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Hybrid pigments
Organic and inorganic pigments differ in performance
and costs. Organic pigments have strengths in
chroma and tint strength but are weaker in
weatherfastness and opacity; it is the other way round
with Inorganic pigments. Hybrid pigments provide an
alternative and are growing in the market. Hybrid
pigments help to bridge the gap between performance
and costs without neglecting environmental
considerations.
Blends and co-finishes produce pigments with a good
balance of properties
The pigment industry faces many challenges in the near
future as raw material prices are expected to continue to
rise. Some forecasts indicate that the coatings industry will
continue to soften due to economic conditions. The
current trend for pigment manufacturers is to devote
research and development budgets to the modification of
surface treatments and particle morphologies instead of
trying to create new chromophores. Some pigment
manufacturers are focusing R&D funding on a new "type"
of pigment, described here as hybrid. Coloured pigments
give aesthetic enhancement, while at the same time
providing functionality. Hybrid pigments can offer
advantages such as lower cost as well as the ability to
meet the needs of a particular application. In the past,
conventional wisdom suggested that one pigment in a
particular colour space must work in every application,
system and condition all of the time. It must also to be
easy to handle, environmentally friendly and able to
deliver high performance and still be economically priced.
Today, hybrid pigments offer the coatings industry a way
to bridge the technological gap between price and
performance.
Common organic and inorganic pigments
Coloured classical pigments, excluding effect pigments,
can be divided into two main groups of coloured organic
pigments and inorganic pigments.
There are four types of organic pigments:
azo pigments, polycyclic pigments, lakes, and others
(Figure 1). Azo pigments are middle to lower quality
materials that contain an N=N linkage. Half of the global
consumption of pigments comes within the azo
classification [1]. Most Colour Index numbers for azo
pigments used in coatings contain an o-nitro group. This
gives them good acid and base resistance, but limited
weatherfastness and bleed-resistance. Polycyclic
pigments, also known as high-performance pigments
(HPP), have the highest quality. HPPs offer the best
durability and have become both specialized and
commoditized. HPPs represent some of both the oldest
and newest technologies in organic pigments. Indanthrone
Blue (PB 60) is 107 years old while the most recent "new"
chromophore, Diketo Pyrrolo Pyrrole (DPP) being
developed in 1983. Lake pigments, used most often in
solvent systems and powder, are metal salts, and are
considered to be in the middle to low performance
category. Finally, the "others" sub-division is a catch-all for
other salts of dyes and aniline black.
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Inorganic pigments likewise can be divided into four
categories: coloured, white, clear, and others (Figure 2).
Coloured is the only category of interest in this article from
inorganic pigments. They usually contain transition metals
with partially filled "d" orbitals exhibited as oxides.
Complex, inorganic, coloured pigments (CICP) are
transition-metal containing oxides that are produced by
using high-temperature solid-state reactions. CICPs
inorganic coloured pigments have the highest durability
and are considered inert. CICPs often come under
scrutiny, as many contain chrome, nickel and antimony
which are elements which appear on harmful-metals lists
of organizations such as the United States Environmental
Protection Agency (EPA). Dr. Hartmut Endriss of BASF
AG, head of the product safety group for inorganic
pigments from 1992 to 2003, wrote many papers on the
safety aspects of using CICPs. He states: "but regarding
their chemical, toxicological and ecological properties,
they are practically inert and cannot be considered as
nickel, chromium or antimony compounds. They cannot be
identified with risks which might occur from the use of
such compounds. They are real rutile pigments with only a
low hazard potential. Their stability, insolubility and
non-bioavailability are key." [2] In contrast to the CICP
chemistry, other transition-metal oxides are chemically
reacted and precipitated. One of the best known examples
of a non-CICP inorganic pigment is bismuth vanadate.
This material has not always been an important pigment,
because lead chemistry dominates the yellow colour
space. Increasingly, lead chromates and molybdates have
become prohibited in many coatings systems around the
world, but they are still used in developing countries and in
developed countries in some exempt coatings.
Hybrid pigments are not new to the industry, but have only
now started to gain market acceptance. In 2005, Roland
Valin, the technical manager for the former Engelhard
Corporation, developed a range of hybrid pigments that
help formulators reduce costs and at the same time,
maintain key properties. Mr. Valin states that hybrid
pigments "achieve the colour spaces of bright orange,
bright yellow and bright red, offering the best-priced
alternative for many heavy metal-free formulations." [3]
During the 1970s, a number of pigment manufacturers
started to introduce pigment combinations as an
alternative to lead pigments, hence the birth of hybrid
pigments.
Hybrid pigments can be pigment combinations in one of
the following permutations: organic plus organic, inorganic
plus inorganic, or organic plus inorganic (Figure 3).
Pigment manufacturers have always blended quantities of
the same pigment to reduce the variability in production. In
todays hybrid pigment world, combinations of dissimilar
pigment chemistry are used to achieve a wide range of
properties and colour spaces.
Hybrid pigments an alternative
As lead-containing pigments have been banned in
coatings in many countries, formulators have had to select
other materials to produce coatings suitable for specific
needs. Organic pigments offer high chroma and high tint
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strength, but are deficient in the ease of dispersion,
weatherfastness, and opacity. Some organic pigments
exhibit solubility, heat stability issues and generally cost
more per unit weight. Inorganic pigments meet the
demands of dispersion, weatherfastness, and opacity, but
are low in chroma and tint strength. Inorganic pigments
have a lower per-unit cost compared to organics, but the
usage rate can be high, thus raising the final usage costs.
Many formulators simply compromise on one or more
attributes of the pigment selection in order to help satisfy
the needs of their customers.
A pigments ability to be durable in coatings is a function
of the chemistry. This in turn is mostly a function of cost.
Weatherfastness is an area in which many formulators are
unwilling to make sacrifices, as durability deficiencies can
be primary claims cost against coatings manufacturers.
Weathering of pigments is always a topic for debate. In
order to understand the weatherfastness of pigments, two
example-mechanisms are described here. In these
examples, it is assumed that the coating is a hiding,
one-coat or enamel coating.
Some facts about weathering of organic pigments:
- The rate of degradation of pigments is independent of
concentration. Typically, full shades weather better than
white reductions.
- Titanium dioxide reflects part of the ultra-violet (UV)
energy. Organic pigment particles experience
multi-attack of UV energy.
- Colouring of a coating takes place at the surface.
- Clear-coated systems perform much better than
single-coat systems.
The first example of the mechanism of weathering of a
coating containing titanium dioxide, extender, and copper
phthalocyanine, is surface polymer degradation (Figure 4).
As moisture and energy from the sun interact at the
surface, the binder is degraded so that only large particles
such as inorganic pigments and extenders are anchored
to the film. The small, coloured copper phthalocyanine
pigment particles do not have an anchoring point and
wash from the coating surface. The resulting colour
appears to be "faded" as only the non-coloured large
particles are seen. The second mechanism is
demonstrated using a yellow coating. There are three
ways to achieve a brilliant yellow shade. The first
possibility (A) is an organic yellow pigment plus titanium
dioxide. The second possibility (B) is a coloured inorganic
product, such as bismuth vanadate, plus an organic yellow
pigment. The third possibility (C) is to use a hybrid
pigment. It is assumed here that the yellow organic
pigment and the inorganic pigment have the same
chemistry. In example (A), organic yellow plus titanium
dioxide, over the life of the coating, the organic yellow
degrades (chromophoric loss) over time with a
"concentration" gradient of coloured yellow pigment that
changes from a high concentration near the substrate to a
lower concentration near the surface. The result is a faded
yellow that will ultimately become almost white. In
example (B), coloured organic and inorganic, the same
weathering phenomenon occurs as the organic yellow is
destroyed. However, the end point is no longer white, but
yellow. Thus the perceived fading is less. In the hybrid
example (C), a co-finished hybrid pigment, the organic
part is partially protected by the inorganic part, giving a
synergistic positive impact on fade. Figure 5 shows
(A),(B), and (C) respectively from left to right.
Blending easy process
There are two basic types of hybrid pigments: blended
and co-finished. The blended technology is the simplest to
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produce, as two or more pigments are blended using low
or high mechanical shear. Low-shear technology offers
the market a consistent colouristic blend of pigments
giving formulators better colour reproducibility.
Formulators can perform the same task at the mill but
would have to compensate for each component in the
tolerances allowed. In the example (A) above, most
formulators would use a reddish yellow and a greenish
yellow to adjust the shade. If the formulator receives both
pigments on the greener side of the tolerance, the colour
may be difficult to achieve.
The high-shear blending technique allows the pigment
components to have a wider range of particle sizes. Many
formulators grind pigments of different particle size and
chemistry together. If the chemistry and particle sizes are
similar, and the pigments disperse at nearly the same
rate, there are rarely problems. When pigments of very
different particle sizes and dispersibility are milled
together, the larger particles, which are typically inorganic,
can act as milling media for the organic pigments. Figure 6
shows the relative sizes of inorganic pigments and organic
pigments. Formulators must therefore mill these pigments
separately to achieve a full colour development of each
pigment while not impacting the aggregate size of each.
The high-shear blending technique allows the pigment
components to have a wider range of particles sizes by
partially impinging the organic pigment upon the inorganic
pigment surface. This high-shear impinging technique
brings bimodal distributions more toward a broad
monomodal distribution, allowing greater ease of
dispersion.
Co-finishing highest performance
The most advanced hybrid technology uses co-finishing. It
involves the placement of the organic pigment on the
inorganic pigment surface before the finishing steps of
production. The organic-inorganic co-finished combination
acts as only one pigment. Compared to the high shear
mechanical blended hybrids, the co-finished hybrids often
exhibit lower viscosity in mill bases, thus allowing
formulators to increase the pigment loading at the mill.
The co-finished hybrid pigments often interact with
systems similar as its inorganic base with regard to milling
and loading. Thus hybrid pigments can be treated like an
inorganic pigment while giving high chroma and tint
strength similar to an organic pigment.
Custom approach
Roland Valin noticed that often pigments are
"over-engineered" for the intended application. He also
observed that, as pigment process technologies improved,
the pigment morphology and surface treatment improve
the performance of that pigment. Often in the coatings
industry, purchasing agents want to focus on the colour
index of the pigment, instead of the effective use of the
pigment. Thus, the message that the formulator gets is
that pigment companies have developed pigments with
the broadest application possible.
Hybrid pigments create value as demonstrated in Figure 7
below. In this example, an initial organic pigment is
modified by surface treatment and particle morphology,
making it higher in tint strength with an adjustment in
colour space. Likewise, the inorganic pigment is modified
in colour space with a slight improvement in tint strength.
The hybrid pigment at the target colour space achieves
that which the two pigments individually can not
accomplish. With optimization of components together
with material science discipline, the customer receives
maximum benefit with a product designed to perform
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exactly in the application specification.?
References
[1] Kirk-Othmer Encyclopedia of Chemical Technology,
Fourth Edition, Volume 19 [2] April 2004 CPMA
Conference, Chicago, Ill. Dr. Endriss, BASF AG. [3] JCT
CoatingsTech, Vol. 2 #18, July 2005, Mr. Roland Valin,
BASF Corp. [4] Coatings World, August 2005, High
Performance and Special Effect Pigments Update.
Results at a glance
- Hybrid pigments in combinations of organic-organic,
inorganic-inorganic, and inorganic-organic are growing in
our market.
- While inorganic pigments do offer best in class
weathering properties, they also tend to be less
saturated compared to their organic counterparts.
- Lead chromate and molybdate-containing formulations
are becoming extinct. Legislation in the past was the
largest market driver; however, consumers are looking
for "green" solutions and appear to be willing to pay for it.
- The single biggest challenge is that pigment
manufacturers bring value and performance. Low priced
alternatives are not always the answer and formulators
need to work more closely with purchasing to make the
usage cost the primary technical driver. Paint
manufacturers are driven to deliver finishes that perform
to higher standards along with cost and environmental
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considerations [4].
- Hybrid pigments stand poised to help bridge the gap
between performance and rising costs.
* Corresponding Author. Contact:Lee Young (Mr.)BASF
CorporationTel. +1 973 245 7399Fax +1 973 332 5080
THE AUTHOR
Lee Young received a bachelor of science degree in
chemistry from Wingate University in North Carolina. He
has a combined experience of more than 15 years
working with pigments and coatings. He began his career
at a small chemical company near Raleigh, North
Carolina, that produced small quantity speciality inorganic
and organic compounds, including special functional
pigments. Lee joined BASF in 1997, where, until 2001, he
worked in R&D and Marketing of functional polymers for
architectural coatings. Lee is currently the Coatings
Technical Manager for the Performance Chemicals
business group of BASF for North America, supporting
company efforts in the area of pigments and dispersions
for architectural coatings along with classical and effect
pigments for Industrial and Automotive coatings.
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Figure 5: The three alternatives "A", "B" and "C" (left to right)

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Figure 6: The relative sizes of inorganic pigments and organic pigments

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Figure 7: Value creation of hybrid pigments

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Figure 1: Types of organic pigment

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Figure 2: Types of inorganic pigment

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Figure 3: Permutations pf hybrid pigments

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Figure 4: Surface polymer degradation

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