should meet functional requirements
coating process whereby sputtering material is eject- (durability, scratch, corrosion, and chemical resis-
ed due to bombardment of ions to the target surface. tance) and decorative appearance. Another impor-
The vacuum chamber of the PVD-coating machine is tant application includes metallized and transparent
filled with an inert gas, such as argon. By applying inorganic gas-diffusion barrier layers on packaging
a high voltage, a glow discharge is created, result- films.
ing in acceleration of ions to the target surface and a As plastics themselves are relatively soft and
plasma coating. The argon ions will eject sputtering have a limited possibility for colorization, metals or
materials from the target surface (sputtering), result- ceramics need to be deposited on the plastic product
ing in a sputtered coating layer on the products in surface. Historically, there are basically three ways
front of the target. High Power Impulse Magnetron to do that: electroplating, painting, and PVD depo-
Sputtering (HIPIMS) has given a third dimension to sition. Electroplating is normally the deposition of
PVD-coating technology. HIPIMS technology shows a copper–nickel–chromium layer with a thickness
that it is possible to combine the advantages of high of about 30 µm and a typical surface hardness of
ionization-like arc evaporation with the advantages around 600 HV. The thickness levels the surface
of magnetron sputtering. The result is good adhesion imperfections. Electroplating, however, is a wet, en-
and a dense, very smooth coating [197]. The differ- vironmentally unfriendly process based on the chro-
ent PVD processes differ with respect to the type mic anhydride used as a source of hexavalent Cr+6,
of evaporation of the metallic components and the which is considered cancerogenic. For this reason,
plasma conditions employed during the deposition Cr+6-based processes are banned in Europe [2007
process. The transition of the metallic component (to Restriction of Hazardous Substances Directive] and
be deposited) from a solid to a vapor phase (in which heavily regulated in the United States by the Envi-
metal atoms are ionized in different ways) may be ronmental Protection Agency. Furthermore, chro-
performed by heating of an evaporation source (as mium plating is mainly limited to ABS and the color
in cathodic arc) or by sputtering of a target (as in possibilities are very narrow. The main disadvantage
Table 20.5 Typical Parameters and Quantity of Target/Cathode Ions/Atoms of Different PVD Processes [198]
Processes
Magnetron Anodic Arc Electron Beam Cathodic
Parameters Sputtering Ion Plating (EB)-Ion Plating Arc-Ion Plating
Evaporation tool Sputter effect EB EB Thermal arc
Phase transformation Solid-vapor Solid-vapor Liquid-vapor Solid-vapor
Geometry of target/ Flexible Limited Limited Flexible
cathode
Quantity of ionized 1–5 5–40 <1 50–100
target atoms (%)
Additional ionization Aimed Unusual Aimed Not necessary
Inert gases necessary Yes No Variable No
Reactive deposition Yes Yes Yes Yes
possible
(Reproduced with permission from Elsevier).
of painting is lack of hardness, primer requirement substrates, are used in many applications, including
for many plastics, and absence of an attractive metal- automotive interior and exterior parts, consumer
lic look. PVD processes, either sputtering or evapo- products, such as, mobile phones, computers and
ration, have several advantages compared with elec- cameras, jewelry and watches, bathroom equipment,
troplating and painting. It is an entirely dry process door handles, and eyewear. Other PVD applications
(thus environmentally safe) and offers a wide range for plastic substrates include, for instance, antire-
of coating materials. The PVD sputtering process flection coatings for the ophthalmic industry and
is nicely presented and explained in Ref. [199] and metallized layers on CD and DVD discs. The PVD
an example of a PVD–chrome deposition process is layer is usually applied with a thickness ranging
presented in Ref. [200]. PVD coatings can be used from 0.5 µm to 3 µm, which will not give a leveling
both as basecoat and topcoat. The advantage of such effect. This can be overcome by using a lacquer with
a system is that the functionalities of the whole coat- enough thickness to have a leveling effect and to de-
ing can be split in two; the basecoat brings hardness, posit the PVD coating on top. Alternatively, a high-
whereas the topcoat adds the bright color in as many quality mold can be used to obtain a highly polished
shades as possible. Diamond-like carbon (DLC) has surface. PVD in combination with PECVD offers
been evaluated as a basecoat on plastic substrates. the additional possibility to apply a thin transparent
The advantages of using DLC are low production top coat that further improves the scratch resistance
costs that can be combined with tunable mechani- without deteriorating the color. This top coat could
cal properties and an atomically smooth surface. The for instance be deposited from a HMDSO precur-
hardness of a DLC basecoat can be tuned by chang- sor. The siloxane coating has a low-surface energy
ing the acetylene flow. In this way, it is possible to leading to strong hydrophobic properties with water
achieve the optimum thickness and hardness for the contact angles exceeding 90 degree. This protective
specific application. The deposition rate is also de- coating largely improves the fingerprint resistivity
pendent on the acetylene flow. Increasing the acety- of the coating. The combination PVD + PECVD is
lene flow from 5 to 80 cm3/min for example, results available in most industrial systems today. One ex-
in almost triple the deposition rate [201]. ample is shown in [202] where automotive light re-
Plastics as a material offer advantages, such as, flectors are prepared by deposition of high-reflective
they can be easily shaped with details and reduce PVD coatings, that is, aluminum is evaporated
weight and manufacturing cost as compared to the onto polycarbonate substrates followed by plasma
use of metals. Decorative coatings, being scratch re- polymerization of an organosilicon, for example,
sistant, and giving a bright color to metal and plastic HMDSO [164].
Figure 20.35 Examples of some industrial PVD coaters. (A) PlastiCoater from Impact Coatings, reproduced with
permission from Impact Coatings; (B) Flexicoat 1200 from Hauzer Techno Coating. (Reproduced with permission
from Hauzer Techno Coating).
Commercial PVD coating systems are provided used material for creating such barrier coatings is
by several companies, for example, Hauzer Techno aluminum, which makes opaque films, even though
Coating B.V [203], Oerlikon Balzers [204], Impact transparent inorganic coatings are also used to an in-
Coatings [205], and Bühler Leybold Optics [206]. creasing extent.
Some examples of industrial PVD coaters are shown Aluminum vacuum web coating (or metallization)
in Fig. 20.35. for packaging applications is an established produc-
tion technology for high-volume mass production. It
is performed using a PVD process where aluminum
20.4.4.2 Vacuum Deposition of Barrier is the most common metal used for deposition but
Coatings on Plastic Films other metals, such as, nickel or chromium are also
The conventional packaging materials that protect used. The coating is either evaporated or sputtered
the products are paper, metal, and glass, which have onto the plastic film substrate. The basic layout of a
been used in the packaging industry over centuries. vacuum web coater consists of vacuum equipment,
Metal and glass have excellent barrier properties; winding system, and an evaporation source. Vacuum
however, they are heavy and expensive. At present web coaters are with very few exceptions operating
polymeric materials are mostly used in the packaging semicontinuously. When the machine is loaded with
industry. Polymeric materials are flexible, lighter, the roll and is pumped down to the necessary vacuum
and for the production of the packaging less material level, the coating source is heated to evaporate alu-
can be used. Polymer materials are often also trans- minum while the web is winded from unwinder to
parent and cost-effective. The common disadvantage rewinder. To protect the web from thermal damages
of polymeric materials is their lower barrier proper- during coating, it is placed on a chilled drum. While
ties against gases and vapors. Besides using other tra- oriented PP and PET are the most common films
ditional barrier films, such as, polymeric layers, such used for metallization, nylon, PE, and cast PP are
as, poly(vinylidene chloride) and ethylene vinyl al- also used. Typical coating thickness is around 50 nm,
cohol, the barrier properties of plastic films are often which is less than 1% of the thickness of an alumi-
improved by using inorganic barrier layers prepared num foil [207]. The evaporated Al coating reduces
in different PVD processes. The most frequently the permeability of the film to light, as well as, water
vapor and oxygen. Typical barrier improvement fac- [159–161]. Silicon oxides and aluminum + oxygen
tors for a metallized 12 µm PET film are 40 and 380 are the most commonly used evaporation materi-
with respect to water vapor and oxygen, respectively als to produce SiOx and AlOx coatings for packaging
[208]. applications. During thermal or EB evaporation of
Applications of metallized films include the fol- glass-like SiOx, coatings SiO or SiO2 is heated up in
lowing. a crucible in a vacuum chamber. The evaporation is
achieved either by means of a resistive or inductive
• Decorative purposes (e.g., as Christmas tinsel, heater (thermal evaporation) or an EB gun (EB evapo-
wrappers and ribbons, metallic helium-filled ration). When SiO is used, the vapor is oxidized in
novelty balloons) [208], packaging (metallized a controlled reactive atmosphere in order to obtain a
PET and PP have replaced foil laminates for degree of oxidation between x = 1.5–1.8 in the coated
products, such as, snack foods, coffee, and can- layer. As the material evaporates, it condenses on the
dy, which do not require the superior barrier of film, which is passing above the crucible. Although
aluminum foil. the process is very hot (1350–1400°C in the SiO
• Packaging (for products, such as, snack foods, case), the film does not melt because it is cooled using
coffee, and candy, which do not require the a chilled drum.). EB evaporation is today the preferred
superior barrier of aluminum foil, susceptor evaporation method as it is the most flexible high-
for cooking in microwave ovens, for example, power source to evaporate nearly any kind of mate-
popcorn bag. rial [207]. To deposit AlOx coatings, it is possible to
• Insulation (radiation resistance, heat insula- evaporate aluminum and later oxidize it to Al2O3. Al-
tion, in spacesuits, blankets, etc.) ternatively, aluminum can be sputtered onto the plas-
tic film from a plasma composed of a mixture of Ar
• Electronics (e.g., as dielectric in the manufac- and O2 [210]. Ceram–AlOx transparent barrier films
ture of capacitors used in electronic circuits, in are an example of a commercially available coating
antistatic bags). for various packaging applications. It is claimed that
they have outstanding barrier properties against gases
and water vapor and also exhibit extremely high-sur-
20.4.4.2.1 Inorganic Transparent Barrier face energy, which enhances the adhesion of coatings,
Coatings adhesives, and inks to the surface [211]. Industrial
During the last years the trend in flexible packag- coaters for deposition of transparent barrier coatings
ing has gone toward the use of inorganic transparent are provided by, for example, Bühler Leybold Optics
barrier films as they offer several advantages com- [206], and coated films can be obtained from, for ex-
pared to existing barrier materials. ample, FILMtech [211] and Toppan [212].
Many technical applications, for example, flexible
• They can provide barriers against oxygen, wa- organic light emitting devices, lighting, flat panel dis-
ter vapor, and aroma similar to those of metal- plays, flexible solar cells have strict requirements with
lized plastics. regards to the maximum oxygen and especially water-
• They are transparent, allowing visual inspec- vapor transmission rate of their encapsulation. In or-
tion of the package content. der to obtain the flexibility, glass has been replaced by
plastic films, such as, poly(ethylene naphthalene) and
• They are microwave-transparent and ideally
PET, and transparent coatings, such as, SiOx and AlOx
suited for microwave applications.
have been applied to give protection. However, it has
• They are not adversely affected by moisture. been found that single layers of SiOx and AlOx are not
• They allow for detection of any metal particles sufficient to protect the moisture-sensitive devices.
in the product. High-barrier values are needed to prevent the single
• They are environmentally friendly in terms of layers from being damaged and to maximize the over-
recycling and source reduction [209]. all lifetime of the complete device [213]. Multilayer
high-barrier films on flexible substrate, for instance,
There are different PVD-based coating techniques based on SiOx or AlOx are state-of-the-art technology
available for the production of inorganic transpar- realized by high-vacuum sputter roll-to-roll deposi-
ent barrier films, for instance thermal-, reactive- and tion, where the inorganic coatings are separated by dif-
EB-evaporation processes, as well as, sputtering. It ferent types of organic layers. A few examples are the
is also possible to use PECVD, as described earlier Barix multilayer coatings from Vitex Systems [213],
the 3M Ultra Barrier Solar Film from 3M [214], and Inorganic transparent coatings are also used as
an ORMOCER-based coating from the Fraunhofer transparent conductive oxide layers (TCO), which
Polymer Surfaces Alliance POLO in Germany [215]. are thin films of optically transparent and electri-
Another application involving inorganic transparent cally conductive material. TCOs are an important
coatings is the use of low emissivity (low-e) and elec- component in a number of electronic devices includ-
trochromic coatings for architectural and automotive ing liquid-crystal displays, OLEDs, touchscreens,
glazing. A huge part of the primary energy produced photovoltaics, and solar cells. Touch panels of smart
worldwide for heating or cooling of buildings is lost phones and tablet PC s and front contact layers in
by heat transfer through the glazing of the buildings. flexible photovoltaics are only a few examples [224].
Foils with low thermal emissivity (low-e) or smart Some applications, such as solar cells, often require
glass coatings can minimize the energy losses drasti- a wider range of transparency beyond visible light to
cally when integrated into the glazing. There are both make efficient use of the full solar spectrum.
hard and soft low-e coatings. A soft low-e coating is TCO films can be deposited on a substrate through
a multilayered low-e coating deposited on glass or various deposition methods, however, conventional
plastic film, normally by magnetron sputtering in a fabrication techniques typically involve magnetron
roll-to-roll deposition process. It typically consists of sputtering of the film. The sputtering process is quite
three primary layers with at least one layer of metal. inefficient, with only 30% of planar target material
Sputtered coatings often use one, two, or three metal available for deposition on the substrate. Cylindrical
layers and must be protected from humidity and con- targets offer closer to 80% utilization. While ITO
tact. For this reason, they are often referred to as “soft (or tin-doped indium oxide) is the most widely used,
coat.” Sputtered coatings are today typically used in alternatives include other TCOs, for example, fluo-
insulated glass units with the low-e surface inside the rine-doped tin oxide, or Al-doped zinc oxide (AZO)
sealed air space but can also be applied to plastics and [225]. In the case of ITO, recycling of unused tar-
used in suspended films or retrofit window films [216]. get material is required for economic production
Sputtered dielectric/metal/dielectric multicoatings are because it is so expensive. There is some concern
by far the most commonly used. These multicoatings as there is a physical limit to the available indium
can be composed in many different ways. The most for ITO [226]. For AZO thin-film deposition, for
commonly used and most suitable metal is Ag, owing instance, the coating method of reactive magnetron
to its small absorption over the whole solar spectrum, sputtering is a very economical and practical way of
but also Al, Cu, Cr, Ti, and so on, can be used. In addi- mass production. For AZO or Zn–Al sputtering tar-
tion, TiN and other transition metal nitrides have been get material is sufficiently inexpensive that recovery
used as an alternative to noble metals [217,218]. The of materials use is of no concern. In this method,
dielectric materials may comprise of high-refractive a Zn–Al metal target is sputtered in an oxygen at-
index materials, such as, pure ZnO, Al- and/or Ga- mosphere such that metal ions oxidize when they
doped ZnO, SnO2, TiO2, TiON, ITO, In2O3, ZnSnOx, reach the substrates surface. By using a metal target
Bi2O3, HfO2, and Si3N4, and low-index dielectrics, instead of an oxide target, direct current magnetron
such as, SiO2 and metal nitrides (TiN, CrN, ZrN, HfN). sputtering may be used which enable much faster
The multilayer structure may also include corrosion- deposition rates.
impeding layers, such as Al2O3 [219]. The metals and
dielectrics can be combined in many different ways
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20 Surface Modification of Plastics: Kenth S. Johansson

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20 Surface Modification of Plastics

20.1 Introduction: Surface contaminant with another. Solvent surface treat-

Applied Plastics Engineering Handbook. http://dx.doi.org/10.1016/B978-0-323-39040-8.00020-1

20.3.1.3 Plasma Treatment at form of two opposing electrically conductive elec-

method include polypropylene fibers, polyethylene

hydrophobicity by incorporating oxygen-containing

gowns and surgical drapes [61,62]. It is hypothe-

20.3.2 Corona Treatment material’s surface. A typical corona treatment station

released energy is low and thus the region is negli-

Time-Averaged Concentrationsa in an Air Corona

Experimental Conditions Dispersiona Acid–basea Surface Energya

Number of Laser Pulse Laser Pulse Weld Strength Ultimate

As shown, the Parylene coatings can be deposited

20.4.3.1 Plasma-Deposited Coatings a variable composition; they should also be durable

free-radical sites on the surfaces. The low pressure in

20.4.3.2 Plasma-Deposited Coatings is provided in Fig. 20.31. To ensure stable plasma

on plastic substrates. For instance, SiOx- and AlOx

[55] <http://www.enerconind.com/treating/plas- [71] Savolainen A, Kuusiapalo J, Karhuketo H.

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