Surface chemistry of paper

The surface chemistry of paper is responsible for many

important paper properties, such as gloss, waterproofing,
and printability. Many components are used in the paper-
making process that affect the surface.

Pigment and dispersion medium

Coating components are subject to particle-particle,
particle-solvent, and particle-polymer interactions.[1] Van
der Waals forces, electrostatic repulsions, and steric
stabilization are the reasons for these interactions.[2]
Importantly, the characteristics of adhesion and cohesion
between the components form the base coating
structure. Calcium carbonate and kaolin are commonly
used pigments.[1][2] Pigments support a structure of fine
porosity and form a light scattering surface. The surface
charge of the pigment plays an important role in
dispersion consistency. The surface charge of calcium
carbonate is negative and not dependent on pH, however
it can decompose under acidic conditions.[3] Kaolin has
negatively charged faces while the charge of its laterals
depend on pH, being positive in acidic conditions and
negative in basic conditions with an isoelectric point at
7.5.[1] The equation for determining the isoelectric point is
as follows:

In the papermaking process, the pigment dispersions are

generally kept at a pH above 8.0.[1]

Pigments, binders, and co-binders

Binder spheres coated with acrylic acid (a) and anionic surfactant (b).
The molecular structure of cationic starch. The repeating unit of starch is
derived from glucose interconnected with glycosidic bonds.

Binders promote the binding of pigment particles

between themselves and the coating layer of the paper.[2]
Binders are spherical particles less than 1 µm in
diameterr. Common binders are styrene maleic anhydride
copolymer or styrene-acrylate copolymer.[1] The surface
chemical composition is differentiated by the adsorption
of acrylic acid or an anionic surfactant, both of which are
used for stabilization of the dispersion in water.[4] Co-
binders, or thickeners, are generally water-soluble
polymers that influence the paper's color viscosity, water
retention, sizing, and gloss. Some common examples are
carboxymethyl cellulose (CMC), cationic and anionic
hydroxyethyl cellulose (EHEC), modified starch, and
dextrin.

Sizing
The contact angle is the angle between a droplet of liquid and a paper
surface.

The molecular structure of co-styrene acrylate

The molecular structure of co-styrene-maleic anhydride

In sizing, the strength and printability of paper is

increased. Sizing also improves the hydrophilic character,
liquid spreading, and affinity for ink. Starch is the most
common sizing agent. Cationic starch and hydrophilic
agents are also applied, including alkenyl succinic
anhydride (ASA) and alkyl ketene dimers (AKD).[5]

Cationic starch increases strength because it binds to the

anionic paper fibers.[6] The amount added is usually
between ten and thirty pounds per ton. When starch
exceeds the amount the fibers can bind to, it causes
foaming in the production process as well as decreased
retention and drainage.[6]

Surface modification
Plasma surface modification

Surface modification makes paper hydrophobic and

oleophilic.[7] This combination allows ink oil to penetrate
the paper, but prevents dampening water absorption,
which increases papers printability.

Three different plasma-solid interactions are used:

etching/ablation, plasma activation, and plasma
coating.[7] Etching or ablation is when material is removed
from the surface of the solid. Plasma activation is where
species in the plasma like ions, electrons, or radicals are
used to chemically or physically modify the surface.
Lastly, plasma coating is where material is coated to the
surface in the form of a thin film. Plasma coating can be
used to add hydrocarbons to surfaces which can make a
surface non-polar or hydrophobic. The specific type of
plasma coating used to add hydrocarbons is called
plasma enhanced chemical vapor deposition process or
PCVD.[7]

Contact Angle

An ideal hydrophobic surface would have a contact angle

of 180 degrees to water. This means that the
hydrocarbons lie flat against the surface creating a thin
layer and preventing dampening water absorption.
However, in practice it is fine or even preferred to have a
low level of dampening water absorption because of a
phenomenon that occurs when water settles at the
surface of paper.[7] This phenomenon is when ink is
unable to transfer to the paper because of the water layer
at the surface. The contact angle value for hydrocarbons
on a rough pigment-coated paper can be found to be
approximately 110° through a contact angle meter.

The Young's equation can be used to calculate the

surface energy of a liquid on paper. Young's equation is:

where is the interfacial tension between the solid and

the liquid, is the interfacial tension between the
liquid and the vapor, and is the interfacial tension
between the solid and the vapor.

An ideal oleophilic surface would have a contact angle of

0° with oil, therefore allowing the ink to transfer to the
paper and be absorbed. The hydrocarbon plasma coating
provides an oleophilic surface to the paper by lowering
the contact angle of the paper with the oil in the ink. The
hydrocarbon plasma coating increases the non-polar
interactions while decreasing polar interactions which
allow paper to absorb ink while preventing dampening
water absorption.[7]
Applications
Printing quality is highly influenced by the various
treatments and methods used in creating paper and
enhancing the paper surface. Consumers are most
concerned with the paper-ink interactions which vary for
certain types of paper due to different chemical
properties of the surface.[8] Inkjet paper is the most
commercially used type of paper. Filter paper is another
key type of paper whose surface chemistry affects its
various forms and uses. The ability of adhesives to bond
to a paper surface is also affected by the surface
chemistry.

Inkjet printing paper

Co-styrene-maleic anhydride and co-styrene acrylate are

common binders associated with a cationic starch
pigment in Inkjet printing paper.[8] Table 1 shows their
surface tension under given conditions.

Compound Monomer Proportion pH Surface Tension (mN/m)

Cationic Starch - 5.0 32.9

Co-styrene-maleic anhydride 3:1 7.6 38.51

Co-styrene acrylate 3:4 4.3 49.99

There have been several studies that have focused on
how the paper printing quality is dependent on the
concentration of these binders and ink pigment. Data
from the experiments are congruent and stated in Table 2
as the corrected contact angle of water,[9] the corrected
contact angle of black ink,[8] and the total surface
energy.[10]

Contact Angle of Contact Angle of Black Total Surface Energy

Sample Sizing Formulation (% w/w)
Water (˚) Ink (˚) (mN/m)

1 no surface treatment 103.1 81.7 39.5

2 100% cationic starch 39.2 36.1 51.25

80% cationic starch/ 20% co-styrene-maleic

3 80.5 65.2 38.39
anhydride

4 80% cationic starch/ 20% co-styrene acrylate 60.2 60.5 42.39

The contact angle measurement has proven to be a very

useful tool to evaluate the influence of the sizing
formulation on the printing properties. Surface free
energy has also shown to be very valuable in explaining
the differences in sample behavior.[8]

Filter paper

Various composite coatings were analyzed on filter paper

in an experiment done by Wang et al.[11] The ability to
separate homogenous liquid solutions based on varying
surface tensions has great practical use. Creating
superhydrophobic and superoleophilic filter paper was
achieved by treating the surface of commercially
available filter paper with hydrophobic silica
nanoparticles and polystyrene solution in toluene.[11] Oil
and water were successfully separated through the use of
the filter paper created with an efficiency greater than
96%. In a homogenous solution the filter paper was also
successful in separating the liquids through
differentiating for surface tensions. Although with a lower
efficiency, aqueous ethanol was also extraced from the
solution when tested on the filter paper.[11]

See also
Paper chemicals
Papermaking
Sizing

References
1. Fardim, Pedro (2000). "Paper and Surface Chemistry
Part 2- Coating and Printability". Institute of Quimica: 1–
13.
2. Fardim, Pedro (2000). "Paper and Surface Chemistry
Part 1- Fiber Surface and Wet End Chemistry". Institute of
Quimica: 1–14.
3. Gaudreault, Rodger; Weitz (September 2009). "The
Structure and Strength of Flocs of Precipitated Calcium
Carbonate Induced By Various Polymers Used in Paper-
making". Fundamental Research Symposium. 14: 1193–
1219.
4. Granier (1994). "Adhesion of latex particles on inorganic
surfaces". Tappi J. 77 (5): 419.
5. Hubbe, Martin. "Cationic Starch" .
6. Hubbe, Martin. "R&D Chemicals: How they Impact
Papermaking" .
7. Pykonen, M; Johansson, K.; Dubreuil, M.; Strom, G.
(2010). "Evaluation of Plasma-Deposited Hydrophobic
Coatings on Pigment-Coated Paper for Reduced
Dampening Water Absorption". Adhesion Science and
Technology. 24: 511–537.
doi:10.1163/016942409x12598231568302 .
8. Moutinho, Isabel (15 July 2007). "Impact of Surface
Sizing on Inkjet Printing Quality". Industrial and Engineering
Chemistry Research. 46: 6183–6188.
doi:10.1021/ie070356k .
9. Gruyter, Walter (16 December 2009). "Effect of surface
sizing on the surface chemistry of paper containing
eucalyptus pulp". Holzforschung. 63: 282–289.
doi:10.1515/hf.2009.046 .
10. Moutinho, Isabel (27 September 2011). "Paper Surface
Chemistry as a Tool to Improve Inkjet Printing Quality".
BioResources. 6 (4): 4259–4270.
11. Wang; Li (March 2010). "Filter paper with selective
absorption and separation of liquids that differ in surface
tension". ACS Applied Materials & Interfaces. 2 (3): 677–
683. doi:10.1021/am900704u .

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