Diamond-Like Carbon as a protective coating

for decorative glass

Rolf Petrmichl1, RPetrmichl@guardian.com; Victor Veerasamy1, VVeerasamy@guardian.com;
Nestor Murphy1, NMurphy@guardian.com; Jiangping Wang1, JWang@guardian.com;
Fabio Reis2, FReis@guardian.com; Maximo Frati1, MFrati@guardian.com; Jens Peter Mueller3, JMueller@guardian.com
1
Guardian Industries USA
2
Guardian Industries Brasil
3
Guardian Industries Luxembourg

Keywords
1 = Diamond-Like Carbon 2 = glass surface protection 3 = abrasion resistance
4 = corrosion resistance 5 = easy clean

Abstract

Challenges of Large Area Coating Processes

leads to complicated stress fields around surface treatments can provide some
and below the point of contact during protection due to low friction but
Though glass is a remarkably stable with increasing load the effect is lost
impact, static loading and sliding
material, able to withstand most as the surface layer is scraped away.
contact with abrasive media, resulting
environmental stresses indefinitely Further improvements in durability have
in various types of surface damage and
without bulk failure, its surface is been demonstrated using organic-
loss of optical quality [1]. The inherent
relatively easy to damage through inorganic hybrid coatings, but these
chemical stability of the silica backbone
mechanical contact with hard materials are not immune to wear, even by soft
enables glass to withstand most types
(e.g. glass or hardened metal) or materials such as wiper blades [4]. In
of environmental exposure indefinitely
through chemical exposure to corrosive addition, polymer based treatments
without bulk failure, however long term
chemicals (such as alkali solutions or must be applied in the glass shop after
exposure to a variety of organic and
certain types of hard water), leading fabrication and thus increase labor cost
inorganic agents results in the gradual
to readily visible cosmetic defects. In and in some cases require the use of
degradation of the appearance and
as much as the ability to see through hazardous chemicals.
cleanability, which are key features of
glass is one of its primary selling points, At the other end of the material
new glass [2]. The primary culprit is
its resistance to marring, scratching or spectrum, inorganic thin films provide
roughening of the glass surface which
corrosion directly influences its value. limited benefit though they may
can occur just through prolonged
Historically, efforts to protect be harder than glass, because the
contact with static water through ion
glass have relied on organic surface inherently high friction causes lateral
exchange reactions. Degradation
treatments or films which lower its contact forces to be transferred into
can also occur through formation
coefficient of friction or yield under the substrate. Accordingly, reports
of tenacious chemical bonds with
impact, or on the use of inorganic of improved abrasion resistance are
inorganic contaminants, that cannot
oxide or nitride coatings to produce a invariably linked to friction reducing
be broken by common cleaning agents
hard surface layer. The drawback of surface contaminants [5]. In cases
but require abrasive action; invariably
the organic treatments is they wear where inorganic films are combined
contributing to surface roughness by
off, and of the inorganic coatings that with organic surface treatments, e.g.
leaving microscopic bonded residues
they are easily marred due to inherently on glass containers, their benefit is
and scratches. During installation, glass
high friction. Diamond-Like Carbon is limited to enhancing the adhesion [6].
can be exposed to concrete splatter
a unique material that combines the Real surface hardening requires either
which becomes difficult to remove
benefits of both organic and inorganic extremely hard polycrystalline ceramic
after hardening [3], but exposure to
materials and thereby provides superior coatings, which can be produced only
and precipitation of dissolved silica
glass protection without wearing away. at very high substrate temperature
present in some tap water is a more
Since its discovery in the early 1970s, (or by exotic techniques such as laser
obscure problem that greatly increases
the protective properties of Diamond- sintering [7]) or extremely thick (> 1
the maintenance effort and frequency
Like Carbon have been exploited in μm) amorphous inorganic coatings
required to keep glass clean.
a diverse assortment of small-scale [8]. In both cases cost, poor scalability,
Historical approaches for protecting
products, including razor blades, hard and loss of transparency make these
glass have limitations, particularly
disk media, and bar-code scanner approaches unsuitable for large area
when applied to decorative products
windows. This paper focuses on the glass applications.
such as table tops, display cabinets,
development and commercialization of
shelving, mirrors and shower enclosures.
DLC for large area glass applications –
Paramount for these applications is the Carbon coatings produced by
specifically as a transparent and robust
preservation of cosmetic quality, clarity vacuum deposition
protective coating for decorative glass
and transparency over the life of the
products. A wide variety of carbon-based
product at a reasonable cost.
coatings can be produced by vacuum
Hydrocarbon and fluorocarbon
Introduction surface treatments and films
processes, with a wide range of
properties (Figures 1 and 2). This is
The need to protect glass from surface have been used, in some cases to
a consequence of the carbon atom’s
damage has been discussed extensively provide temporary protection from
unique ability to readily hybridize and
in the technical literature. As a relatively contamination during installation [3],
form different types of covalent bonds
hard (indentation resistant) material, but for the most part to generate
with neighboring atoms. Carbon
the brittle nature of glass not only hydrophobic properties, e.g., on
coating materials range from very soft
reduces the practical strength from its automotive windshields where improved
graphitic or polymeric films made by
theoretical limit through propagation visibility in rain reduces reaction times.
evaporation or plasma polymerization,
of cracks from surface flaws, but also Under low contact loads, polymeric
sputtered amorphous carbon (a-C)

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 with low hardness, hard hydrogenated
amorphous carbon (a-C:H) produced
by biased-plasma or plasma beam, and
very hard “tetrahedral” a-C or a-C:H
deposited by cathodic arc sputtering
or high energy ion beam deposition.
Polycrystalline diamond coatings are
also possible, using thermal CVD, flame
CVD or microwave plasma, however
high substrate temperatures are
required (> 700o C). The amorphous
forms of carbon are preferably grown
at low temperatures (<200o C), and
the also have the advantage that they Figure 1 and 2
resist brittle failure and can be made Ternary plot and material properties of carbon coatings
smoother since they have no crystalline
grains.

Diamond-Like Carbon (DLC)

The term Diamond-Like Carbon, first
used by Aisenberg and Chabot in 1971
Challenges of Large Area Coating Processes

[9], is used in industry today to cover

amorphous carbon with a broad range
of mechanical and optical properties,
included both hydrogenated and non-
hydrogenated forms, made with low
or high energy vacuum deposition
techniques.
The DLC coatings described in
this paper were produced by high-
energy ion-beam deposition. The
beneficial properties of these coatings
when applied to glass, including high
mechanical hardness, low coefficient
of friction, low chemical reactivity, and Figure 3
high transparency/neutral appearance,
Types of ion sources
are a consequence of sp3 rich carbon-
carbon bonding, low (but nonzero)
hydrogen content, and high mass
density.
Impressive is the list of DLC
applications that have either been
commercialized or are in development
in a wide range of industries – this
includes low friction razor blades,
overcoats for hard disk media and
heads, durable-barcode scanner
windows, biocompatible implants and
surgical tools, durable high end optics,
various electronic applications, and
wear resistant tools [10]. However,
in all cases the deposition techniques Figure 4 and 5
used have limited scalability. Plasma Anode layer source in operation and DLC thickness uniformity over the width of jumbo lite.
deposition (biased or not) is difficult
to achieve uniformly over large areas
due to electrical interactions with the parameters are largely decoupled from restricted due to space charge effects.
substrate surface and vacuum chamber the size and shape of the substrate, and The grids have limited lifetime due to
walls. The limitations of plasma beam are determined by the design of the ion impact erosion, and are sensitive to
deposition are discussed in the next ion source instead (see Figure 3). The contamination and alignment as well.
section. Cathodic arc deposition is gridded type was pioneered by Kaufman At the present time gridded ion sources
difficult to scale because the arc is in in the USA in the 1970s, while gridless have been scaled to roughly 1 meter
fact a small (travelling) hot spot on designs were concurrently developed in length.
the cathode, and the requirement the former Soviet Union. In the gridded Gridless ion sources are more robust
for magnetic filtering to eliminate source, ion extraction and focusing and their output is not constrained by
macroparticles complicates scale-up as is achieved by applying appropriate space charge. Gridless ion sources best
well. More exotic techniques such as potentials to multiple electrostatic suited for low voltage - high current
laser ablation and mass-selected ion grids, while in the gridless designs the operation are the End-Hall (not shown)
beam are similarly restricted. accelerating field is generated through and the Closed-Drift types. Such beams
interaction between the source plasma produce diffusive plasmas that extend
Ion source technologies and a transversely applied magnetic well beyond the ion source and hence
field. generate “plasma beams”. Ion energy
Ion beam processes differ from plasma
On the plus side, the gridded ion and consequently the hardness of the
deposition (also known as PECVD) in
source provides best control of the DLC produced are limited. Scaling
that generation and acceleration of ions
ion beam parameters including ion plasma beam sources has had little
occurs remotely. Hence the deposition
energy; however the beam current is successful due to poor plasma stability/

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Figure 6 Figure 7 and 8
Surface damage on half-coated glass, caused by Basic scratch tester and scratch track on half coated sample (10 kg, 3 mm borosilicate sphere).
repeated contact with glass and metal objects.

uniformity and due to the high gas

loads require to make them run.
In contrast, the gridless anode layer

Challenges of Large Area Coating Processes

source (the name refers to the compact
acceleration zone near the anode) runs
best at much higher voltage, producing
higher beam energies and harder DLC.
Good source plasma uniformity and low
gas flow requirements make the anode
layer source highly scalable. The DLC
coatings evaluated in this paper were
produced with such sources scaled up
to 3.7m length. Figure 4 provides a
view of the well collimated and highly Figure 9 Figure 10
uniform ion beam produce by a 3.7m Critical scratch-load with 3mm borosilicate or Long term durability test comparing polymeric
ion source mounted in flat glass coater, 3mm sapphire spheres (lower) and %Tvis loss and hybrid surface treatments to DLC coated
(upper) versus DLC thickness. glass.
resulting in excellent uniformity (Figure
5). The ion source is use to produce
thin, dense DLC coatings on float glass,
which produce high abrasion resistance transmission induced by the coating;
and yet are highly transparent. both as a function of the DLC thickness.
Comparing critical loads with abraders
Benefits of DLC on glass made of borosilicate (H ~ 6 GPa) or
alumina (H ~ 40 GPa), the threshold for
Many studies have been carried out to
visible damage is less with the harder
understand the extensive damage that
material. It should be noted however,
can occur on a glass surface during
that the critical load of clean uncoated
contact with glass or metal objects [11].
glass is very low - with either type of
The ability of a thin layer of DLC to
abrader it is less than the 0.2 kg lower
protect against such damage is shown
limit of the instrument. Clearly DLC can
in Figure 6.
greatly improve the abrasion resistance Figure 11
While much tribological testing is
of glass at thicknesses where its impact Stain after 10 days 50oC/95% RH
carried out using sharp microscopic
on transparency is low.
indenters made of diamond, simulation
The high beam energy produced by
of real-world contact damage requires
the anode layer ion source also benefits and hybrid organic-inorganic surface
the use of other abrader materials
adhesion. Ion implanting and ion films. Using contact angle as an
and geometries. Accordingly a simple
mixing occurs during the early stage indicator, the wear rate was found to
abrasion tester (Figure 7) was employed
of growth which produces a transition be much faster – after 600 strokes both
to measure abrasion resistance. In this
layer that penetrates into the glass layers were effectively gone.
device, a sphere of a given material
surface. Excellent adhesion keeps the The low friction of DLC is in large
is dragged across a test sample with
DLC from scraping off during abrasion part due to the chemically inert nature
controllable speed and fixed load.
and the high hardness results in a very of this material. Its non-reactive nature
The micrograph in Figure 8 depicts
low wear rate. This is illustrated in provides additional benefits to glass
an abrasion track on glass partially
Figure 10, where results from long- in the form of enhanced resistance
coated with DLC, produced by a 3 mm
term durability testing are displayed. to corrosion and protection against
diameter sphere made of high grade
In this test a sample mounted in a bonding with inorganic contaminants.
borosilicate glass with a 10 kg load.
reciprocating brush tester is repeatedly The ability of DLC to impede the
The abrader moved across the interface
rubbed with a wet sponge loaded reactions between glass and stagnant
starting on the uncoated side where it
with a 1 kg weight and soaked with water that causes alkali leaching and
left a pronounced scar and ending on
Soft Scrub (a common household ultimately roughening of the surface is
the DLC coated side where no damage
cleaner containing calcium carbonate shown in Figure 11, which compares
is visible.
grit). There is a minor change in visible DLC coated and uncoated glass after 10
The level of protection provided
transmission after 10,000 strokes, day continuous exposure to 50oC and
by DLC and its impact on optics is
indicating that a small reduction in 95% RH. The DLC coating prevented
illustrated in Figure 9. The lower chart
thickness has occurred. For comparison, the pronounced staining which occurred
shows critical load (50% probability
Figure 10 includes results for glass on the uncoated sample.
threshold for leaving a visible mark)
samples with polymeric fluorocarbon
and the upper chart the loss in visible

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 Figure 12 Figure 13
Half-coated glass panel after 1.5 years in a Decorative glass applications
shower.

References
Challenges of Large Area Coating Processes

Protection against the type of

damage that can occur during [1] J.R. Varner, Glass Processing Days, 13-15 Sept.
prolonged exposure to hard water 1997, p. 503
is shown in Figure 12. Installed 18 [2] S. Beyers, Glass Performance Days, 15-18 June
months in a shower stall, the half- 2007, p. 704
[3] T. Rogers, Glass Performance Days, 15-18 June
coated panel has severe and irreparable 2007, p. 325
water spotting on the uncoated half, [4] Y.S. Lim, B.S. Hong, Y.J. Cho, M.S. Park and D.H
while the DLC coated area is clean. The Jung, Glass Processing Days, 13-16 June 1999,
picture shows the panel after it was p. 595
[5] R.H. Dettre and R.E. Johnson, J. Adhesion, Vol 1
cleaned – the coated side with soap and (1969) p. 92
water, the uncoated additionally with [6] G.L. Smay, Glass Tech., Vol 26, No 1 (1985) p46
household vinegar. Generally, organic [7] J. Baber and F. Raether, Glastech. Ber. Glass Sci.
acids are able to dissolve the alkali salts Technol., Vol 72, No 7(2000) p211
[8] F.M. Kimock, G.J. Knapp and S.J. Finke, US
(calcium and magnesium carbonates) Patent 5,268,217
contained in hard water spots, but the [9] S. Aisenberg and R. Chabot, J. Appl. Phys., Vol
tap water this panel was exposed to 42 (1971) p. 2953
contained dissolved silica. Chemically [10] S. Ravi and P. Silva, Amorphous Carbon,
INSPEC, London (2003), p2.
similar to the surface of glass with [11] L. Holland, The Properties of Glass Surfaces,
stain, the hazy, residual surface film Chapman, London (1964), p. 368.
consists of porous silica that precipitate
from drying water droplets and formed
permanent bonds with the unprotected
glass. Attempts to remove this film with
abrasive cleaners were fruitless.

Summary
The Diamond-Like Carbon coatings
presented in the paper are uniquely
suited for providing lasting protection to
decorative glass products such as table
tops, display cabinets, shelving, mirrors
and shower enclosures (examples shown
in Figure 13). Applied by robust linear
ion sources which have been integrated
into large area MSVD coaters these
coatings have the high hardness and
adhesion to float glass necessary to
protect against the contact damage
such products typically are subjected to,
without inducing a significant optical
penalty. The coatings are chemically
inert and consequently provide
additional benefits to glass in the form
of improved corrosion resistance and
easy clean properties.

Acknowledgement
In memory of Mr. William Davidson,
founder and owner of Guardian
Industries, whose foresight and
dedication made this work possible.

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