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C OATINGS
www.european-coatings.com dossier 2018
PIGMENTS
The best technical papers on pigments for
high-performance coatings published in the
European Coatings Journal within the past
three years.
PRESENTED BY
FUNCTION AND
APPEARANCE
Today´s high-performance coatings require high-end raw materials. This in-
Dr. Sonja Schulte
Editor-in-Chief
cludes pigments, of course. No matter if you require brilliant effects, weather
T +49 511 9910-216 and chemical resistance, corrosion protection or specific colour tones -
sonja.schulte@vincentz.net pigments can do the job!
As a formulator, you are continually called on to be au fait with the latest ad-
vances in research and development. Such knowledge is rarely to be found in
a single package. European Coatings Journal is about to change that. This the-
matic dossier is bursting with information on pigments that we have compiled
for you. In it you will find all the relevant technical papers on pigments that
have been published in European Coatings Journal over the last three years.
Now there’s a welcome development!
E U R O P E AN CO AT I NGS J O UR N AL 2018
ECKART EFFECT PIGMENTS
ECKART offers metallic and pearlescent pigments for the paints and coatings industry, the
printing industry, the plastics, lightweight concrete industries and the cosmetics industry.
Whether you require brilliant effects, corrosion protection, weather and chemical resistance or simply
sensational metallic and pearlescent colour shades, we provide the right effect pigments for your every
need – in various delivery forms: powders, pastes, pellets and concentrates.
For us, efficiency and environmental sustainability are of the highest priority. As the first company to
pioneer effect pigments for aqueous painting systems in the global market, ECKART continues to focus
on innovation in this field.
Source: BASF SE
MARKET REPORT
Global market forcast
for pigments from
2014
08
Source: Werner Rudolf Cramer
PRODUCT
OVERVIEW
Interference
pigments
16 22
EFFECT PIGMENTS
How metallic effects can be best
achieved in UV curing finishes
32 FORMULATING EXCELLENT
14 TOP INDUSTRY MOVE II AUTOMOTIVE EFFECTS
Ferro Corporation acquired Capelle Pigments NV Eight golgen rules
and certain assests of Delta Performance Products Werner Rudolf Cramer, Cramer
E U R O P E AN CO AT I NGS J O UR N AL 2018
C O NT E N T S 5
Source: Heraeus
60
Source: Matthias Haas - Fotolia.com
IRON OXIDES
Establishing FORMULATION TRAINING
the causes of How to formulate a
colouring conventional metallic basecoat
74 94
60 A MORE INTENSE COLOUR FOR ALL SYSTEMS 86 FAST FADING BLUES: THE INSIDE STORY
Coated aluminium flake interference pigments are Indoor durability of phytaloyanines can be worse
highly stable than expected
Gehard Pfaff and Kirsten Fritsche, Merck KGaA Roberto Mazzari, Umberto Dainese and Giovanni
Marsili, Colorificio San Marco S.p.a.
66 IN SEARCH OF THE PERFECT BLACK PEARL
Darker colour enhances tining options in powder 90 GLOWING WITH PROMISE
and liquid coatings Daylight fluorescenzt pigments for paints, PVC and
Jonathan D. Doll, Aaron Hollman and PU open up new applications in packaging
Adam Andreas, Sunchemical Rami Ismael, Aralon
The global market for high-performance pigments (HPPs) is es- At the other end of the scale, the two smallest end-use markets, non-
timated at 144,098 tonnes for 2011, a figure expected to climb impact printing (NIP) and electronics, are each forecast to show pig-
to 168,289 tonnes by 2017. The value of the market is estimat- ment sales levels of less than 2,000 tonnes. We expect sales into the
ed as $3,603 million in 2011; rising to $4,208 million by 2017 - in NIP segment to stand at just under 1,000 tonnes and those into the
constant money terms. This represents a fairly conservative electronics industry at about 1,400 tonnes in 2017. While these num-
CAGR of 2.6% per annum, reflecting the high level of uncer- bers are small, these are expected to be the fastest growing areas.
tainty over the world economic prospects.
ORGANIC PIGMENTS: LOWER VOLUMES, HIGHER VALUE
O ur estimate for the HPP markets in 2011 and forecasts for 2017 are
presented in Figure 1, given in thousand tonnes and broken down
by application area.
Among the different classes of HPP, the market in 2011 was split as
follows.
The largest end-use sector, by some margin, is coatings, forecast to ąą Inorganic effect pigments: 79% by tonnage and 57% by value (of
consume just over 90,000 tonnes by 2017, slightly over half the total which aluminium and bronze contributed 45% by volume and 38%
at 56%. This sector is forecast to reach $2,434 million in value by 2017. by value; pearlescent 34% by volume and 18% by value).
This is followed by the plastics segment, which is forecast to account ąą Organic HPP: 20% by volume, 42% by value. This shows how much
for almost 38,000 tonnes of HPP sales in 2017, or 22% of the total, higher prices are for this class of pigment compared to the effect ones.
valued at $915 million. We expect this split to remain the same in 2017.
E U R O P E AN CO AT I NGS J O UR N AL 2018
Source: Smithers Rapra MA R KE T R EP O R T 7
Figure 3: Global forecast for HPP by end-use market, 2011 and The almost unprecedented economic issues prevailing at the time of
2017 (thousand tonnes) writing mean that these figures have a higher degree of uncertainty
than would normally be the case. In particular, the Asian growth rates
could be higher if they can substantially isolate themselves from the
problems of the Western economies, especially Europe.
China is now the biggest pigment producer in the world with rapidly in-
creasing output in recent years. It is estimated that total pigment out-
put (including titanium dioxide, carbon black and iron oxide) in China
USA REMAINS LARGEST SINGLE MARKET reached 2.4 million tonnes in 2010. Organic pigment production was
estimated as 200,000 tonnes in 2010; 40% of the world total. HPP pro-
In 2011 the European and Asian markets are estimated to have been duction, on the other hand was quite modest.
similar in size and value at 54-56 thousand tonnes and $1.3 -1.4 bil- China is also the world’s biggest pigment exporter. Exports of all pig-
lion. The faster growth of most Asian markets leads to our forecasting ment types reached 900,000 tonnes in 2007, and increased to 1.1 mil-
that Asia will move slightly ahead of Europe by 2017 at 66 thousand lion tonnes in 2009, a year-on-year rise of 11%. Organic pigment exports
tonnes and $1.56 billion compared with 63 thousand tonnes and reached 140,000 tonnes in 2010, up a staggering 30% on the previous
$1.55 billion. year, with foreign exchange earnings of just over $1 billion. Pigments
We estimate that the United States was the largest single country produced in China are exported mainly to the US, Germany, Belgium,
market in 2011 at 26-27 thousand tonnes, followed by Japan at just Japan, the Netherlands, South Korea, Italy, the UK and some south-east
under 22 thousand tonnes and China at close to 20 thousand tonnes. Asian countries.
We forecast that the US will grow to 30 thousand tonnes by 2017 Other countries worth mentioning are Russia and Turkey. Both of these
and remain the leading market, but that China will have moved into are relatively small markets, but have grown significantly recently. In nor-
second place at 25-26 thousand tonnes overtaking Japan at around mal circumstances they would be expected to continue their progress,
24 thousand tonnes. but they are strongly influenced by the developed European markets
Due to the economic problems in Europe, we are expecting weak and so we have scaled back expectations of annual volume growth to
growth in this region of only about 2% per annum over the next five 2.9% for Russia and 4.4% for Turkey.
A COLOURFUL PICTURE
An over view of the pigment market. By Damir Gagro (published in ECJ 01/2015).
The developments in the pigment market were pleasant in grow significantly supported by increased printed packaging across
2014. At least, this is the pigment producers’ perception who F&B, pharmaceutical, and consumer health industries as well as the in-
talked to the editorial staff of European Coatings Journal. For creased use of colour printers. GIA, too, expects the market to reach a
the coming years they are expecting further growth in the volume of 11 million tonnes, but not before 2020 (Table 1 and Table 2).
pigment market. Read their views on further market develop-
ments, challenges through regulations and possible over ca- 2014: POSITIVE DEVELOPMENT
pacities in the pigment business.
As usual, Asia-Pacific holds the leading position in the pigment con-
sumption with a share of roughly 41 % of the total volume. The players
E U R O P E AN CO AT I NGS J O UR N AL 2018
MA R KE T R EP O R T 9
Tab.1: Organic Pigment consumption in tonnes by country/region Tab 2. Inorganic pigment consumption in tonnes by country/region
South America was difficult in 2014 and even China did not generate coatings sector and, combined with continued underlying growth in
the usual growth rates, in particular at the beginning of the year”. the construction sector globally. “We expect a constant rise in de-
The uneven picture is confirmed by Axel Schneider, mand for synthetic iron oxides. The global economic crisis of 2009
Cathay, Industries: “The market situation is certainly different with had a significant impact and since then we have experienced greater
regards to the various pigment types. Looking at our own core busi- volatility and regional variation due to macro-economic factors. This
ness, synthetic iron oxides, the market is in significant movement. Old development is mainly driven by the urbanization megatrend and
production plants are closing, new ones are being built. The currency thus increasing demand for pigments in emerging markets and a re-
developments hit producers in the regions in different ways. On the bound of construction activities in North America and Europe”, says
consumption side we have experienced the year 2014 pleasantly viv- Thomas Pfeiffer, Lanxess.
id, which has shown this market deviating from the overall economy”.
CONSOLIDATION INCREASES
MODERATE GROWTH EXPECTED
The pigment producers expect an increasing competitive environment
The suppliers are looking into the future with confidence. “Without in the market. “A further market consolidation in favour of large paint
a doubt the demand will grow in North America and in the currently and coatings manufacturers is expected, whereby global competition
very dynamic African region. Governmental investment programs will puts pressure on pigments”, says Metz. The consolidation is noticeable
determine for iron oxides if there will be reductions on a regional ba- in the market for iron oxides, agrees Pfeiffer: “The global manufacturing
sis. If savings receive priority to investments, there could be decreases industry for synthetic iron oxide is undergoing a period of consolida-
in consumption on a country to country level. In total we expect a tion. This effect is most noticeable in China where a significant number
continuous moderate growth”, predicts Schneider. of small and medium-sized producers have exited the market in the
The unstable situation in Ukraine as well as in the Near East is another last 18 months. Enforcement of environmental regulations by the Chi-
factor that is going to hamper growth in Europe, however Sütterlin an- nese authorities is having a significant impact and will continue to do so
ticipates little tailwind from the economic situation: “In Asia, the growth in the coming years, something that is confirmed also in the five-year
engine China is bound to kick back albeit on a slightly lower level. We plans of the People’s Republic of China. The country remains the larg-
believe that the demand for coatings in North America is going to con- est source of synthetic iron oxide but total manufacturing capacities in
tinue. Concerning the automotive industry, we anticipate overall growth China have fallen significantly in recent years”.
in 2015 to be slightly stronger than in 2014, above all driven by the eco-
nomic recovery in South America and China. We expect stable growth EXPANSIONS DO NOT LEAD TO OVER-CAPACITIES
in the construction sector, which is bound to be a bit more pronounced
in the US and slightly weaker in Asia”. Recent announcements regarding increasing production volumes
The segments automotive and industrial coatings are very promising and investments in expansions may lead to the thought that capaci-
for high performance pigments, according to Michael T. Venturini, Sun ties are rapidly growing around the globe. The producers are not con-
Chemical. “ Automotive and industrial coatings will remain the founda- cerned about over-capacities. “This is particularly the case in the iron
tion for growth of high performance pigments markets, however, grow- oxide market. Different manufacturers are erecting new capacities for
ing requirements for improved stability and functionality will position different reasons, Cathay Industries included. On the other side there
architectural and building materials for tremendous potential growth. are also some capacities that have been closed down and further
Globally, we expect to see further growth in high performance pigments closures will follow, so that in total we do not expect over-capacities.
as the replacement of heavy metal pigments continues. Legislative re- Hopefully we will see some excess capacity after all these changes
quirements will play an increasing role in the reformulation. that can then cover the future growth in demand”, says Schneider.
The underlying long-term trend is for continued global growth in the A similar view on the situation is shared by Pfeiffer: “In reality, global
synthetic iron oxide manufacturing capacities have significantly fallen pigment producers do not see this as a burden. “For many years the
in recent years due to the many plant closures in China. This trend is regulatory side has increasingly been impacting the market players,
likely to continue as the capacities being closed down are larger than who have become familiar with such movements. Who considers
the new additional capacities which are becoming available and we this exclusively a thread, uses his resources for developments that
do not anticipate any risk of over-capacity”. He adds: “A lack of clarity are hard to hold up. But who takes on the challenges pro-actively,
about the development of manufacturing capacities can also arise as will have best chances to shape his future business successfully,
a result of joint ownership of manufacturing facilities. The iron oxide avoiding a too fast commoditization of his products”, says Schnei-
industry in China has a strong network of intercompany trading and a der. A similar attitude shares Metz, who points at the chances for
history of joint venture ownership. In many cases, joint venture part- the pigment suppliers. “Short-termed new and more stringent regu-
ners – often relatively junior ones – each claim to own the total manu- lations often give the impression of an increase in pressure on the
facturing capacity of the joint enterprise and this results in misleading coatings manufacturers as well as pigments manufacturers and raw
cumulative capacity figures”. material suppliers. In reality, these changes almost always are an
advantage for companies along the supply chain, which foster inno-
DIFFERENT PICTURE FOR STANDARD PIGMENTS vation and use forward-looking existing and future possibilities for a
sustainable pigment and paint and coating manufacturing. Thereby,
Regarding standard pigments, there is a little different picture, according companies are able to differentiate and develop their market po-
to Sütterlin. “Most of the announced capacity increases concern the clas- sition”. However, it must be remembered that in regulations new
sical standard pigments such as Azo pigments and they are mainly taking limits and transitional periods for the realization should be chosen
place in China and India. Even in today’s market there are overcapacities in a way that a realistic change to more sustainability in the supply
for these pigments, which has resulted in intense price pressure and has chain is possible, adds Metz.
ultimately led to a consolidation among the manufacturers. We expect this “Environmental regulations and social change for sustainable raw
trend to continue. Further capacity increases have been announced for materials are driving rapid change and innovation in all segments of
some high-performance pigments such as PV 23 or PR122, of which some the paints and coatings market. The trend is well established in Eu-
have already been completed. Similar to standard pigments, we are aware rope and the United States, but is quickly growing in other regions.
of greater competitive pressure in this field”, he explains. Metz explains: “An We see self-regulation by paint producers and trade organizations
over-capacity for certain pigments in the market already exists for years. In playing a larger role affecting everything from end-of-life directives
the medium and long term, we expect a reduction of capacities, because to VOCs to environmental footprints. This drives change and cre-
an economical production will become more and more difficult. Neverthe- ates opportunities that will favour those that manufacture to the
less, there will also be a selective expansion of capacities of traditional pig- highest global standards. We see these challenges as great oppor-
ment manufacturers in emerging markets, e.g. BRIC, in the future to quickly tunities for growth”, says Venturini.
serve markets with economic and local production”.
SEEING CHALLENGES THROUGH REGULATIONS AS CHANCES THIS ARTICLE CONTAINS INFORMATION AND DATA FROM THE
FOLLOWING MARKET STUDIES:
An increased focus on technical service, quality, performance and
environmental considerations is expected by Venturini. “Consumers „Pigments and Dyes - a Global Strategic Business Report” by Global
today have access to more information than ever before and in- Industry Analysts (GIA)
creasingly educate themselves prior to making purchases to be sure E-Mail: info411@strategyr.com
the product meets their socio-environmental requirements. Paint
producers are responding and this in turn drives upstream sup- „Dyes and Pigments Market - Global Trends & Forecast to 2018“ by
pliers, including pigment suppliers”, he explains. However, even if Markets and Markets
the regulations are increasing regarding the topic environment, the E-Mail: ishita.sarkar@marketsandmarkets.com
E U R O P E AN CO AT I NGS J O UR N AL 2018
OUR NEW AQUEOUS PIGMENTS:
MORE STABILITY, MORE BRILLIANCE,
MORE DARKNESS!
Get to know our new, intriguing HYDROSHINE WS-6001, the darkest shade ever within this water-based
effect pigment series. Our novelty HYDROSHINE WS-4140 combines a slightly brighter nuance with high-
est brilliance.
Make sure to discover the latest advancements in silverdollar production technology: the aqueous STAPA®
IL HYDROLAN® S 400 series features alluring flop behaviour. These chemical and gassing stable pigments
show glossy metallic effects or precious silver sparkle.
The total investment at the Ningbo site is around EUR 60 mil- In the future, the company will market their new red iron oxide pig-
lion for an initial annual synthesis capacity of 25,000 metric ments globally under the well-known “Bayferrox” brand. The main
tons. On the same site, Lanxess is building a mixing and milling customers for these pigments are manufacturers of paints and
plant for inorganic pigments with an annual capacity of 70,000 coatings, as well as the plastics industries. „The mechanical com-
metric tons. The company has created a total of around 200 pletion of our plant was in September. Currently we are in the start-
new jobs with these two plants which are scheduled to start up phase and conducting further tests. It is important to bring the
production in the first quarter of 2016. new pigments into the market with a reproducible quality“, said
Hellwig. As this is the case now, the production is scheduled to start
E U R O P E AN CO AT I NGS J O UR N AL 2018
T O P I N DU S T R Y M O VE 13
“No danger of
overcapacities“
Jörg Hellwig, Head of Lanxess Inorganic Pigments business unit
Employees: 200
Five questions to Jörg Hellwig
Why did you choose China for your new plant? The entire Asia-
Pacific region, and in particular China, remains the largest market for
pigments. Apart from the high demand, China offers an excellent raw
materials supply situation.
How do you rate the demand for your new reds? We can offer
more yellowish reds. Especially the paints industry likes mixing colours.
Now they can start mixing with a brighter colour tone. Our customers
Production capacity: 25,000 tonnes per annum have shown that there is a great demand for our new pigments. This
puts up the pressure to start production as early as possible. But it is
important to make sure that we can supply reproducible quality once
we go on-stream. This is now the case. We have scheduled to start with
production in the first quarter in 2016.
What is so special about the new plant and process? It will be the
first sustainable iron oxide production process in China with a conse-
quent recycling and treatment of all by-products. Compared with the
Another example is that a recycling process of off-gases will lead to traditional Penniman Red process, the Ningbo Process uses a special
fresh raw materials for production. Compared with the traditional catalyst to convert laughing gas to air and water. We have named it
Penniman Red process, the „Ningbo Process“ uses a special catalyst Ningbo Process to show our appreciation to the city.
to convert laughing gas to air and water. Thanks to the particularly
energy-efficient process, the plant will meet the highest international To what extent do you see the danger of overcapacities in the
environmental standards. market? Not all announcemnets are actually realised. In many cases
these projects are replacement investments. Environmental restric-
EXPANDING FOOTPRINT IN CHINA tions are becoming more similar worldwide, one could even say they
are becoming almost standardized. If this is advancing further, older
“The new pigment plant in Ningbo will further expand our footprint in sites in China will not be expanded or will be completely closed. An
the China market which is of strategic importance to Lanxess. It will new-built is most likely linked to a previous reduction in capacities. The
also enable us to meet local customers’ needs for customized and demand for pigments is increasing, therefore I do not see the danger
innovative products in a more efficient manner,” said Rafael Suchan, of having an overcapacity now or in the future.
Vice President - Asia-Pacific for Lanxess Inorganic Pigments.
Lanxess already operates one of China’s largest plants for iron oxide How do you rate the competition in the market for iron oxide
pigments in Jinshan, Shanghai. This plant has an annual capacity of pigments? In the past we had some 70 players in the market, now
38,000 metric tons of iron oxide yellow and black pigments each year. the number has declined to roughly 30. The competition stirs the en-
The company has an annual production capacity of roughly 375,000 vironmental restrictions and this will lead to a further consolidation.
tonnes of iron oxide pigments around the globe – once the Ningbo in the market. This may bring advantages for producers from mature
site goes on-stream. Apart from China, the pigment producer opera- regions. It is not possible to produce cheaply if you have a certain
tes manufacturing facilities in Germany and Brazil as well as running demand of quality for products.
additional mixing and milling facilities in Australia, the UK, Spain and
the United States.
GROWING THE
PIGMENT BUSINESS
Ferro Corporation has announced entering into an agreement to acquire Cappelle Pigments NV (“Cappelle”) and the
acquisition of certain assets of Delta Performance Products (“Delta”), for aggregate consideration of approximately
EUR 55.2 million. By Damir Gagro (publishec in ECJ 11/2016(.
Sales for the two businesses in 2016 are estimated to be coatings, inks and plastics and sells its products in more than 75 coun-
approximately EUR 69.9 million in the aggregate and ad- tries. The company specializes in weather-, heat-, and light-resistant
justed EBITDA in 2016 is expected to be approximately organic pigments. The pigment producer is also a market leader in
EUR 10.1 million. Based on estimated 2016 adjusted EBITDA, certain inorganic pigments that complement Ferro’s market positions
excluding expected synergies, the purchase price of the two in complex inorganic coloured pigments (CICP) and ultramarine blue
businesses represents a combined transaction multiple of ap- pigments.
proximately 5.6. Cappelle is headquartered in Belgium with an additional production
site in France and has a worldwide representation and sales in more
is expected to close by year end, subject to customary closing condi- ADDITIONS TO FERRO‘S GROWING PIGMENTS BUSINESS
tions, including regulatory review.
Cappelle is a 125-year-old, privately held company that produces On August 1, 2016, Ferro purchased certain assets of Delta Perfor-
specialty, high-performance inorganic and organic pigments used in mance Products. This business produces customised colourant
E U R O P E AN CO AT I NGS J O UR N AL 2018
T OP I NDU S TRY MO VE 15
ADD SOME
SHINE TO YOUR
Ulrich Poth
METALLIC EFFECT PIGMENTS
blends that utilise Ferro’s CICPs for the concrete and outdoor
hardscape markets. Silver cars, gold labels on beer bottles, glittering
Peter Thomas, Chairman, President and CEO of Ferro Corpora- lipsticks, and sparkling fireworks: metallic effect
tion, said: “These acquisitions are great additions to our growing pigments and their applications are becoming
pigments business. Both fit extremely well into the strategy for
more widespread and more diverse every day.
our colour solutions businesses, and we are excited about the op-
portunities these assets present to enhance shareholder value. Get a concentrated overview of these pigments
Over the next 12 to 24 months, between the two businesses, we and learn more about their chemical, physical,
expect to realize commercial and operating synergies of EUR 2.7 and optical properties, and their wide range of
million to EUR 3.7 million.
applications – including related specifications
He further compared these acquisitions to the Nubiola acquisition
Ferro made last year for EUR 149 million. The new additions both and future potential for development.
increase the breadth of options Ferro can offer, they increase tech-
nical capabilities and enhance the company‘s market position. The
2006, 234 pages, hardcover,
transactions will increase Ferro’s PPO business by approximately 30%
155 x 225 mm, 149 €,
and expand its addressable market for pigments by a factor of four,
order no. 310
to approximately EUR 3.7 billion, Thomas elaborated. The addition of
Look inside
Cappelle’s proprietary pigments and capabilities is expected to advan- the book!
ce expansion into the specialty organic pigment market and round
out Ferro‘s product portfolio. The Delta transaction enhances posi-
tion as a manufacturer of engineered colorants and custom blends.”
Thomas concluded: “These businesses demonstrate the value pro- EUROPEAN
position of our Pigments business. We create value for our custo-
mers by combining and manipulating pigments to produce spe- C OATINGS library
cialised color solutions that provide functional attributes for our
customers’ end products, or improve the effectiveness and efficien-
cy of their supply chain and manufacturing processes.”
Vincentz Network · P.O. Box 6247
30062 Hannover · Germany
E UR OP E AN COAT I N GS JOUR N AL 2018 info@european-coatings.com
16 P R O D U C T O VE R VIE W
GREAT-LOOKING THANKS TO
INTERFERENCE PIGMENTS
The first interference pigments were only used for automotive styling. Today, they are an indispensable part of the automo-
tive industry and OEM finishes containing them come in all colours. By Werner Rudolf Cramer (publishes in ECJ 06/2016).
Pigment Name Pigment Name Pigment Name Pigment Name Pigment Name
group group group group group
XillaMaya Crystal Silver Adamas Splendor Paliocrom® Bright Orange Iriodin Pearl Gold Symic OEM Medium
White Silver
XillaMaya Galaxy Blue Adamas Splendor Paliocrom® Bright Gold Xirallic Crystal Silver Symic OEM Medium
Blue Copper
XillaMaya Electric Blue Adamas Dazzling Mearlin Fine Red Colorstream Viola Fantasy Luxan CFX Red
Red Exterior
Setallic Desert Orange Kromax Corona Mearlin Aztec Gold Pyrisma Liquid Blue
Violet Exterior
Automotive Rutile Green Automotive Splendor Glacier Ext. Frost White Meoxal Wahiba
Pearl Red Orange
E U R O P E AN CO AT I NGS J O UR N AL 2018
P R O DU C T O V ER VIE W 17
HOW TO EFFICIENTLY CHARACTERIZE
SPECIAL EFFECT COATINGS
In this paper, a simple and efficient approach is present-
ed on how to characterize the appearance of surfaces
composed of metallic and interference pigments.
100
Schlenk Viavi Solutions (Flex Products)
ChromaFlair 190
80
Pigment Name Pigment Name
group group
60
Multiflect Polychromatic ChromaFlair Green/Purple 190 65°/15°
40
20°/15° 20
SpectraFlair Silver 1500
0
-100 -80 -60 -40 -20 20 40 60 80 100
-20
45°/25°
-40
-60
45°/15°
interference -80
aspecular
-100
In paint formulation, achieving the right colour depends on ąą 91015 Pearl Blue pure
the pigments used. When conventional pigments and modern ąą 91237 pure Xirallic Galaxy Blue
effect pigments are mixed, many things have to be considered ąą 91006 Aluminium Silver Dollar + solid_2
to obtain the desired result. ąą 91019 Pearl Blue + solid_2
ąą 91229 Xirallic Galaxy Blue + solid_2
E U R O P E AN CO AT I NGS J O UR N AL 2018
C O L O U R DE S IG N 19
VISUAL OBSERVATION
Figure 1: The shift of the interference line in mixtures of a pearl blue interfer- Figure 2: The unchanging, typical interference line of Color-
ence pigment with colour pigments at different concentrations
In visual observation and assessment of sample panels at the window BRINGING COLOUR TO LIFE
and in most light booths, the offset angle between illumination and
observation is always the same. If the panel is held at the window such The yellow, orange and red colour families are strong pigments that have
that you are looking at it at the gloss angle, the illumination angle is high chroma and high lightness. Both characteristics have a disruptive
15° from the perpendicular, for example. The gloss angle – and in this effect when mixed with interference pigments, particularly transparent
position also the angle of observation – is therefore -15°. The result interference pigments which are less prominent when they are close to
is an offset angle of 30° between illumination and observation. This the gloss angle, because of the colour reflection. For the above colour
remains the same when the panel is tilted backwards and forwards. groups, interference pigments whose platelets are coated with iron ox-
The panel always remains in the cis-position when it is tilted towards ide or a combination of titanium dioxide and iron oxide are more suit-
the observer, it, i.e. the sample is always seen on the illumination side. able. This particularly applies to reds, which are very much in demand at
If it is tipped it away from him, it is initially seen in the trans-position, present, intersesting colour reactions can be created with interference
i.e. on the opposite side of the gloss angle to the illumination. Tipping pigments coated with iron oxide.
it further away, moves it into the cis-position. Green, blue and violet are the most interesting colour groups for use
with transparent interference pigments.
OPTICAL BEHAVIOUR IMPORTANT When aluminium and interference effect pigments are mixed with sol-
id-colour pigments, similar behaviour is seen to that achieved by mix-
Unfortunately, current portable devices offer hardly any method of ing solid-colour pigments with white (titanium dioxide). For example,
measuring interference. The -15° aspecular geometry established in if a yellow or red solid-colour pigment is mixed with white, the colour
the “ASTM E2539-12 Standard Practice for Multiangle Color Measure- line travels from yellow or red towards white. Green or blue solid-col-
ment of Interference Pigments” provides an interim solution. Compar- our pigments look black and become coloured only when diluted, i.e.
ing reflection curves at +15° and -15° enables coloured interference by mixing them with white, the chroma and lightness increase initially,
pigments to be distinguished from aluminium and white interference until the chroma peaks and then falls away again. Further addition of
ones (see Figure 3). A significant difference regarding optical behav- white makes the colour paler and lighter.
iour should be considered when creating new effect paint. Aluminium Similar behaviour is seen in interference pigments. A white interfer-
pigments and white interference pigments show an increase in their ence or an aluminium pigment is brought to life by using them in
reflection when the observation point changes from the cis-position mixtures. The overall colour impression initially increases in chroma
(+15° aspecular) to the trans-position (-15° aspecular). and brightness. Once the peak, has been reached, only the lightness
Coloured interference pigments also demonstrate colour travel to- increases and the chroma falls away to create an achromatic effect
wards the shorter wavelengths. mixture. This is illustrated in Figure 4. Mixtures of coloured interfer-
The second illumination at 15° formulated in the ASTM standard prac- ence pigments with solid-colour pigments show direct colour gradi-
tice is also helpful. With these measurement values and those at 45° ents between the pigments.
illumination, an interference line can be created, although it is only a Interference and aluminium pigments can also be mixed with white
stopgap. However, it can be used to describe optical properties. pigment(titanium dioxide). However, the effects achieved are quite
During visual assessment of effect paints at the window or in the light weak. Titanium dioxide pigment particles are comparatively large,
booth, the sample panel should not be tilted backwards and forwards. which means that the effects may turn out to be inadequate.
Rather, it should be viewed with arms outstretched against the light Some specific features need to be taken into consideration when
source. The arm is then moved downwards with the panel held parallel. interference and aluminium pigments are mixed. Fundamentally,
Thus, the distance to the light source is simultaneously reduced, so that coloured interference pigments move towards shorter wavelengths
the sample is always viewed close to the gloss angle. In this way, the when the angle of illumination becomes flatter. However, this travel
colour travel of the interference can be identified. This can be seen very is reduced and restricted by the presence of aluminium pigments. As
clearly with the modern developments in interference pigments. from a certain mixture ratio, it is worth replacing a coloured interfer-
Figure 3: A comparison of geometries of 45°/-15° and Figure 4: Mixtures of aluminium and pearl blue effect pigments
45°/+15° with blue at 45°/15°
250 50
200 40
150 30
R [%]
R [%]
100 20
50 10
0 0
400 500 600 700
Wavelength λ [nm]
Alu + blue 45°/15° Viola Fantasy + blue 45°/15°
Alu + blue 45°/–
45°/–15° Viola Fantasy + blue 45°/–
45°/–15°
E U R O P E AN CO AT I NGS J O UR N AL 2018
C O L O U R DE S IG N 21
ence pigment with a white version. on the overall colour impression. The work does not necessarily have
Samples painted with an aluminium pigment appear grey. Corre- to start off in the colour range required. The colour can be shifted
spondingly, those painted in white interference pigments are per- with other interference pigments of the same type or of a different
ceived to be white. The panels, which are of a normal size, are studied one. For example, a green interference pigment can be moved in two
vertically across their whole surface at an angle of about 20°. When directions by adding a yellow or blue pigment. With a white or a red in-
observed close to the gloss angle, the reflection of the aluminium pan- terference pigment, the interference becomes smaller and therefore
el is stronger than the interference panel. The addition of white inter- the interference line as well. And with a white interference pigment,
ference pigments would reduce its lightness close to the gloss angle. the mixture becomes paler.
Close to the gloss angle (illumination 45°/observation 60° = -15° as- Interestingly, transparent and other interference pigments can be
pecular), different pigments reflect differently: Silverdollar aluminiums mixed in almost any combination. As they obey additive mixing rules,
(91014) reflect more strongly than cornflake aluminiums (91265), Xiral- a pearl green and a pearl red result in a whitish yellow. Adding a pearl
lic Galaxy Blue (91237) more strongly than Iriodin Pearl Blue (91015). blue to the yellow can make it travel in the direction of the colour
The effect can also be changed with the addition of a flop controller or position of the starting pigments. If, for example, a mix of Xirallic Stel-
micronised titanium dioxide. This applies in particular to formulations lar Green and Solaris Red together with a “dash” of Galaxy Blue gives
containing aluminium. an interesting white with a different sparkle effect to that of Xirallic
Crystal Silver. As shown in Figure 6, the interference line can be shift-
STRATEGIC APPROACH ed completely by mixing with other interference pigments. Here the
black mixture of Viola Fantasy has been mixed respectively with Pearl
In most cases, a new paint is created by replacing the effect pigments Lilac, Pearl Green and Pearl Blue. The aspecular lines (grey) all run in
in an existing formulation. The advantage of this method is that the the same direction.
formulation has been already used and tested. The disadvantage, At the next stage, absorbent, perhaps even transparent, colour pig-
however, is that it is impossible to predict how prominent the effect ments are added. Here it should be noted that these have the biggest
pigment will be in the formulation and how strong it may become. It influence on the overall colour impression at angles a long way from
is rather like putting a new F1 racing car engine in a small used car. It the gloss angle.
can give surprising results! If interference and aluminium pigments are to be mixed, it is best
A strategic approach is always better. It is certainly possible to use to begin with the stronger partner in the mixture. In the case of an
existing formulations as a guide, but effect pigments are unique, in- aluminium pigment, this is then added to the interference pigment
terference pigments in particular. The choice of effect pigment should required in order to create colour in the interference geometries (dif-
therefore be considered at the outset. ferent illumination angles with the same aspecular angle). Although
The intensity of an effect can be shown in a comparison between ge- the aluminium pigment flop effect is substantial in terms of lightness,
ometry close to and far away from the gloss angle. For example, alu- it can be altered by using an appropriate flop controller – if the inter-
minium pigments of the cornflake and silverdollar type and various ference pigment added has a crucial effect on the colour close to the
types of interference pigments show comparatively strong differences gloss angle. The addition of solid-colour pigments and appropriate
in reflection between these geometries. Figure 5 demonstrates that, white pigments serves to steer the character of the aluminium and
away from the gloss angle (illumination 45°/observation -20° = 25° interference effects in a coloured or achromatic direction.
aspecular), the reflection of pigments such as aluminium Silverdollar
and interference pigments reduces significantly, which illustrates the
intensity of the effect.
Having chosen the colour range of a new paint and what effects are to
be achieved, if it is decided to use one or more interference pigments,
one begins with that which is intended to have the greatest influence
Figure 5: A comparison of the reflection of Silverdollar and inter- Figure 6: How the interference line shifts when differing interfer-
ference pigments with other effect pigments ence pigments are mixed
150
100
R [%]
50
0
400 500 600 700
Wavelength λ [nm]
91014 91015 91006 91229
91265 91237 91019 91002
The challenges of achieving a good metallic finish in UV-cura- and gelling in comparison to additive-stabilised types.
ble coatings are assessed. Aqueous systems provide the best In addition to the dispersion, drying is especially important for the
compromise between visual and performance properties. To orientation of aluminium pigments. High film shrinkage and rapid
achieve effective cure despite the UV-reflection of the pig- physical drying favour parallel alignment of the pigments. This is not
ment, the pigmentation level must be optimised for the ap- available in the case of high solids and 100 % solids systems, which
plication and pigment grade. thus leads to less effective flop characteristics.
In UV systems, the effect attainable therefore essentially depends on
the type of formulation. Aqueous, conventional or solvent-free sys-
Solvent-free, conventional or aqueous: in what system can the ad- ADVANTAGES AND DISADVANTAGES OF VARIOUS APPROACHES
vantages of UV technology be combined with attaining highly brilliant
effects? As a rule, the following factors must be considered to attain What UV coating system represents the ideal solution for combining
metallic effects with ideal flop characteristics in coatings: the desired brilliance with a high resistance? This question can only
ąą Correct pigment selection and formulation; be answered definitively if the objective is clearly defined. The relevant
ąą Coating production; requirements can range from purely visual applications through to
ąą Application as well as drying and curing. functional purposes, including all conceivable combinations. The first
Visual criteria as well as the particle size distribution or particle struc- step involves illustrating the fundamental advantages and disadvan-
ture and the stability of the aluminium pigments are crucial for pig- tages of the various approaches.
ment selection. For UV coatings in particular, it must be noted that
aluminium has a catalytic effect on the radical curing reaction. This SOLVENT-FREE: MODERATE EFFECTS BUT BEST ECONOMICS
catalysis leads to a gelling of the coating after only a short storage
period [1]. Solvent-free systems represent the ideal case for the development of
In aqueous UV formulations, the pigment must also be protected UV-curable metallic coatings. Only in the case of 100 % systems can the
against water. The use of encapsulated aluminium pigments is there- advantages of UV technology be utilised to the full. They allow curing
fore recommended, as these provide maximum resistance to gassing immediately after application, leading to considerable savings – both in
E U R O P E AN CO AT I NGS J O UR N AL 2018
R ADI AT I O N CU R I N G 23
Figure 1: Schematic representation of the effects of metallic pigment orientation: optimal (left) and unfavourable (right)
Figure 2: Comparison bet ween application of an aqueous UV Figure 3: Development of covering power as pigmentation level
coating and a conventional chemically cured coating increases, for three different sizes of aluminium pigment
Figure 4: Double bond conversion at the underside of coatings, Figure 5: Results of the König pendulum hardness test
in per cent
Figure 6: Results of the cross-cut tests Pigments used, wiht average particle size
Silver dollar 10 µm 5 10 10
Silver dollar 15 µm 7 15 26
Silver dollar 20 µm 10 20 32
E U R O P E AN CO AT I NGS J O UR N AL 2018
R A DI AT I O N CU R I N G 25
AQUEOUS: GOOD RESULTS WITH AN INTERMEDIATE STEP it is clear that the conversion decreases as the pigmentation level in-
creases (Figure 4). This is a logical consequence of the increasing re-
Aqueous UV technology represents a promising way to exploit the ad- flection or scattering of the incident radiation.
vantages of UV technology in the best possible manner while attaining This increasingly poor curing leads to a gradient in respect of cross-
brilliant effects at the same time. The only drawback is that a drying linking and hence also of hardness within the coating layer. This dif-
step has to be implemented upstream of the actual curing process. ference has an adverse effect on the properties of the coating. König
It is necessary to remove water and cosolvents from the coating, pendulum hardness tests and cross-cut tests among others were car-
which has a significant effect on the finished coating. A time saving ried out for the evaluation. These are standard tests for curing in the
nevertheless results as, in comparison to other chemically curing coatings industry.
coatings, this preliminary drying only takes a fraction of the process
time (see Figure 2). PENDULUM HARDNESS TEST FAILS TO CORRELATE WITH CURING
Aqueous UV systems are free of monomers and can guarantee high
resistance properties through the use of high molecular weight dis- A decrease in hardness as the pigmentation increases can be observed
persions in combination with radical crosslinking [3]. The formulation in the pendulum hardness test. It is notable that the varying degrees of
is in principle similar to known aqueous metallic formulations. decrease in the cross-linking between the test series that can be seen in
Essentially, the same adjustment techniques can be used to optimise Figure 5 cannot be found here. Rather, the aluminium pigments have
the effect as for other aqueous metallic coatings, thus for example a negative effect on the hardness of the coating film as the pigmenta-
dispersing additives, thickeners or wax dispersions may be used. Ow- tion level increases, irrespective of the particle size.
ing to the high resistance properties that result from the crosslinking, The pendulum hardness obviously depends more strongly on the
an additional clear coating can even be omitted in some cases. aluminium content than on the degree of cross-linking and is there-
fore not a suitable test for evaluating the chemical cross-linking in this
WATER AND UV CURING: REFINING THE BEST APPROACH case.
The adhesion testing values reveal a similar picture. Here too, the
This combination of waterborne systems and UV curing represents compositions are significantly more complex and do not permit any
the best solution at present, in order to attain both metallic brilliance clear conclusion in respect to the degree of curing determined by
as well as high chemical resistance properties, especially in the area FTIR spectroscopy (see Figure 6). In the case of low pigmentation, the
of single-layer coatings. coating tends towards embrittlement and reduced adhesion, as a very
This insight led to extensive test series being conducted in an aque- close-meshed network can form.
ous formulation based on a polyurethane dispersion suitable for UV The cross-linking density decreases as the pigment content increases.
cross-linking. These tests were to demonstrate what effect various Nevertheless, this decrease cannot be observed in the conversion of
types of effect pigments have on the properties of the coating. the double bonds. At first, this leads to an improvement in the adhe-
Coated silver dollar pigments with an average particle diameter of 10, sion test (see Figure 6), but the values deteriorate further upon reach-
15 and 20 µm were used for the tests (Table 1). The particle size dis- ing the coverage limit. This return to a negative development can also
tribution is approximately the same here. The pigmentation level was be observed from the double bond density (Figure 4).
increased incrementally from one per cent (pigment solids) to five per
cent. FORMULATION RECOMMENDATIONS
Of all the finished coatings, the conversion of double bonds was de-
termined using FTIR spectroscopy and the degree of coverage was The formulation must be precisely coordinated to the aluminium pig-
measured. Further tests evaluated the hardness and adhesion. ment for covering UV metallic coatings. Excess pigmentation results
in less favourable coating properties. The ideal coating properties in-
EXPLORING THE CONFLICT BETWEEN COVERAGE AND CURING volve working precisely at the limit of coverage during the pigmenta-
tion. This limit should be determined via a test series for every type of
The visual impression of a metallic coating results from light reflection coating or pigment.
and scattering by the aluminium pigments. The higher the compo- These tests consider pigments with similar particle size distribution,
nent of reflected light, the more brilliant and appealing the coating which means the D50 value can be compared here. In general, the
appears. particle size distribution should be used for the evaluation of the pig-
In the case of a ‘covering’ coating, no light from the substrate reaches ment.
the viewer’s eye, but instead it is reflected or scattered from the pig- When selecting the binding agent, aqueous systems are recommend-
ments beforehand. This can be measured by determining the colour ed to satisfy high visual requirements. These can be formulated with
values on a black and white substrate. If a colour difference of less relatively low solids, thereby ensuring a better orientation.
than one unit occurs, this denotes a covering coating [4]. The finer Solvent-free UV metallic finishes are achievable, but contain a signifi-
the pigment, the lower the pigment level required to attain this value cant content of monomers in the case of spray application and only
(see Figure 3). achieve moderate effects owing to the lack of film shrinkage.
For the production of UV metallic coatings, it is necessary for the high-
ly energetic UV radiation to penetrate as deeply as possible into the
coating layer so as to start the polymerisation reaction. This is in con- REFERENCES
trast to the desired light reflection of the pigments. In order to evalu-
ate whether the complete conversion of the reactive double bonds is [1] Wissling P., Metalleffekt-Pigmente, Vincentz Net work, 2005.
still ensured in the case of covering coating layers, their content was [2] Garret P. G., Strahlenhärtung, Vincentz-Verlag, 1996.
determined by FTIR spectroscopy. [3] L ippenmeier J., Weikard J., Wässrige UV-Technologie: effizient,
The percentage conversion can be determined based on measure- vielseitig,umweltfreundlich und zukunftsweisend, VILF Conference
ments on both the top and underside of the coating. No effect can be 2007.
discerned at the coating surface –either in relation to the particle size [4] M eichsner, Metzger, Schröder, Lackeigenschaften messen und
or the pigmentation level. On the underside of the coating, however, steuern, Vincentz Net work, 2003.
A new type of aluminium pigment is de- is through a controlled oxidation process in Colour travel in aluminium pigments is also
scribed which shows gold to blue colour which water and a basic catalyst are added achieved by blending them with nano-sized,
travel as a result of controlled oxidation to a suspension of aluminium in a water-mis- transparent titanium dioxide (TiO2) particles
of the flakes. This creates a uniform na- cible solvent [1, 2]. This strategy produces [1,4]. In this case, the colour travel extends
nostructured surface on the pigments, champagne-coloured metallic pigments. In subtly from the first to the fourth quadrant
promoting scattering of blue light and re- both cases, colour travel is limited mainly to of CIELab colour space, giving a ‘frosted’ ef-
flection of red and green light. These prop- the first quadrant of CIELab colour space. To fect. However, it is difficult to obtain highly
erties lead to further interesting effects extend the colour space of metallic pigments chromatic colours by this method. Addition-
when blended with other colour pigments. to other quadrants, other fabrication strate- ally, nano-TiO2 must be dispersed in a liquid
gies are needed. system prior to blending, restricting its use
E U R O P E AN CO AT I NGS J O UR N AL 2018
EFFE C T P I G MEN T S 27
RESULTS AT A GLANCE
űű A new type of aluminium pigment
is described showing gold to blue col-
our travel. Colour generation is due
to the nanostructured surface of the
pigments, which promotes scattering
of blue light and reflection of red and
green light.
Figure 1: SEM micrographs of (a) oxidised aluminium and (b) colour travel aluminium; the scale bar in each picture is 2.5 µm
ics, and plastics. The mechanism of colour of water in isopropanol and a basic catalyst tem results in a non-uniform surface that is
generation and the properties of the colour where the amount of each determines the composed of particulate Al(OH)3, as shown in
travel aluminium pigments in both liquid degree of oxidation and, the thickness of the the SEM micrograph in Figure 1b.
and powder coatings will be described. Al(OH)3 layer. uring oxidation and escapes Although not regularly arranged, the particu-
by tunnelling through the Al(OH)3 layer. From late moieties on the flake surface are relatively
HOW OXIDATION CHANGES THE COLOUR a morphological standpoint, this makes the monodisperse (about 250 nm in Figure 1b), and
OF ALUMINIUM FLAKES layer uniform but porous as shown in the can be described as a ‘pseudo diffraction grat-
SEM micrograph in Figure 1a. The colour of ing’. The presence of these particles results in
Oxidised aluminium pigments are metallic these pigments ranges from champagne to a colour change from gold to blue as the ob-
pigments in which the surface of the alumini- gold, depending on the purity of the starting servation angle is increased from 15 ° to 110 °.
um flake is modified by oxidation reaction (1): flake and the thickness of the Al(OH)3.
2 Al + 6 H2O 2 Al(OH)3 + 3 H2 (1) By using a two-phase oxidation system, a new COLOUR BEHAVIOUR OF DIFFERENT
This class of pigments have a metallic alu- type of oxidised aluminium pigment, display- ALUMINIUM PIGMENTS
minium core and a hydrated aluminium ox- ing colour travel from gold to blue, can be
ide (Al(OH)3) shell. Traditionally, oxidised alu- produced. The two-phase system comprises Because it has a nanostructured surface,
minium pigments have been made through water, a water-immiscible solvent, a surfactant colour travel aluminium has different colour
surface oxidation in a single-phase system and a base. Using a multiphase oxidation sys- properties in comparison to unoxidised and
oxidised aluminium pigments. This is exem-
plified in Figure 2 which shows a display of
Figure 3: Brightness comparison at five different observation angles for unoxidised, colour colour travel aluminium (centre) compared
travel and oxidised aluminium pigments to unoxidised (left) and oxidised (right) alu-
minium pigments of similar particle size and
distribution.
On the face, unoxidised aluminium appears
silver and is the brightest of the three pig-
ments. Meanwhile, oxidised and colour
travel aluminium pigments are champagne
and have a slightly decreased brightness. At
steeper angles, the silver and oxidised alu-
minium pigments behave predictably, show-
ing a dark flop and a relatively consistent hue.
In contrast, colour travel aluminium has a
light flop that is in a different region of col-
our space (i.e. blue) from the face. The effect
is pronounced, and the drawdown of colour
travel aluminium appears to ‘lighten up’ at
large angles, an effect not previously ob-
served in unblended metallic pigments.
E U R O P E AN CO AT I NGS J O UR N AL 2018
EFFE C T P I G ME N T S 29
In contrast, the FI for colour travel aluminium flection are suppressed for the 110 ° measur- ber of different applications. It has a light flop
is 14.96, indicating that the pigment scatters ing angle. while maintaining the sparkle and shine that
light to steep angles. In some respects, the physics of colour is characteristic of most effect pigments. Fab-
The colour of the pigments in CIELab colour generation are similar to that of blends of rication of these pigments is also simple and
space is shown in Figure 4 for all five angles. transparent nano-TiO2 dispersions with alu- can be tuned for a variety of aluminium flake
The colour of unoxidised aluminium is always minium flake pigments in liquid paint system types (i.e. cornflake, metallic, silver dollar)
located in the achromatic region of colour [5]. However, because the Al(OH)3 particles and sizes, making these pigments suitable for
space and is within ± 5 units from the origin are directly attached to the surface of the a number of different applications. The effect
at all angles. aluminium flake, the colours observed are of colour travel aluminium is readily appar-
For the oxidised aluminium pigment, the col- more coherent and the scattering patterns ent in a number of different media, including
our is initially chromatic (champagne) and are sharper. liquid coating, powder coatings, liquid inks,
travels to a location near the origin in the plastics and cosmetics, among others.
achromatic region, a characteristic that is PRACTICAL APPLICATIONS OF THE TECH- In liquid coatings, the behaviour of colour
typical of interference pigments. Finally, the NOLOGY travel aluminium with respect to stability and
hue of the colour travel aluminium pigment dispersability is similar to standard unpassi-
begins in the first quadrant, passes through Because of its unique behaviour, colour trav- vated aluminium pigments. Thus, these ma-
the achromatic region, and ends in the third el aluminium has a colour desirable in a num- terials can be readily incorporated into these
quadrant, corresponding to a colour shift
from gold to blue.
It is also worth mentioning that the hue of col- Figure 5: Colour travel for a variety of colour travel aluminium pigments plotted in
our travel aluminium pigments can be tuned CieLAB colour space
by changing the reaction conditions. Figure
5 shows the colour graphs of a few different
colour travel aluminium pigments for all five
angles. Generally speaking, although it is not
always the case, a more oxidative environment
during fabrication leads to a more red-gold
pigment with higher chroma, more drastic
colour travel and a brighter flop, while a less
oxidative environment leads to a lighter, silver/
champagne-coloured pigment with less chro-
ma and colour travel and a darker flop.
systems with minimal modification to coating minium at 5 % loading. The bases used in the These pigments can be used in a number of
formulation, although their higher surface shapes in Figure 8 are black (left), clear (cen- applications, such as liquid and powder coat-
area may require tuning the pigment to bind- tre), and white (right). ings, where their unique colouration prop-
er ratio to get an ideal formulation. When colour travel aluminium is blended erties can lead to interesting colour blends
Colour travel aluminium has unique behav- with a black base, interesting speckled an- and effects that have not been previously
iour both as an unblended and as a blended tique effects can be obtained, while blending achieved.
pigment. Figure 7 shows various colour blends with a white base causes the flop colour to
of colour travel aluminium with organic and become accented. Blending with coloured
effect pigments. The champagne to gold face bases results in colour properties similar to REFERENCES
colour is ideal for blending with red, orange, the cases reported for liquid coatings, al-
or yellow pigments to give intense chromatic though the effect in powder coatings is more [1] Wißling P., Metallic Effect Pigments,
reds (Figure 7 top), while blending with blue subtle due a lower alignment of the pigment Vincentz Net work GmBH & Co., Hannover,
or green pigments results in an attractive flakes in these applications. Germany, 2006.
patina (Figure 7 centre). Finally, tinting with [2] Reisser W., Oxidized colored aluminium
carbon black can amplify the gold face col- PIGMENT PERFORMANCE IN SUMMARY pigments, process for their production and
our of these pigments while slightly toning their use, US 5,964,936, Oct. 1999 (Eck-
down the flop colour (Figure 7 bottom). It is im- A new type of oxidised aluminium pigments art).
portant to note again here that colour travel has been devised, characterised by having a [3] Klein G. A., Industrial Colour Physics,
aluminium pigments flop light with respect to structured surface. Although other oxidised alu- Springer Science + Business Media, Inc.,
other metallic pigments, creating an interest- minium pigments exist, structured oxidised alu- New York, USA, 2010.
ing dark to light travel effect when blended. minium pigments have so far not been reported. [4] Shimizu, h., Fujita N., Coating Composition
Colour travel aluminium can also be incor- The structured surface behaves like a pseu- and Coating Film Form-
porated into powder coatings, either by dry do diffraction grating and leads to interest- ing Method, US 2012/0295032, Nov.
blending or bonding, leading to a number of ing optical effects such as gold to blue colour 2012
interesting effects. Figure 8 shows three pow- travel and a light flop as the aspecular obser- [5] http://www.iskiweb.co.jp/eng/products/
der coated speed shapes of colour travel alu- vation angle is increased. functional02.html
Figure 7: Displays showing panels sprayed with various paint Figure 8: Powder coated speed shapes containing a colour
blends containing colour travel aluminium; the unblended pig- travel aluminium pigment; left to right, the pigment is sprayed in
ment used in each of the blends is sprayed on the panel to the black, clear and white bases
far bottom
E U R O P E AN CO AT I NGS J O UR N AL 2018
W O R LD O F C O L O UR 31
LESS IS MORE
Only small amounts of coa-
ting are needed to coat a
pencil – less than one gram
is used apiece. The pencil
has a long history – its first
precusors were produced in
1565 in England.
Source: Deutsches Lackinstitut
FORMULATING EXCELLENT
AUTOMOTIVE EFFECTS
Eight golden rules for creating automotive coatings using effect pigments. By Werner Rudolf Cramer (published in
ECJ 01/2016).
colours.
Modern automotive surfaces shine through the use of inter-
ference and aluminium effect pigments. Effective use of these MINDING THE GEOMETRIES
pigments in formulating automotive coatings depends on deep
knowledge on their properties and features in application. In most cases, modern automotive coatings have visual effects that in-
volve differences – either in the lightness of the coating, or in both the
E U R O P E AN CO AT I NGS J O UR N AL 2018
EFFE C T P I G MEN T S 33
the illuminated side, while “trans” angles are on the opposite side of
the gloss. Manufacturers of measurement instruments refer to these
standard aspecular angles, usually -15°, 15°, 25°, 45°, 75° and 110°,
which correspond to absolute observation angles of -50°, -30°, -20°,
RESULTS AT A GLANCE 0°, 30° and 65° (see Figure 3). The measurement results at 45°/as-
15° are similar to those at 65°/as15°: if the connecting line between
űű Angle-dependent visual effects have arisen since the 80s the two geometries 45°/as15° and 45°/as-15° in the extension of the
and can be characterised by multi-angle measurements. two geometries 45°/as25° und 45°/as15°, then the coating mix does
not contain a colour interference pigment. With a colour interference
űű Interference pigments create angle-dependent colour ef- pigment, the curve bends counterclockwise. Coatings with aluminium
fects and can be used additively. pigments do not have this kink; the connecting line for these occurs
between the measured values at 45°/as25°, 45°/as15° and 45°/as-15°
űű Aluminium pigments can be used to create metallic effects. and is nearly straight (see Figure 4).
űű Mixing colour pigments with the effects of interference pig- GETTING TO KNOW EFFECT PIGMENTS
ments and aluminium pigments creates dazzling new coatings.
While colour pigments partially absorb incoming light and partially scat-
ter it undirected in all directions, interference pigments additionally
partially transmit the light. Particularly, in the case of transparent inter-
ference pigment types, one can recognise the intense reflection colour
and the transmission colour, which are complementary to each other.
Transparent interference pigments consist of a substrate particle
(of e.g. mica, aluminium oxide, or silicon oxide) covered with a highly-
refractive metal oxide layer. When light strikes the surface, a part of
this light is reflected, while the other part travels through the metal ox-
ide layer until it arrives at the boundary layer to the substrate, where it
hicle (i.e. if the observer were to be at the same angle as the reflected is, again, partially reflected. This reflected portion of the light exits the
light, as in Figure 1), the aspecular angle between gloss and observer pigment particle parallel to the first reflection component, and both
would be 0°. However, if the observer’s eye moves away from the component light waves then interfere with each other constructively
gloss direction, the aspecular angle starts to grow. In the example in or destructively, depending on the path length difference (the “phase
Figure 2, the car body panel has been tilted and the illumination and shift”) taken by the passage through the metal oxide layer. The degree
the gloss/specular angle are now both at 5° from the new normal, but, of constructive or destructive interference differs by wavelength of
as a result of the tilt, the gloss has moved 20° away from the observer. light, and the thickness of the metal oxide layer can be tailored to
The ASTM E2539 Standard Test Method for Multiangle Color Meas- interference of certain wavelengths. Light of certain wavelengths is
urement of Interference Pigments proposes characterising the colour therefore seen to be selectively reflected, depending on the thickness
reflection effects of effect pigments in a coated surface by collecting of the highly refractive layer (or layers), their refractive indexes and
measurements at multiple angles in the plane formed by the illumina- the angle of the incoming light.
tion, the normal and the gloss, including on the “opposite” side of the The rays of light that pass all the way through transparent interfer-
gloss. ence pigments experience something similar on the reverse side of
For formal reasons, these aspecular angles are given a negative sign. the pigment and also interfere. Since the rays of light are moving from
Thus, the aspecular angle of -15° corresponds to an observation angle optically denser to optically thinner media, the phase shift is absent.
at -60° when illuminated at 45°. To distinguish between the positions, For this reason, the transmission colour complements the reflection
the prefixes “cis” and “trans” may be cited. “Cis” angles are located on colour: if the interference pigment reflects blue, then its transmission
Figure 1: The geometries of the illumination, the surface and its Figure 2: If a test panel is tilted by the obser ver, the angle
normal, the obser ver and the gloss (= reflection). In this exam- bet ween the light source and the obser ver does not change: it
ple, the obser ver is obser ving from the same angle from the remains at 30°, but there is now an aspecular angle bet ween
normal as the gloss/reflection. the obser ver and the gloss/reflection.
colour is yellow. This can be observed when the pigment on a trans- aluminium pigments are formed by pulverising aluminium into tiny
parent film or a white substrate is applied: the colour perceived on particles, after which small particles that resemble potato tubers are
the surface appears to be blue while the transmission colour is yellow. formed. When these are flattened, they become aluminium pigment
Figure 5 shows how there can be a viewing angle transition from the “flakes” (so named because of their irregular appearance, similar to
reflection colour to the transmission colour. “cornflakes”). When the pulverisation is carried out with an inert gas
There are different types of interference pigments, which can roughly process, then the result is small beads, that, when flattened, lead to
be distinguished by how they were produced: transparent, or semi- flat, round pigments called “silver dollars”. Aluminium pigments vary in
transparent ones are made in wet-chemical processes for which the sizes ranging from 11 µm to 24 µm for the cornflakes and 14 µm to
carrier materials consist of natural mica, aluminium oxide or silicon 34 µm for the silver dollars (the numbers quoted are median diam-
oxide. These carrier particles can be coated with metal oxides such as eter, or D50).
titanium dioxide, iron oxide or chromium oxide. In a visual assessment, for example, when tilting the test panel at the
window, the illumination and observation angles change. However, as
APPLYING SPECIFIC INTERFERENCE PIGMENTS can be seen in Figure 2, during this process, the positions of the illu-
mination (sun) and the observer – and thus the angle between them
Since interference pigments are mostly transparent, appropriate pig- – remain the same. The geometries for visual observation do not cor-
ments need to be added to the coating formulation to increase hid- respond to those of measuring instruments. This would require that
ing power. By mixing transparent interference pigments with blue, or the light source would always have to shine at the same angle.
green colour pigments, the transparency of the mixture decreases. Aluminium pigments and pastes react to colour pigments in the same
Simultaneously, the chroma (colour intensity) of the mixture initially way that white or colour interference pigments do: the chroma in-
increases, only to decrease again after a certain point. This phenom- creases to a maximum, and then falls again, while the lightness in-
enon is also common in white colour mixtures: a blue pigment or its creases continues to increase.
corresponding paste is usually bluish black. When more white is add-
ed, the mixture becomes more colourful and chromatic (bluer) – up SELECTING THE DESIRED COLOUR RANGE
until a certain point. Beyond this point of the highest chroma, further
addition of white makes the mixture start to become paler and more To create a new colour with visual effects, start with a special effect
achromatic again.
These days, aluminium pigments are also added to finishing mixtures
to achieve an optimum colour mix with maximum chroma of the in- Figure 4: Coloured interference pigments show significant colour
terference pigment and also a high degree of hiding power. However, changes depending on the illumination and aspecular angle.
it should be noted that both coloured and aluminium pigments can Tilting a panel in the light booth or at the window, the geometries
strongly influence the interference effect, or even prevent it. When mix- are different to those of portable instruments.
ing a new colour, it is crucial to make sure that using an interference
pigment only makes sense when it emphasises or enhances the colour.
45° illum.
Figure 3: Modern portable measurement instruments illumi- 45° asp.
nate at 45° and measure at -15°, 15°, 25°, 45°, 75° and 110°
aspecular.
45° illum.
75° asp.
Transition area
E U R O P E AN CO AT I NGS J O UR N AL 2018
EFFE C T P I G MEN T S 35
pigment and observe its behaviour. If, for example, one takes a col- ments can also produce beautiful green hues. If one wanted to mix
ourful interference pigment, then the first step is to mix it with black to bright metallics or silver, as in the coating seen in Figure 6, then one
determine the effect. The next step is to repeat the experiment with a could conveniently choose an aluminium pigment from the beginning.
blue or green colour pigment (or their corresponding pastes). The ac- Since different types and sizes are offered, the decision for the level
tual colour and effect possibilities of such interference pigments can of shine and the coarseness of the complete mixture is made at this
be very quickly recognised in experimenting with these combinations. point. Afterwards, colour pigments can be added to provide a gen-
From these trials, a number of ideas will arise for new colours, which eral, directional tint to the colour. Interference pigments can also be
can be prepared in OEM applications. added, depending on the type and proportions of the overall mixture,
On the other hand, one can also control the desired colour range to give a more, or less pronounced colour effect – as in the bright red
in a targeted manner by adjusting the combination of different pig- in Figure 7.
ment types: if the formulation is dominated by a colour pigment, then
this will determine the overall colour. The addition of an aluminium THINKING IN COLOUR SYSTEMS
pigment will determine the shine effect of the mixture; here one can
choose from a spectrum, between fine to coarse aluminium pigments, The portfolio of colour and effect pigments offered is so expansive
as well as between “cornflakes” and “silver dollars”. Additional interfer- that it is possible to create virtually any colour, nowadays. Neverthe-
ence pigments allow one to determine the visual effect behaviour of less, it is always important to remember that these pigments are real
the complete mixture. Here again, there is a large range of options and not theoretical. It is not possible to produce an “ideal” (neutral)
that opens the door to many possibilities. yellow. Yellow colour pigments have either a red, or a green compo-
If, for example, one starts with a blue pigment, then white and colour nent. Furthermore, a red colour pigment, can produce many red col-
interference pigments may be added. White interference pigments our effects. The reason for this is, firstly, the same as for the yellow,
give a silvery effect, while colour interference pigments create more and, secondly, the reaction of red pigments with white or in mixtures
colour effect. Even gold or red copper interference pigments can be is not ideal, and instead can turn to, for example, violet, or more blu-
added to the original blue pigment: since they have absorbent ele- ish hues in mixtures with white. Adding a colour pigment to a mixture
ments, subtractive mixing behaviour also occurs in such mixtures, and leads to a movement of its location in all three dimensions of colour
therefore blue colour pigments combined with gold interference pig- space, changing chroma, colour and lightness.
Figure 6: Metallic colours show a powerful change in intensity Figure 7: The effect of a metallic red (left) is very clear.
depending on the obser vation angle.
Figure 8: Matte finishes are the latest trend, but are still not that Figure 9: Black, white and silver are favourites around the
popular. They can pose difficulties in OEM coatings and refinish- world. Very few bold colours become an OEM finish.
ing repair jobs.
What difficulties pose matte clearcoats for OEM coatings and refinish jobs? The result of a
painting with matte clearcoat depends on components such as the hardener and thinner as well of
application conditions such as booth temperature and humidity. This applies to OEM coatings and
refinishes. In refinishes, there are different grades of matte clearcoats which are caused by different
car models and parts.
How do colour and aluminum pigments influence the interference effect? Colour pigments Werner Rudolf Cramer
affect the overall colour impression. The interference effect is usually reached. Aluminum pigments Freelance
have a direct influence on the interference effect because both have their strongest reflection near consultant and journalist
gloss. You obtain fairly “hard” colours with aluminum pigments and their blends with colour pig- wrcramer@muenster.de
ments, while interference pigments lead to more “soft” blends in ad-mixtures with colour pigments.
In addition to metallic paints, what are other popular effects coatings? Besides metallic col-
ours, interference pigments are often used in combination with colour and aluminum pigments. De-
pending on the area of application, various popularities of interference pigments can be determined.
Currently, golden pigments – aluminum as well as interference pigments – are in the focus. They are
not only useful to create gold-yellow colours, but also helpful to create different colour compositions
Interference pigments with a strong colour effect are singular pig- lar tint: a blue does not become more reddish with a red, but with a
ments, meaning that they do not constitute a colour system of many violet. A yellow becomes more reddish when mixed with an orange. In
components. On the other hand, they can still also be mixed with this case, a red would force the mixture too quickly into the red area;
other coloured and interference pigments. The latter is, however, less and one would not begin with a greenish yellow, but with a reddish
advisable since it is quite likely that the overall final effect is not pre- yellow.
dictable. Transparent interference pigments blend more or less ideally to cre-
ate intermediate colours. Semi-transparent or hiding interference pig-
OBEYING THE MIXING LAWS ments can also be mixed to achieve the desired effect. However, many
attempts and a lot of experience are necessary for successful results.
Automobile finishes and many industrial mixtures are typically blends
of various pigments or pastes. These not only have different colours FINDING AN EXTRAORDINARY COLOUR CREATION
and effects, but also behave differently when mixed. When colour pig-
ments such as yellow and blue are combined to make green, this is The variety of colours and effects is so expansive that selecting or
referred to as subtractive mixing. If, on the other hand, transparent discovering a new colour is hard to do, at first glance. Here are three
interference pigments such pearl yellow and pearl blue are blended suggestions for modern colours relevant to today’s taste:
together, the result is not green, but a white. They mix additively. ąą To create a radiant, plain white, avoid adding pigments in the
It is possible to imagine the different mixing characteristics by using yellow-red-brown area. A little blue does wonders to make a white
two colour filters of yellow and blue as an example: in subtractive mix- turn into a bright white. To create a corresponding whiter-than-
ing these two filters are in sequence, light passes through one, then white effect, use a pure white interference pigment instead of an
the other. The first filter – the yellow one, for example – first filters out interference pigment based on natural mica. These do not appear
all wavelength ranges from the white light except for the yellow range. yellowish at higher aspecular angles.
After that, the blue filter filters out all rays of light except wavelengths ąą A metallic colour may have a slightly glossy effect if fine aluminium
in the blue range. The transmission profile of both filters overlaps in pigments are used. By combining coarse “silver dollar” and fine
the green area of the spectrum so green remains as the resulting “cornflake” pigments, a metallic effect can be “taken to extremes,”
colour of light allowed through both filters. as one might say. Additional interference pigments can enhance
For additive mixing, imagine the filters in parallel, alongside one an- this effect because this type of pigment reflects extremely close to
other: in this case, again, the yellow filter allows all the light rays of the the gloss.
yellow spectral range to pass through and the blue filter allows all the ąą Colour effects that dazzle the onlooker can optimally be created
light rays of the blue spectral range to pass through. Where the light using colour interference pigments. These pigments can more or
from both filters converge, they add up to white again. less be mixed haphazardly together with colour pigments. Applying
To shift the colour of absorbing pigments in a certain direction, one such pigments allows one to control not only the colour effects, but
can conveniently use neighbouring pigments, or pigments with a simi- also their chroma. All in all, there are so many fascinating interfer-
ence and aluminium pigments available that their full potential is
E U R O P E AN CO AT I NGS J O UR N AL 2018
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38 E F F E C T P IG MENT S
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Interference pigments can deliver a wider range of optical ef- visible region, while white becomes a yellow. If the layer thickness
fects than other pigment types, since their angle-dependent of titanium dioxide is further increased, this minimum shifts further
behaviour involves superimposing light waves rather than into the longer wavelengths, which results in a red. The maximum
purely absorbing or reflecting them. Factors affecting the ap- following the minimum in the UV range migrates into the visible
pearance of these pigments are discussed and the use of dif- range, while the maximum in the long wavelength range travels into
fraction pigments is considered. the invisible infrared range.
With higher layer thickness the blue maximum shifts into the green
involve superimposed light waves that are shifted together due to ORIENTATION, ANGULAR AND SUBSTRATE EFFECTS
reflections and refractions. This causes strengthening or weakening
of the resulting light waves. Various factors, such as the structure Interference pigments have been used in automotive paints since the
of the pigment, its application and the lighting, make for optimum mid-Eighties. Since that time, there has been increasing interest in
conditions. quantifying their colours and effects. They are applied as so-called
Pigments manufactured with wet chemistry generally have a carrier basecoats, which are then sealed with a clear coat. These basecoats
platelet of natural mica, silicon dioxide or aluminium oxide. High re- have a layer thickness of 10-15 µm; the interference pigments are in
fractive index metal oxides such as titanium dioxide or iron oxide are the range of 5-100 µm long and about 0.05 µm thick. Due to their
applied to this carrier platelet. Depending on the layer thicknesses size, the pigments can only be situated as platelets lying more or less
of the oxide, these pigments change their colour from white, yel- parallel to the coating layer in the paint. This orientation is enhanced
low, red or blue to green. This unusual colour shift results from the by additives during the drying process of the basecoat. The theoretical
fact that the maxima - and also the minima - move to longer wave- calculation of the orientation of the pigments on the basis of measur-
lengths. For yellow, the minimum shifts from the UV range into the ing angles must therefore be studied.
E U R O P E AN CO AT I NGS J O UR N AL 2018
EFFE C T P I G MEN T S 39
Patterns in the electron microscope show a relatively flat orientation; Figure 1: Up to 25° aspecular, both the reflection and transmis-
in the light microscope, the change in the illumination angle shows sion colours are obser ved when the transparent pigment is
that the colours observed almost always arise from the type of pig- applied over a white background. The transmission colour is
ment and not from differently oriented pigments. Most interference absorbed over a black background.
pigments are transparent, which is why the colour of the background
or environment also plays a role. Since the incident light is divided
into the reflection colour and complementary transmission colour,
the change can be observed well on a white background.
With measurements close to the gloss angle, the reflection colour is
detected and the transmission colour is removed from the gloss. This
transmission colour is produced on the opposite side of the pigment,
reflected by the white background. If angular differences are meas-
ured aspecular with an illumination angle of 45°, the reflection colour
in the range can be detected up to about 20°. Between 20° and 30°
aspecular there is a so-called transition range.
With large aspecular angles, the complementary transmission colour
that is reflected from the white background is measured. A black back-
ground absorbs the transmission colour. Coloured substrates as well
as admixtures of colour pigments show similar patterns (see Figure 1).
affected by the colour pigments, as they also reflect close to the gloss. ALL THE COLOURS OF THE RAINBOW IN ONE PIGMENT
But measurements at a constant illumination angle and varied angu-
lar differences to each gloss angle are not limited to an illumination In addition to the known interference pigments, which are prepared
angle of 45°. In principle, 45° illumination has simply emerged as the by wet chemistry or in a high vacuum, there are special types of inter-
most suitable for characterisation. ference pigments. Their optical response corresponds to reflections
The combination of these measurements results in the so-called ‘as- on a diffraction grid. The incident light is spectrally fragmented, from
pecular line’; the combination of the measured values at a constant blue-violet over blue, green, yellow to red.
differential angle is referred to as the ‘interference line’. Again, the Unlike ‘normal’ interference pigments, which show a colour gradient
indication of the aspecular angle is necessary because there may be depending on the angle of illumination, a complete rainbow is always
multiple connection lines. At an aspecular angle equal to or greater evident in the polychromatic pigments. Their colours can be meas-
than 30°, the transmission colours are measured with transparent in- ured individually - the eye has a greater observation and detection
terference pigments on a white background. range than a measuring instrument and sees a complete rainbow.
Figure 2: At 25° aspecular, no maximum is detectable in the vis- Figure 3: The colours of the rainbow flow clockwise in the a*b*
ible region. When the aspecular angle is increased, the maxi- diagram. Modern colour instruments detect the rainbow at 45°
mum shifts into the visible region and moves away from it again and 75° from gloss.
at or above 65° aspecular.
Figure 4: Different pigment concentrations reflect the rainbow in Figure 5: The rainbow can be obser ved on both sides of the
various strengths. gloss angle (top); an interference pigment that shows its reflec-
tion colour at up to 25° aspecular is placed in this ‘gap’ (bottom).
E U R O P E AN CO AT I NGS J O UR N AL 2018
EFFE C T P I G MEN T S 41
The range of the rainbow lies in an angular range of 20 to 30 degrees combination are limited. Admixtures of black are ideal, because in this
depending on the angle of illumination. With flat 65° illumination the case the rainbow colours are not affected. And because of the greater
rainbow starts at about 45° and extends to about 75° aspecular. With contrast, the rainbow effect is more intense. When such pigments are
steeper illumination at 45°, the range shifts from 35° to 65°. These are used, the full rainbow is always seen; there are no pigments which
the limits for the colours of the first order. The colours of the second show only a half or a quarter of the rainbow. In this case the effect
order follow in this range; they are measurable, but barely visible. must be controlled with admixtures with other pigments (Figure 4).
From the reflectance curves it is clear that the reflections and their ąą The rainbow starts at about 35°-45° aspecular; interfer-
maxima shift from the UV range into the visible range as the aspecular ence pigments show – depending on the type – their reflec-
angle increases in relation to the gloss angle. With further increases in tion colour up to about 25° aspecular. In this respect, two
the aspecular angle they leave the visible spectral range, moving into colour ranges can be used by mixing both types of pigment.
the infrared region, while maxima of the 2nd order move from the UV ąą Looking at a spray-out of a polychromatic pigment from above,
into the visible range (see Figures 2 and 3). one can detect the ‘gap’ between the two rainbows on either side
The interference laws - the shift of the reflections to shorter wave- of the angle of observation. An interference pigment can be in-
lengths with flatter illumination - also apply to these pigments. Presum- corporated that so to speak fills this ‘gap’. Such mixtures can be
ing aspecular geometry – for example, at 55° – and if the reflections of created in various ways, where the selected colour of the interfer-
different illumination angles have this constant differential angle, the ence pigment may also affect the rainbow (see Figures 5, 6 and 7).
shift of the maxima to shorter wavelengths with flatter angles of illumi- ąą Admixtures of colour pigments influence the colour impres-
nation can be clearly seen. Thus, in these pigments, the optical reflec- sion over the entire illumination and observation range. De-
tion laws apply both on the diffraction grid and in terms of interference. pending on the shade of the colour pigment, the rainbow is
affected and may no longer be recognisable in its entirety.
MODIFYING THE APPEARANCE OF EFFECT PIGMENTS ąą Like the colours of the interference pigments, the rainbow ap-
pears intense only in a narrow angular range. Despite their rela-
Interference pigments have typical reflection colours with a small or tively lower intensity close to the gloss, colour pigments produce
large colour gradient. They are found in many car colours in combina- a stronger overall colour impression. As such, they often have
tion with colour and aluminium pigments. In order to create a blue a strong influence on the rainbow, which can only demonstrate
colour effect, for example, a white interference pigment can be mixed a strong presence in combination with dark colour pigments.
with a blue colour pigment. Instead of the white interference pigment
a blue or green may also be used. The possibilities for combinations DETAILED EXAMPLE OF MIXING DIFFERENT PIGMENT TYPES
here are almost infinite.
In the case of polychromatic pigments, the combinations are made Examples of mixtures of a pigment of this rainbow type called “MultiFlect”
rather differently: admixtures of colour and aluminium pigments in- with blue colour pigment and blue interference pigment show the respec-
fluence the polychromatic rainbow effect. Polychromatic pigments tive influences in the geometrics areas: near the gloss at 15° aspecular - in
are inherently silver-white to silver-grey from their base colour. The this case with an illumination of 45° - the rainbow pigment reflects with
rainbow effect occurs most clearly with these neutral pigments. Ad- a slight valley in the green range; away from the gloss angle - in this case
mixtures of colour pigments suppress the rainbow partially or even at 50° aspecular - the green of the rainbow can be seen. By adding a
completely, so that in principle some preliminary considerations are blue pigment, the 45° aspectral reflectance curve shifts to higher values,
necessary. above all in the blue spectral range; close to the gloss the 15° aspectral
ąą The complete rainbow exists only in polychromatic pigments alone or reflectance curve is slightly increased in the blue and red range. The differ-
with minimal admixtures. To retain the rainbow, the possibilities for ences in mixtures with blue interference pigment are even more distinct.
Figure 6: The initial values of the rainbow are shifted toward the Figure 7: The reflectance cur ves also show the combination of
admixed interference pigment. As anticipated, the influence of the the optical properties of both pigments: the mixture shows colour
polychromatic pigment predominates at or above 35° aspecular. reflections both close to the gloss as well as away from it.
“Individuality is in the
foreground.“
Can the optical properties of mixing diverse pigment types easily be obtained? There are
two main points that help facilitate the introduction into the mixing behaviour of different kinds of
pigments: firstly, it should be noted that two different mixing behaviours encounter each other, namely
the subtractive and additive mixing. Secondly, it is always worth looking at the reflectance curves, which
show the real optical behaviour of effect pigments.
Their reflections close to the gloss affect the resulting reflectance curve Certainly the use of this type of pigment is particularly limited in the
with a strong maximum at 15° aspecular. The reflections of this pigment automotive sector, but it can be used for attractive concepts in special
shift, so to speak, between the rainbow reflections of the special effect pig- series. This requires detailed knowledge of the geometric constraints
ment. This optical behaviour can also be observed visually: left and right of the colours. The difficulty in developing this knowledge stems from
of the gloss the rainbows can be seen as well as the blue interference the fact that the geometries of the rainbow are only partially recorded
colour between them. Interference pigments in other colours provide the by the measuring geometries of most spectrophotometers.
same results, where their reflection colour provides a more or less strong
contrast to the rainbow. Plotting the a*b* values shows a shift of the
rainbow circle into the blue area with the addition of a blue colour pig- LITERATURE
ment. The addition of a blue interference pigment causes the unfold-
ing of this circle in the blue region. Experiments with different colour [1] Maile F.J., Martins A.C., A new Generation of Aluminum-based Pigments,
pigments and interference pigments show similar colour responses. Paper 137, ABRAFATI Coatings Congress, São Paulo, Brazil, Oct. 2015.
[2] Maile F.J., Pfaff G., Reynders P., Prog. Org. Coat., 2005, Vol. 54 pp150–
MAKING MOST EFFECTIVE USE OF POLYCHROMATIC PIGMENTS 163.
[3] Loewen E.G., Popov E., Diffraction Gratings and Applications, Marcel Dek-
As with all effect pigments, the use of polychromatic pigments re- ker, Inc. N.Y., Basel, 1997.
quires an intensive examination of illumination and observation [4] Cramer W.R., Visual & instrumental geometries in colour matching, CCJ,
geometries, if useful and interesting colour creations are to be pro- 2012, No. 7.
duced. Although these pigments ‘only’ show a rainbow, admixing in- [5] Cramer W.R., Reflections on the right angle, ECJ, 2012, No. 4.
terference pigments in particular can create effects that exploit the
optical properties of both types of pigment.
In addition, colour pigments can be used, which can have a crucial
effect on the overall colour across all geometries. Starting from the
polychromatic pigment, different approaches for colour creations can
be implemented.
E U R O P E AN CO AT I NGS J O UR N AL 2018
W O R LD O F C O L O UR 43
A LOOK BACK
Airbus, the largest European
plane manufacturer, was
founded in 1970 in Tou-
louse, France. Two years la-
ter, their first model called
Airbus A300 was released.
Planes of this family were
sold until 2007.
A SPARKLING FUTURE
FOR EFFECT PIGMENTS
Advances in technology will open up a wealth of opportunities. By Carsten Handrosch, Carsten Plüg, Merck KGaA
There is great potential in the coatings industry for high-sparkle, sparkling pigments based on alumina, highly chromatic, opaque pig-
highly reflective and photonic pigments. While research has pro- ments based on aluminium, and photonic crystals. These three class-
duced exciting results, challenges lie in their industrial applica- es of pigments are current focus fields of research in both industry
tion before these types of pigments become commercially viable. and academia. They have good potential to create further unique and
new effects in coatings.
try to mimic these effects by using combinations of materials with dif- Since the early 2000s, effect pigments based on alumina flakes have
ferent refractive indices. enjoyed attention particularly in automotive coatings. The flat nature
In particular, effect pigments that create interference effects through of mono-crystalline alumina, particularly in the corundum crystal form,
a layer structure of high and low refractive materials have gained allows the formation of well-defined effect pigments (Figure 1) when
significant importance in applications such as automotive coatings. coated with highly refractive oxides such as titania and iron oxide. The
These materials can create an illusion of depth due to their parallel resulting alumina-based pigments provide an extremely even and paral-
arrangement in the coating and semitransparent appearance. The op- lel orientation in the coating process, e.g. by bell spraying. The resulting
tics, physics and functional properties of these fascinating materials coatings reveal an outstanding effect, referred to as living sparkle [4].
have been reviewed in various papers [2]. The impression of the depth of the coating is created through individual
Typical decorative applications of these effect pigments include coat- sparkle points. This living sparkle is a complex phenomenon. There is
ings, plastics, printings and ceramics, whereas functional applications evidence that the flatness of the individual particle predominantly de-
include security, heat management, laser marking, and thermal or fines the area of sparkle in the observer’s eyes [5]. Alumina as a single
electrical conductivity applications. The application of these pigments crystalline substrate is almost perfectly flat. In contrast, glass as a sub-
in coatings has been described in detail [3]. strate has some tilt in the particles that cannot be avoided during the
This paper therefore focuses on the impact of recent developments manufacturing process of flakes made from glass melt [6].
in effect pigments on coatings in general, and automotive coatings Particles of alumina-based pigments range in thickness from 300-1200
in particular. By discussing examples of three different technologies, nm, depending on the colour, and are often provided in a narrow particle
their potential for coating applications shall be demonstrated: high size distribution of 5-30 µm (this applies to 80% of particles). These di-
E U R O P E AN CO AT I NGS J O UR N AL 2018
EFFE C T P I G ME N T S 45
Special Effect Pigments Specific colour, luster and colour flop due to interference
(Pearl Luster Pigments) (reflection and refraction) of light
Photonic Crystals Specifc colour and colour flop due to multiple interferences
of light
oxide layers of varying thicknesses. The thickness of the layer defines aqueous environment, very dense and homogeneous layers of iron
the resulting colour [9]. oxide can form (Figure 5, Figure 6). This new technology leads to even
The resulting pigments provide attractive shades and can be easily more chromatic pigments compared with those obtained by the dry
combined with transparent organic pigments to achieve reflective and coating process. The very high chroma of the aqueous-coated pig-
brilliant coatings. ments allow new styling options (Figure 7). The potential of this pro-
Iron-oxide coated alumina pigments are offered as pastes, e.g. in cess has still not been fully explored. Research is currently focused on
Naphta. Pigment pastes obtained by dry deposition of iron oxide have providing new highly chromatic pigments with outstanding reflectivity
a limited shelf life and when used in waterborne systems require fur- and a high level of opacity.
ther stabilisation due to the undesired formation of hydrogen[10]. Recently, the use of ultra-thin aluminium platelets as obtained by
Recent developments of such pigments employ a wet-coating technol- physical vapour deposition was suggested for iron oxide-coated pig-
ogy, which is standard for depositing metal-oxide layers on platelet sub- ments [13]. It remains to be seen if these materials can outperform
strates [2a]. This technology requires the use of entirely inert aluminium existing pigments. Until now, there has been little interest in titania-
flakes to prevent hydrogen forming in an aqueous environment. This coated aluminium pigments due to their weak interference colour.
passivation is achieved using a new technology [11, 12] and uses phos- In summary, iron oxide-coated aluminium pigments continue to enjoy
phates as its key ingredients. The new passivation technology provides a high level of research. It is highly possible that new pigments com-
robust protection and allows layers to be added with good bonding. bining high chroma, reflectivity and opacity will be commercialised in
As metal oxide coating of alumina particles can be performed in an the near future.
Figure 2: Microscopic image of high sparkle dark-silver pigment. Figure 3: Electron micrograph image of alumina flakes coated
with multiple layers of TiO 2 (rutile), SnO 2 and SiO 2.
Figure 4: Colour travel (in a*b* plain, aspecular line: 45°/- Figure 5: Electron micrograph image of homogeneous iron-oxide
30°/+15°, 45°/-20°/+25°, 45°/0°/+45°, 45°/30°/+75°, coated aluminium platelets.
45°/65°/+110°; PMC =18%, black background, angles marked
according to DIN 6175-2) of new alumina blue pigment in
comparison to mica and existing alumina-based blue pigments
indicates high chroma at neutral blue shade.
10
Face
5
Full shade over black
0
0 -50 -100
-5
-10
-15
b*
High performance Mica Blue New alumina blue
Existing Alumina Blue Mica Rutile Blue Pearl
E U R O P E AN CO AT I NGS J O UR N AL 2018
EFFE C T P I G MEN T S 47
STRUCTURAL COLORS - ARTIFICIAL OPAL EFFECTS A similar approach uses organic beads with very narrow particle size
distribution, typically composed of a hard, rigid polystyrene (PS) core
Effect pigments with a photonic effect (“photonic effect pigments”) are and a soft, curable polyacrylate (PA) shell. The arranged photonic crys-
a class of their own and not related to the pigment types discussed tal can be cured radically to obtain a polymeric material that can be
earlier. Colour is obtained through microscopically structured surfac- cut into particles. Curing conditions and particle size determine the
es that exhibit periodic variations in dielectric constant in up to three resulting colour (Figure 8) [19]. This technology enables brilliant colour
dimensions. The period of the differences has to follow the order of travel effects.
the wavelength of visible light to allow colour-creation through inter- The distance between the PS particles determines the resulting col-
ference effects. We observe this interference effect as vivid iridescent our, which means these pigments are very sensitive to process condi-
colours. As these structures resemble macroscopic crystals, the terms tions, preventing commercialisation for now.
“photonic crystals” and “structural colours” are used [14]. Although the concept of photonic pigments offers attractive options
The interference colours in birds feathers and the wings of butterflies for new colour effects and has been studied for more than 15 years,
and beetles are created by periodical structures of channels, gratings, obstacles such as colour reproducibility are still a challenge. However,
holes or fibres consisting mostly of chitin or proteins. It was found new methodologies being explored might offer a solution soon [20].
recently that the colour change of chameleons is based on photonic
structures too. The ability of specialised skin cells to change the form EXCITING OPORTUNITIES - SOME DEPEND ON ADVANCES IN
and dimension of their photonic structure enables the body to mimic TECHNOLOGY
its background [15].
Researchers have been particularly interested in trying to copy the Focus areas for research for new effect pigments are high-sparkle pig-
“fire” of opal, which is based on very regular-sized silica beads with a ments, highly reflective gold-orange-red pigments and photonic pig-
diameter of 150–300 nm +/- 5% [16]. Attempts to mimic the photonic ments.
effect of opal started with synthesising monodisperse silica particles The area of decorative photonic systems is still in the early stages of
of 150-300 nm that arranged themselves into photonic crystals from becoming an industrially viable technology. The specified application
alcoholic suspension [17]. This principle has been extended to poly- hurdles will have to be overcome first, before these attractive prod-
mer-bound matrices in order to freeze the high orientation [18]. ucts are ready to enter the market.
Figure 6: Electron micrograph image of a single damaged particle Figure 7: Examples of lacquer panels with a golden, orange and
illustrating the homogeneous iron-oxide layer (white micro-struc- red aluminium-based pigment obtained by aqueous metal-oxide
tured area) and the dense passivation layer (dark grey area). coating.
Figure 8: Angle dependent colour of t wo polymer-opals according to ref. [19a]: top left image - obser vation at flat angle of view; top
right image - obser vation at medium angle of view; bottom image - obser vation at steep angle of view.
E U R O P E AN CO AT I NGS J O UR N AL 2018
EFFE C T P I G MEN T S 49
TIME FOR
SPECIAL EFFECTS!
www.european-coatings.com/shop
Gerhard Pfaff
SPECIAL EFFECT PIGMENTS
A complete introduction to the world of
special effect pigments: get a profound
knowledge of the properties, manufacturing
processes, and specific applications of special
effect pigments in coatings, plastics, printing
inks, and cosmetics and learn more about
related colorimetry and quality assurance
methods.
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EUROPEAN
C OATINGS library
Vincentz Network · P.O. Box 6247 · 30062 Hannover · Germany · T +49 511 9910-033 · info@european-coatings.com
E U R OP E AN COAT I NGS JO UR N A L 2018
50 E F F E C T P IG MENT S
SPECIAL EFFECTS
Development of new effect pigments that add more than just colour to paint. By Raimund Schmid (published in ECJ
05/2014).
The development activities of pigment producers are driven Figure 1: Unground synthetic mica is cleaner compared to natu-
by the market needs of the coatings industries. In the field ral mica
of effect pigments the main driver for ongoing innovation is
the desire of industrial paint designers to get the best tools
for exciting colour styling. Innovation in pearl pigments based
on synthetic mica, as well as iron oxide-coated silver dollars,
provide the basis for visually striking whites and other exciting
colours for paints.
E U R O P E AN CO AT I NGS J O UR N AL 2018
EFFE C T P I G MEN T S 51
‘vintage look’ is sometimes used to enhance the value of goods. In the 1. New substrates / effect pigments via:
industrial paint industry, the equivalent effect is achieved by coatings Crystallisation
with crazing, patina or rusty appearances. As an alternative to natural mica (muscovite), synthetic mica (fluoro-
Also of interest to designers are changing colours influenced by view- phlogopite) has been developed as a substrate for pearl pigments
ing or illumination angles, temperature, sound, electric or magnetic with higher transparency [1]. Alternatively, alumina flakes grown us-
fields. In the coatings area, so-called goniochromatic colours and ther- ing a melt-and-crystallisation process provide substrates for attractive
mochromic colours can be realised. sparkling pigments [2].
Only an attractive colour that can be applied with ease is acceptable Web technologies
for demanding industries like the automotive sector. The main re- The coating of a moving web with silica layers, aluminium films or mul-
quests from the technical side of paint manufacturing are for effect tilayer systems, followed by the breaking of the film into flake form,
pigments with the following properties: yields interesting substrates for pigments:
Improved hiding of pigments Silica flakes provide substrates for subsequent oxide coatings in order
Narrower particle size distributions to form goniochromatic colours.
Better mechanical stability in circulation lines Similarly prepared aluminium films (thin Al-flakes) yield the so called
Low abrasiveness vacuum metalised pigments [3-5], which provide liquid metal effects.
Better gloss and distinctness of image (DOI) The first patented, web produced multilayer pigments, consisting of
Improved weather fastness semi-transparent Al-films, transparent SiO2-films and opaque Al-layers,
Better humidity resistance provided effect pigments with strong interference colours [6]. They
Consistency of quality were, however, never produced at commercial scale. In security inks
Colouristic equivalence in waterborne and multilayer pigments like Cr/MgF2/Al/MgF2/Cr are in use [7].
solvent-borne systems Improved processing of glass
A final, important driving force for new developments is Recent developments in glass processing allowed access to borosili-
the ‘green’ image of goods and the resulting requests for cate glass flakes with flake thicknesses < 1µm. Instead of breaking
banning of heavy metals, the reduction of volatile organic compounds glass bubbles, as previously used, the thin glass flakes are made by
(VOCs) and for sustainable production processes. using a spinning cup into which molten glass is injected [8].
TECHNOLOGY TRENDS IN 2. Better colouristic properties like higher chroma, higher lightness,
MANUFACTURING EFFECT PIGMENTS goniochromaticity, sparkle, liquid metal, higher transparency can be
achieved by the use of:
The above-described requirements of the paint industry are driving thinner flakes with narrower particle size distributions
the development of new effect pigments. The main development ac- more uniform pigment shapes
tivities fall into three groups: smoother flake surfaces
Figure 3: Colouristic performance of newly developed sparkling Table 1: Liquid metal factor of Silk White S1303V in
pigments vs. state of the art comparison to the state of the art (Test system: 90:10 black
reduction in a solventborne basecoat / clearcoat)
Fi G LMF
Figure 4: Iron oxide-coated aluminum flakes of the cornflake Figure 5: Iron oxide-coated aluminium flakes of the silver dollar-
type (Paliocrom Orange) type (Paliocrom Brilliant Orange)
E U R O P E AN CO AT I NGS J O UR N AL 2018
EFFE C T P I G ME N T S 53
use of multilayer systems (chemical synthesis [9] or Figure 6: Colouristic performance of iron oxide-coated silver dol-
physical vapour deposition [7]) lars vs. cornflake types in orange / red metallic. Full shade and
For luxury items, the shimmering and noble gloss of pearl-based pig-
ments is very popular in coatings. Conventional pearl pigments based
on titanium dioxide-coated natural mica flakes typically show a yellow-
ish tint due to iron impurities in the natural mica. Brand owners usu-
ally wish to avoid any yellowish appearance in white colours, favouring
the more bluish ‘ice’ whites.
A recently launched new series of clean, slightly bluish pearl pigments
based on synthetic mica is now available. In contrast to natural micas,
the synthetic mica substrates are absolutely transparent and free of
coloured impurities, as shown in Figure 1. These pearl pigments allow
the formulation of neutral to slightly bluish white pearl shades. Opti-
mised tricoat formulations allow for whiter whites at all observation
angles. In combination with carbon black, cool greys and noble blacks,
(gunmetal shades) with a slightly bluish appearance, are possible.
Depending on the particle size distribution, silky, brilliant or even spar-
kling effects are possible with these new pearl pigments. The ‘silk’ white
is a bluish pearl pigment with a smooth, velvet appearance. Despite
the small particle size of 12 µm the lightness flop is pronounced. The
‘frost’ white pigment is a bluish pearl with brilliant appearance. With
a medium particle size of ~19 µm the ‘frost’ white provides a good Figure 7: Sparkling performance of iron oxide coated silver dol-
balance between lightness flop, sparkle and feasibility in demanding lars vs. cornflake types and blends of both types
applications like automotive basecoats. The ‘crystal’ white pigment is
designed for strong sparkle effects not only in gloss angle, but also at
steeper viewing angles. The typical application for these 30 µm large,
sparkling pigments is industrial coatings where a good compromise
between strong sparkle and technical feasibility is requested. Bigger
flakes usually provide stronger effects, however, in some applications
technical feasibility is lower.
Flop index (Fi) and liquid metal factor (LMF) are tools to characterise
modern pearl shades. A well-established formula to quantify angle de-
pendent lightness with a number called the ‘Flop index’ was published
in 1992 by DuPont [10].
Fi = 2.69•(L*15°-L*110°)1.11/(L*45°)0.86
The ‘glacier silk’ white pigment is a powerful tool if smooth pearl appear-
ance in combination with a pronounced lightness of flop is requested
by paint designers. In the face angle high lightness is required, while in
the down-flop, the maximum dark appearance is the target.
In diffuse light usually the smoothest appearance is required in the
colour styling. In terms of colour measurement a low value for graini-
ness (G) is in that case the target. The surface of a liquid metal like
mercury for example has extremely low graininess in diffuse light and
a strong lightness of flop in directed light. The LMF quantifies this ef-
fect:
LMF = Fi/G
The higher the flop index and the lower the graininess, the better the
liquid metal character of a styling will be. It is important to compare
only LMF values of pigments with similar particle sizes. If effect pig- cently launched innovative pigments are bluish pearl pigments based
ments with strongly different particle sizes (e.g. d50 = 12 µm with d50 = on synthetic mica and iron oxide coated silver dollars.
25 µm) are compared, the LMF values become meaningless.
The ‘glacier silk’ white was designed as a bluish pearl pigment with an
optimised LMF (see Table 1). Part 1 of this t wo-part paper highlights the requirements of the coat-
Typical applications for fine-sized pearl pigments are the so called ings industry, technology trends in effect pigment synthesis and effect
white tricoat systems, where a hiding white solid shade basecoat is pigment innovations based on synthetic mica and iron oxide coated
over-coated with a second layer containing the pearl pigment fol- aluminium.
lowed by a conventional clearcoat, as shown in Figure 2.
Depending on the design target, bluish white shades (blue line) or yel- Part 2 with more new effect pigments will be published in the October
lowish white pearl shades (green line) are possible. Blends of natural 2014 issue.
mica based pearls and synthetic mica based pearls give access to a
range of shades in between (eg. red line).
Coarser types of pearl pigments are used if an eye-catching sparkling REFERENCES
appearance is required in a styling. Usually in the face angle such
paints are showing strong sparkling effects. At steeper angles the [1] T eiqing L., Zongxi L., Wenyuan Z., Guangqing Y., Preparation of syn-
sparkle effect is usually weaker. Especially for bigger surfaces it can thetic mica pearly luster pigment, Journal of synthetic crystals, 1990,
be a disadvantage to have good sparkle only in the face angle view Vol. 19, pp 166-171
and low sparkle effect at all other angles. A recently introduced new [2] T eaney S., Pfaff G., Nitta K., New effect pigments using innovative
sparkling pigment based on synthetic mica – glacier crystal white – substrates, Eur. Coat. J., 1999, Vol. 4, pp 90-96
offers high sparkle intensity also at higher angles, as demonstrated [3] S eubert J., Fetz A., PVD aluminium pigments: Superior brilliance
in Figure 3. for coatings & graphic arts, Paint & Coatings Industry, June 2000,
The sparkling area value (S_a) is related to the number of light re- available online
flections for a given surface area, while the sparkling intensity (S_i) is [4] U S Patent 3,949,139
quantifying how intense the corresponding light reflections are. For [5] U S Patent 4,321,087
normal coarse micas the red line is characteristic. In 15° illumination [6] US Patent 3,438,796
angle both values Sa and Si are high. At higher illumination angles [7] US Patent 5,135,812
both values are lower. The ‘crystal’ white pigment behaves differently: [8] EP 0289240
higher illumination angles, which correspond to down-flop show high- [9] S chmid R., Mronga N., Radtke V., Seeger O., Luster pigments with
er sparkling intensity. This makes the new pigment interesting for ap- colour variable properties, Eur. Coat. J., 1997, Vol. 7, pp 702-705
plications where strong sparkle intensity at all angles is required, for [10] R odriguez A., JOCCA, 1992, Vol. 4, pp 150-153
example in decorative wall coatings or in powder coatings for facade [11] O stertag W., Mronga N., Hauser W., Eisenoxidbeschichtete Alu
elements. miniumpigmente, Farbe und Lack, 1987, pp 973-976
[12] E P 033457
IRON OXIDE COATED SILVER DOLLARS WITH HIGH BRILLIANCY [13] E P 338428
[14] M ronga N., Radtke V., Baumann B., Paliocrom lustre pigments – their
More than 20 years ago iron oxide-coated aluminium flakes of the production, properties and application, 3rd Nürnberg Congress
cornflake-type were introduced to the coatings market, as shown in 1995, paper 18
Figure 4. Depending on the thickness of the iron oxide film on the [15] U S 7,387,669W
aluminium surface golden, orange and red interference colours are
possible [11-13]. The unique combination of high chroma, gloss and
hiding provided by iron oxide coated aluminium flakes allowed hiding
automotive effect shades with a so far, unmatched, brilliancy [14].
Recently iron oxide-coated aluminium flakes of the silver dollar type
were introduced in order to further improve the performance of auto-
motive coatings [15]. The perfectly light reflecting surfaces of the iron
oxide coated silver dollar substrates further boost the brilliancy of red
metallic, as shown in Figure 5.
The colouristic potential of iron oxide coated aluminium flakes can be
fully exploited by combining them with transparent perylene- or DPP-
pigments (diketopyrrolo-pyrole), as shown in Figure 6.
Iron oxide-coated silver dollars typically show stronger sparkle effects
than corresponding cornflake types. Cornflake-substrates are thinner
and for that reason their appearance is smoother. Having both pig-
ment types available in the same colour allows paint designers to eas-
ily adjust the desired degree of sparkle, like in Figure 7.
SUMMARY
E U R O P E AN CO AT I NGS J O UR N AL 2018
W O R LD O F C O L O UR 55
SETTING SAIL
The Queen Mary 2 is one of
the largest ocean liners and
was christened in 2004. The
ship, which houses 1.310 ca-
bins, has an overall lenght of
345.03 m and moves with a
maximum speed of 30 knots
(56 km/h).
Today patina effect constitutes an important tool in industrial The green patina that forms naturally on copper and bronze, usually
design. Apart from the aesthetic appearance and practical pro- consists of a mixture of copper chlorides, sulphides and carbonates
tection of patination, an object is perceived as having greater and can form on pure copper objects as well as on copper-containing
value if it looks as if it has aged slowly and well. In the interior alloys, such as bronze or brass. Such a patina layer takes many years
design industry there is a demand for objects that appear to to develop under natural weathering conditions.
have a long history or which represent long time periods. Dec- Rusty surfaces also belong to the group of patinated surfaces. For
orative coatings providing patina effect, antique appearance example in construction a special type of weathered steel is used,
or a weathered look are becoming increasingly popular. purely for exterior applications. This decorative effect results from
an iron oxide layer formed by a corrosion process which does not
affect the tensile strength of the steel itself.
The second half of this t wo-part paper highlights new special effect pig- For industrial design the time to produce the patinated effect is often
ments for antique effects and patinated surfaces in decorative coatings the limiting factor. Usually, a designer cannot wait the necessary time
and also discusses new interference pigments that exceed the currently for the effect to form. Generally they would like to align shape and
achievable chroma limits. Part 1 of this paper was published in the May colour in a short time period. So-called ‘applied patina’ is of higher
edition of European Coatings J OURN AL [1]. industrial importance, describing:
Use of chemicals (chlorides, sulfides, acids) to speed up the patination
W hen metals are exposed to air and humidity over a long time they
acquire the so-called antique or patina look, which is related to
changes in surface texture, haptic behavior and colour. In colouristical
process. The disadvantage of all these chemical approaches to modify
or patinate surfaces is that they require the handling of chemicals,
which are inconvenient or even dangerous and can also damage the
terms patina or patination can be described as a reduction in gloss and structural integrity of the article itself.
an inhomogeneous colouristic appearance. Haptic properties and sur- If you consider coatings, which provide the desired patina appear-
face texture also change, because the patina layers might show a dif- ance, spray application or brushin techniques are state-of-the-art.
ferent porosity and heat conductivity compared to the original surface. They allow a higher degree of control both for the appearance of
The chemical process by which patina is formed takes place over a long the effect and the standardisation of the colour.
period of time. This type of patina is called ‘acquired patina’, such as: Applied patina colours based on pigments which provide silver and
E U R O P E AN CO AT I NGS J O UR N AL 2018
EFFE C T P I G MEN T S 57
Figure 1: Left side: Concrete plates with plaster and the new
type of pigment coating on top; hidden surface structure. Right
RESULTS AT A GLANCE side: Concrete plates with plaster and conventional coating
based on iron oxide-coated mica; clearly visible structure
űű This paper follows the first half that was published in the
May edition of the European Coatings Journal, which discussed
the requirements of the coatings industry, technology trends in
effect pigment synthesis and effect pigment innovations based
on titanium dioxide coated synthetic mica and iron oxide coated
aluminum.
A new series of effect pigments unify the following features in one Figure 3: Imitation of a rusty steel surface. Glossy, gunmetal-
pigment: type coating based on new pigment techniques and carbon
ąą typical rust colours (yellow, bronze, copper, russet) black, overbrushed with colours based on the advanced pig-
ąą matting properties providing in coatings the tactile sensation of ments discussed in the paper
rust
ąą soft sparkling effect
The basis of this series of pigments is special glass flakes which are
coated with thin films of titanium and iron oxide. By increasing the
thickness of the iron oxide layers the colours gold, bronze, copper
and russet are possible in a similar way to iron oxide coated micas.
However mica/iron oxide-based coatings show high gloss and light-
ness, while in interior design, especially when coating larger areas, the
opposite effect is required. In other words, walls with a strong light
reflective behaviour are not perceived as ‘cosy, relaxing or laid back
enough’, such as one would desire for a living room.
Figure 1 shows the difference between conventional iron oxide-coated
micas (right hand side) and the new type of effect pigment with matte
and soft sparkle appearance (left hand side).
All the samples shown in Figure 1 use the same concrete substrate,
to which a structured plaster has been applied. It can be clearly seen
that the mica-based wall coating reveals the surface structure of the highly refracting metal oxides like titanium dioxide. There is an ongoing
substrate, while with the left hand side coatings, the structure is much demand for improvements in chromaticity for such pigments. Recent
more subdued. This property enhances the robustness of the applica- R&D activities yielded higher chromaticity by optimising the particle size-
tion process, as the wall paint based on such effect pigments is more and thickness distributions. In combination with an optimised pigment
forgiving of application mistakes, while paints based on iron oxide- design the access to so far unreachable levels of chromaticity is now
coated micas show lightness differences caused by surface structures possible. Figure 4 shows chroma and hue graphs for various blue shade
or irregular brush strokes. interference pigments comparing state-of-the-art products from ap-
For simulated rusty surfaces several paints with different colours have proximately ten years ago with the latest and best performing genera-
to be combined side by side. The best and most economical way is to tion of interference pigments.
apply the coating in two steps, first by applying a base colour and then The stronger the performance of the interference pigment in terms
brushing or stippling on top 2–3 other yellow to red shades containing of chroma, the more vivid the colour that can be realised. This is
the new type of effect pigment, as shown in Figure 2. achieved in the blue colour area by combining TiO2-coated micas with
Sometimes a metal surface with the first onset of rust has to be imitated. transparent phthalo- or indanthrone blues.
In such cases metallic finishes based on aluminium flakes or pearl pig- In addition to the design target for ‘maximum chroma’ the high poten-
ments in combination with carbon black are used as a first coating. After tial chroma of the latest range can be used in existing colour shades
drying, ’overbrushing’ with a paint containing the new type of effect pig- to formulate better hiding basecoats which allow the use of lower film
ment coating can be used to create this early rusting effect. weights on application to achieve the same opacity. If, for example,
Figure 3 shows such an effect, by using as a base, a glossy, silver blue in a black reduction based on a state-of-the-art blue interference pig-
metallic shade, based on a bluish pearl synthetic mica pigment/carbon ment, the blue interference pigment is replaced by the new interfer-
black combination described in part one of the present publication [1]. ence pigments, more carbon black can be used to achieve the same
level of chroma. This strongly improves hiding and as a result thinner
NEW MICA-BASED INTERFERENCE PIGMENTS basecoats can be applied, as shown in Figure 5. The resulting lower
ACHIEVE OUTSTANDING CHROMA lightness values resulting from the higher content of P.B.7 can be
corrected by adding small amounts of a fine aluminum flake. A posi-
Interference pigments are typically based on transparent substrates like tive consequence of thinner basecoats is an improved appearance in
natural mica flakes, which are coated with one or more layers of thin, terms of DOI-values.
E U R O P E AN CO AT I NGS J O UR N AL 2018
EFFE C T P I G ME N T S 59
COPPER COLOURED PIGMENTS WITH CHROMA AND SPARKLE Figure 6: Colouristical performance of highly chromatic copper micas
Also in the copper colour area the achievable chroma has been ex-
ceeded by redesigning pigment structures and further optimising the
flake geometry. The copper pigment is an intense, semi-transparent,
copper shade, mica-based effect pigment, which allows formulators
to style colours with tremendous impact in the copper, orange and
red colour area.
In a black reduction, shown in Figure 6, the pigment is about 25 points
stronger in chroma compared to state-of-the-art copper micas. In ad-
dition to the high chroma the total sparkle value S_G is ~60 % higher
than the comparative example. High chroma and good sparkle also
make this pigment an alternative to expensive iron oxide coated alu-
mina flakes.
REFERENCES
MASTHEAD
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Metal oxide coated aluminium pigments have been produced THE GENERAL NATURE OF EFFECT PIGMENTS
by a new synthesis method. These pigments carry a passiva-
tion layer and an iron oxide layer on thin aluminium flakes. Traditional pearlescent pigments consist of high refractive index metal
They show good stability and exposure performance in both oxide layers deposited onto a transparent, low refractive index, plate-
solventborne and water-borne coatings and allow highly satu- let-shaped substrate such as natural or synthetic mica, alumina, silica
rated coloured effect coatings to be obtained. and glass. Various effects ranging from satin to pearl lustre, from spar-
kle with high chromaticity to angle-dependent colour appearance, can
E U R O P E AN CO AT I NGS J O UR N AL 2018
I N T ER FE CENCE P I G MEN T S 61
The three pigments so far developed allow highly saturated “Wahiba Orange” 13.3 3.0 9.9
colour effect coatings to be obtained in the green, gold and red
be expected. The contrast in brightness between the pigments and their Figure 1: Process scheme for aluminium pigments coated with a
vicinity under different viewing angles is desired in many cases, but there passivation layer and with iron oxide
are also limitations when used in combination with strongly scattering and
absorbing pigments.
Special passivation process
(closed dense passivation layer)
COATED METAL FLAKES ADD COLOUR TO EFFECTS
Passivated
Aluminium flakes aluminium flakes
The combination of metal flakes and metal oxide layers was first de-
scribed in the 1980s and 1990s [5-7]. Metal flakes, in particular alu-
minium platelets, can be coated with iron oxide using the Chemical
Vapour Deposition (CVD) process. Aluminium is particularly appropri-
ate because of its availability and low density, a feature which is ad-
vantageous in view of the large surface area of the platelets relative
to their weight. FeCl 3 NaOH
Iron oxide coated aluminium pigments are manufactured by fluidising
aluminium flakes at 450 °C in an atmosphere of nitrogen in a fluid-
ised bed reactor. The reactants – iron pentacarbonyl and oxygen – are Iron oxide coated aluminium flake
streamed into the reactor together with the agitated aluminium flakes.
Iron oxide is formed and deposited on the aluminium as hematite.
Figure 2: Bright-field microscopic images (optical magnification 200 x) of the orange, gold and red pigment particles in a masstone
coating (pigment content = 3.68 wt%, coating thickness 15 µm, on a black substrate)
The resulting pigments display golden and orange effects with high COLOURS AND PERFORMANCE OF THE NEW PIGMENTS
colour brilliance. The layer thickness of the iron oxide determines its
interference colour, which together with the absorption colour pro- These effect pigments are finally wetted with a solvent chosen for opti-
duces the desired colour effects. mum universal use (diethylene glycol monoethyl ether, also known as
carbitol). The solvent choice also provides a decreased tendency to ag-
INTERFERENCE COLOURS WITH IMPROVED PIGMENT STABILITY glomeration in package storage, ease of use and removes the risk of
dust explosion. The passivation technology is unique. It is the basis for
Several years ago, Merck began investigating another technology that the further manufacturing steps and makes the final pigments suitable
could be used for coating aluminium flakes with metal oxide layers. The for use in waterborne systems.
objective was to develop improved and new effect pigments based on These pigments, branded “Meoxal”, can be used in both solventborne
the layer-substrate principle with metal oxides as the layer and alumin- and waterborne systems, which eliminates the need for separate
ium as the substrate. products for different formulations. The process of pigment incorpo-
The technology should allow the synthesis of such pigments with vari- ration in a paint system runs very easily as well as the formulation of
ous structures and effects, also allowing their use in waterborne paints. new colour variations together with other colorants.
The intention was to deposit metal oxides such as iron oxide, titanium The pigments obtained by this route exhibit the following values:
dioxide, tin dioxide and silicon dioxide on passivated aluminium flakes. Chromatic metallic effect with excellent colour saturation
The pigments thus formed should exhibit the well-known advantages Elegant sparkle effect of individual particles
of other effect pigments, for example good application properties in a High brightness coupled with strong depth
variety of binder systems, environmental compatibility and simple han- Easy to use in solventborne and waterborne systems
dling together with a high stability and the possibility of achieving unique Good storage stability in paints
optical effects. Superior shelf life
The newly developed technology is rather unique, combining key steps Three types of these pigments are already on the market:
from different effect pigment technologies. This includes the passivation Orange type (“Meoxal Wahiba Orange”)
of aluminium flakes with special layers, the deposition of colouring metal Gold type (“Meoxal Taklamakan Gold”)
oxides on the passivated flaky particles, conditioning, thermal treatment Red type (“Meoxal Atacama Red”)
and surface treatment. Pigments manufactured by using these sub- All three types are based on silver dollar aluminium flakes coated with
steps are mostly based on aluminium flakes of the silver dollar type. a passivation layer, an iron(III) oxide layer and a surface treatment.
However, other types of aluminium flakes can be used for the synthesis. They are delivered as pigment pastes consisting of carbitol and 70
The flakes are first coated with a passivation layer by a wet chemical % pigment. Carbitol does not affect the performance properties. The
route. The second step consists of depositing metal oxide layers on the special surface treatment developed for this new class of effect pig-
passivated flakes by precipitation. After conditioning and heating up, a ments allows high demands for outdoor applications such as automo-
surface treatment is applied to the pigment as the last layer to improve tive industry and other high-end applications to be met.
the weathering performance of the pigments and make them adaptable Figure 2 shows a bright-field microscopic image of the three alumini-
to different binder systems. um-based pigments in a mass tone coating. The single pigment par-
Figure 1 shows the process for the manufacture of a pigment contain- ticles exhibit a uniform orange, golden or red colour with almost no
ing iron oxide schematically. The layer structure of a pigment particle tendency to agglomeration. The colour properties of these pigments
consisting of an aluminium flake coated with iron oxide formed by the can be seen in Figure 3. A very high luminance occurs, especially at the
process described is shown at the end of the process scheme. specular angle, together with a high saturation.
Figure 3: Colour properties of the orange, gold and red effect pigments in a masstone coating (measured with 45 °/as 15 ° geometry
on masstone sample with 18 wt% pigment concentration and layer thickness of approximately 15 µm on a black substrate)
“Meoxal F120-30 CWT Taklaman Gold” “Meoxal F120-58 CWT Wahiba Orange”
0.6 “Meoxal F121-51 CWT Atacama Red”
0.5
0.4
v’
0.3
Pigment Hue(u’, v’) Su’ v’ Y
0.2
“Taklamakan Gold” 57.6 1.13 141
u’
E U R O P E AN CO AT I NGS J O UR N AL 2018
I N T ER FE CENCE P I G MEN T S 63
Figure 4: (a) Styling with “Taklamakan Gold” (left) and “Iriodin 9307 SW” (right); (b) Enhancement of Y / The particle size distribution of the orange
S[u’,v’] by using the new gold pigment; measurement position varies from -15, +15, 25, 45, 75 to 110 pigment, as an example, with a volume av-
° at a constant illumination angle of 45 ° erage diameter range Dv(0.1) of 10.4 µm,
Dv(0.5) 18.1 µm and Dv(0.9) 30.9 µm, satisfies
45 the requirements for use in high-end applica-
tion systems. The same applies to the other
40 two effect pigments of this series.
35
30 Y HIGHLY SATURATED
COLOURS CAN BE ACHIEVED
25
6
styling with the orange in comparison to the
4 corresponding styling with the mica pigment
“Iriodin 9508 SW”. The clear advantage for the
2 orange related to the saturation of the styling
is obvious and also confirmed by the corre-
– Styling with “Wahiba Orange” sponding colour data (Table 2 and Figure 5b).
– Styling with “Iriodin 9508” 0
0 0.5 1 1.5 2 2.5 3 3.5 The red pigment is naturally even more reddish
S than the orange one and offers new styling pos-
sibilities in the area of deep red colours, which
cannot be reached with commercial pigments
so far. Also the red offers a high saturation over
Figure 6: (a) Styling with “Atacama Red” (left) and “Wahiba Orange” (right). (b) Shift of all angles. Due to its more bluish character, the
the hue (u’,v’) from red to bluish red at the same saturation S(u’,v’) level by using the styling with this pigment shows a reduced light-
red. With decreasing S, the measurement position varies from 15, 25, 45, 75 to 110 ° ness compared to that with the orange.
at constant illumination angle of 45 ° The difference between the orange and the red
in a styling in combination with organic red pig-
ments and carbon black is shown in Figure 6a.
3.5
The visual impression is confirmed by the col-
our measurements depicted in Figure 6b.
3
HIGH STABILITY AGAINST BOTH STOR-
AGE AND EXPOSURE
s
2.5
The combination of passivation technology with
surface treatment ensures very good stability
of the pigment paste itself and good stability in
2
paint systems, even waterborne ones. For both
– Styling with “Wahiba Orange” the gold and the orange, the pigment paste has
– Styling with “Atacama Red” been proved to have a shelf life of two years.
1.5
-6 -4 -2 0 2 4 6 8 10 12 The pigments were tested in an automotive
Hue (°) coating system (black reduction) for colour
changes. The results achieved for the orange
pigment are shown as an example in Figure 7a-c. No significant colour shift Figure 7: Colour shift of a coating (black reduction of “Wahiba Or-
is observed after the orange pigment was stored at room temperature ange”) within 27 months storage of the pigment paste (for each
for 27 months. panel the paint was freshly prepared using the same pigment
The surface treatment improves the incorporation of the pigments into batch); (a) Lightness L*, (b) Chroma C*, (c) Hue H*
many paint systems, especially waterborne ones. Dispersion is easy and
can be achieved in liquid systems using a dissolver. However, a circum-
60 20
ferential speed of 4 m/s should not be exceeded. Triple roll mills, bead
mills or other machinery with high shear forces should not be used. Pre- 18
wetting the pigments with solvent is recommended to avoid agglomera- 55
L*45*/as45*
L*45*/as15*
tion. Well-dispersed pigments show excellent storage stability. 16
For use in waterborne paint systems, aluminium pigments must show 50
gassing stability. The gassing test ensures this type of pigments can be 14
safely used in waterborne paint without an excessive amount of hydro- 45
12
gen being generated during a period of 30 days at 40 °C. It is considered
as acceptable if the gas amount is less than 25 ml from 300 ml paint
40 10
prepared with 4 % pigment. The results for the orange and gold in this 12 21 24 27
test are summarised in Table 3. They were achieved without any addition
of stabilising agents. 90
39
Good weatherability is essential for use in automotive coatings. Ac- 85
37
celerated weathering results (using a xenon arc tester) for the orange 80
C*(a,b)45*/as15*
C*(a,b)45*/as45*
35
pigment are shown as examples in Figure 8. Similar good weathering 75
results have been measured for the Gold and the Red. These results 33
70
are also confirmed by visual evaluation. Visually, no significant colour 31
65
shift is detected. Florida exposure for all three pigments is ongoing. 29
60
27
55
25
REFERENCES 50
12 21 24 27
[1] Pfaff G., Perlglanzpigmente, Chem. unserer Zeit, 1997, Vol. 31, pp 6-16. 56
[2] Pfaff G., Special effect pigments, in Industrial Inorganic Pigments, 54
ed. G. Buxbaum, G. Pfaff, 3rd edition, Wiley-VCH Verlag GmbH & Co.
52
KGaA, 2005, pp 230-252.
H*(a,b)
[3] Pfaff G., Reynders P., Angle-dependent optical effects deriving from 50
submicron structures of films and pigments, Chem. Rev., 1999, Vol. 48
99, pp 1963-1981.
46
[4] Pfaff G., Optical principles, manufacture, properties and types of
special effect pigments, in Special Effect Pigments, ed. G. Pfaff, 44
Vincentz Net work, Hannover, 2008, pp 16–91. 42
12 21 24 27
[5] Ostertag W., Mronga N., Hauser P., Eisenoxidbeschichtete Alumini-
umpigmente, FARBE UND LACK, 1987, Vol. 93, pp 973-976. time/months
[6] Ostertag W., Effektpigmente, Nachr. Chem. Tech. Lab., 1994, Vol. 42,
– 45°/as 15°
pp 849-854.
– 45°/as 15°
[7] Ostertag W., Mronga N., Properties and application of luster pigments,
Macromol. Chem. Macromol. Symp., 1995, Vol. 100, pp 163 - 168.
Blank 8.0 0 1
0,5
0
“Wahiba Orange” 7.9 6
-0,5
-1 15° 25° 45° 75° 110° 15° 25° 45° 75° 110°
full shade black reduction
“Taklamakan Gold” 7.8 6 “Meoxal Wahiba orange CWT” “Meoxal Wahiba orange CWT”
E U R O P E AN CO AT I NGS J O UR N AL 2018
HOW TO EFFICIENTLY
USE TIO2 PIGMENTS
www.european-coatings.com/shop
Jochen Winkler
TITANIUM DIOXIDE
Everything about titanium dioxide in a single
book: get a comprehensive overview of the
properties, working mechanisms, and possi-
ble applications of titanium dioxide pigments
– including possibilities and limits of replacing
TiO2 pigments in formulations. Essential for
anyone seeking to discover how titanium
dioxide can be used efficiently and selectively
to yield the best formulation.
Look inside
the book!
EUROPEAN
C OATINGS library
Vincentz Network · P.O. Box 6247 · 30062 Hannover · Germany · T +49 511 9910-033 · info@european-coatings.com
66 P E R L E S C E NT P IGMENT S
Source: Punto Studio - Fotolia.com
IN SEARCH OF THE
PERFECT BLACK PEARL
Darker colour enhances tinting options in powder and liquid coatings. By Jonathan Doll, Aaron Hollman,
and Adam Andreas (published in ECJ 12/2015).
A new black pearlescent pigment has been developed that HOW COLOURED PEARLESCENT PIGMENT ARE PRODUCED
offers excellent lustre, jetness and sparkle. It can be used in
masstone or as a tinting agent in both liquid and powder coat- Traditional pearlescent pigments can be grouped into ten basic col-
ings. Notably, the new pigment shows no problems with charg- ours. Six of these are produced by coating a transparent substrate
ing or separation in powder coating applications. with TiO2: silver/white, interference gold, red, violet, blue and green.
The colour is mainly dependent on the thickness of the coating, as
E U R O P E AN CO AT I NGS J O UR N AL 2018
P ER LE S CENT P I G MEN T S 67
Figure 1: Masstone in a liquid coating for the new pearlescent pigment (pearl A) compared to three other black pearl pigments (B-D).
A B C D
flection sphere. F.I. and Mc were calculated using Equations 1 and 2, the sparkle effect, flop and jetness creates an effect unlike any of the
respectively, and are reported in Table 2. other pearlescent pigment in this study, demonstrating the unique-
ness of the pigment.
The flop index can be used as a measure of the overall lustre and travel
seen by the pearl, because it takes into account the brightness at three
different viewing angles. A higher flop index will correspond to a lustrous Table 2: Flop index (F.I.) and jetness (Mc) of the five pearlescent
appearance when the sample is viewed by an observer. The jetness is a pigments studied
measure of how black the pigment appears. Higher Mc values mean that
Sample F.I. Mc
the pigment is more black or jet.
Table 2 shows that pearl A, the new black pearlescent pigment, has a Pearl A 7.41 361.92
good balance of jetness and flop. Pearls B and C have good jetness Pearl B 5.43 375.10
but poor colour flop and pearl D has the worst jetness, but high flop. It
would appear that pearl A offers the best balance of properties. Pearl C 5.83 372.66
In addition, the masstone pictures in Figure 1 show that pearl A has a Pearl D 16.58 348.58
sparkle effect which is not observed in pearls B-D. The combination of
Figure 2: Masstone spray panels showing the difference be- Figure 3: Loading ladder of pearl A in a green-tinted powder
t ween pearl A and pearl B; the much more intense sparkle effect coating base, with loading increasing from 0.0% to 8.0% when
of pearl A can be seen. going from left to right.
A B
0. 0% 0. 25% 0. 5% 1. 0% 2. 0% 4. 0% 6. 0% 8. 0%
E U R O P E AN CO AT I NGS J O UR N AL 2018
P ER LE S CENT P I G MEN T S 69
Could you explain in more detail with which kinds of black pearls you compared your pig-
ment in figure 1 & 2? Without providing competitor brand names, Pearl B and Pearl C in Figure
1 were natural mica coated with iron (II, III) oxide. Pearl D was a natural mica coated with titanium
dioxide and iron (II, III) oxide. In Figure 2, Figure B is another example of Pearl B in Figure 1 and it is
a natural mica coated with iron (II, III) oxide.
Which loading do you recommend for a sufficient sparkle and a dark black colour? For
powder, the recommendation for sufficient sparkle is at 1.0% and a dark black color at 6.0%. For
liquid, the recommendation for sufficient sparkle is at 1.0% and a dark black color at 5.0%.
What is the critical pigment volume concentration in your case? The critical pigment volume
concentration is 72.29 %.
used as they provide a high degree of workability and an acceptable A to tint a green shaded clear powder coating base.
amount of tinting. Figure 2 shows a side-by-side comparison of the As the loading of the new black pearl pigment is increased from
masstone of pearl A versus pearl B when sprayed in a clear polyure- 0.25 % to 8.0 % by weight, the shade of the powder coating
thane powder coating base at 6 % loading. Pearl A and B have similar gradually darkens and the sparkle effect becomes more promi-
jetness and opacity; Pearl A, however, shows the unique polychromat- nent. It is remarkable that a significant shift to a darker shade
ic sparkle effect that is uniform and homogeneous. is observed even at low loadings of pearl A. Finally, at about
It is worth noting at this point that the new black pearl pigments do not 1.0 % loading, the sparkle effect becomes readily apparent and in-
show any issues with charging or separation in powder coating appli- creases with loading.
cations. Powder coating bases can therefore be loaded with the black
pearlescent pigment by either dry blending or bonding. ENHANCED EFFECTS FOR MASSTONE AND TINTING
In both cases, there are no observed issues with charging and/or sep-
aration, which lead to problems such as surging, spitting or agglom- In conclusion, a new black pearlescent effect has been developed for both
eration when they are being sprayed. It has also been discovered that liquid and powder coatings that shows exceptional sparkle and jetness. In
the black pearlescent pigment works in both high and low gloss bases, comparison to other black pearlescent pigments, the new pigment shows
and in addition can be used to tint textured powder coating bases. the right balance of lustre and jetness, as well as a unique sparkle.
The use of the new black pearl allows for greater flexibility in tint- The new black pearl is readily incorporated into powder coatings both as
ing, and can lead to shades that have greater appeal and lustre than a tinting agent and in masstone with little issues associated with powder
standard black pearls. Figure 3 shows a picture of a stainless steel coating charging and separation.
floor panel that has been sprayed with a tinting ‘ladder’ that uses pearl
LEAD IS DEAD
Maintain opacity and durability and expand the colour range with new pigment chemistries. By Mark Ryan,
The Shepherd Color Co (published in 03/2013).
A new pigment chemistry, niobium tin pyrochlore yellow, has our Index (C.I.) Pigment Yellow 227 designation (called PY 227 in this
been developed that expands the envelope of durable colours article). It is a bright yellow similar in shade to middle-chrome yellows
available in paints and coatings. It has the chromaticity and (PY34) with excellent opacity, chromaticity, tint strength and inertness.
brightness of organic pigments and the opacity and durability To complement this development, advances have been made to in-
of inorganic pigments. The new yellow is complemented by im- crease the red tone of PY216 rutile tin zinc (RTZ) orange pigment chem-
provements in rutile tin zinc to increase its red value. Together istry. The result is a pigment with a bright, chromatic-orange masstone
these pigments provide an alternative to lead chromate pig- and high tint strength. This tinting ability, especially the RTZ orange’s
ments and expand the envelope of durable colours in the yel- red value, makes it very valuable in blends with the PY 227 to provide
low and orange colour space. chromatic, all-inorganic matches to a number of colours from middle
yellow to red shade yellow to orange. Both pigments also complement
E U R O P E AN CO AT I NGS J O UR N AL 2018
P I G MEN T CHEM I S T RY 71
are standard components in high-durability systems, but are fairly low in and has much higher chroma than standard high-durability inorganic
chroma. PBr24 is redder than PY53. Higher up near the upper left corner pigments such as the titanates mentioned earlier. Due to the need to
of the graph, PY184 (bismuth vanadate) is to be found. It is a very green move away from lead chromates, the PY 227 provides a bridge between
shade, chromatic pigment. Arrayed in an arc to the right are several of inorganic and organic pigments in chromaticity, opacity and durability.
organic pigments ranging from green shade yellows (PY54), oranges, to PY 216 can be found in the lower right quadrant of the graph. The
bright reds (PR254). Along this arc is PY34 (lead chromate). This repre- increase in the redness of the latest product can be seen by the offset
sents a middle-chrome pigment with a reddish-yellow shade. Its chro- to the right of PY 216. This increase in redness produces a more an
maticity, opacity and economics made it a standard pigment until regula- orange colour which is more in demand than previous offerings seen
tions and market pressure necessitated looking for alternatives. to its left. Besides this pleasing masstone, the RTZ Orange makes an
excellent adjunct to other pigments and makes it possible to offer
HIGHER CHROMA redder tones than have been available to date with organic pigments.
Until the redder shade of RTZ pigments were developed, a chromat-
As can be seen, PY 227 is very close to the lead chromate colour space ic red-shade yellow was made from purely inorganic highly durable
pigments. A common option would have been to start with a green- series of colours. RAL 1003 is a very common colour and it can be
shade bismuth vanadate (PY 184) and add red iron oxide (PR 101) to matched in a number of ways.
make the colour redder. Figure 2 is a more selective chroma and hue The two formulations are based on either inorganic or organic pig-
angle plot which illustrates the colours of this combination with the ments. While they give the same colour, they have different costs and
line labelled ‘blends of BiV-RIO’. The iron oxide shifts the yellow from performance characteristics. One of the most apparent properties in
its green-shade to redder shades, but there is a loss of chroma. If bright yellow colours is opacity. The two pigment formulations were
the bismuth vanadate is instead blended with the RTZ orange to shift used with an acrylic binder at a pigment volume concentration (PVC)
to colour redder, the resulting colours are represented by the line of about 22 %. Due to the large difference in the specific gravity of the
marked ‘blends of BiV-RTZ’. These colours shift redder as with the red two pigment formulations, the pigment-to-binder ratio was 1.2 for the
iron oxide blends, but they are more chromatic. The area between inorganic and 0.4 for the organic. Both represent fairly high loadings of
the two lines represents the increase in colour space available to col- pigment as illustrated in Tables 1 and 2.
our formulators if the desire to stay with all inorganic colourants for The acrylic paints were then drawn down at various thicknesses and
durable colours. the opacity of the films recorded and plotted. Figure 5 clearly shows
As can be seen in Figure 3, PY 227 can also be blended with the bis- that the inorganic based match to the RAL 1003 made mainly of PY
muth vanadate and the RTZ orange pigments to make a wide range 227 has much higher opacity at a lower film thickness than the organic
of colours. They are represented by the lines labelled ‘blends of BiV- pigment based match. This relationship holds for other bright yellow
NTP’ and “blends of NTP-RTZ. The difference between these two lines colours.
and the ‘blends of BiV-RTZ’ in Figure 2 represents the increase in col-
our space available to colour formulators for highly durable colours EXPANDING COLOUR ENVELOPE
through the use of the PY 227.
This increase in the colour envelope available with all inorganic pig- PY 227 was incorporated into a polyester resin in a 23-micron film over a
ments represents a very popular and useful colour space. As is appar- chromate primer on a steel substrate. When standard organic pigments
ent from Figure 4, it includes a number of the highly popular RAL 1000 are used to try to match the PY 227 panel, they do not keep enough of
Figure 5: A comparison of contrast ratio v. film thickness for inor- Figure 6: A comparison of the opacity of PVDF/acrylic coatings
ganic and organic pigment matches as the pigment-to binder ratio of different
E U R O P E AN CO AT I NGS J O UR N AL 2018
P I G MENT CHEM I S T RY 73
their chromaticity due to lack of opacity to hide the substrate and reach fact, if the pigment can be protected from oxygen, it can survive much
the colour. However, the combination of PY 227 and RTZ orange dra- higher temperatures than those listed. An example of this would be in a
matically pushes the edge of the durable colour envelope when it comes silicate system based system cured at 500 °C for 10 minutes. PY 154 and
to thin film applications. a PY 184 undergo a significant colour change due to the temperature and
The inherent advantages in opacity over even other inorganic pigments high-pH of the system, but the PY 227 retains its colour.
can be seen in Figure 6 that shows the opacity of PVDF/acrylic coatings Aside from the performance in a basic system, the periodic Kesternich
as the pigment-to binder ratio of different pigments is increased. PY acid stability test was run on cured masstone and tint PVDF/acrylic pan-
227 has much higher opacity than the organic alternatives. A plot of the els. After seven cycles, the PY 227 had similar colour and gloss reten-
opacity of a coating made with bismuth vanadate is used as reference. tion properties when compared to a PY 53 (nickel titanate), the standard
While PY 227 does not compete directly with bismuth vanadate, be- CICP green-shade pigment.
cause of the relative prices, performance and hue it has higher opacity
than the bismuth vanadate. ACCELERATED WEATHERING TESTS AVAILABLE
Besides the appearance properties of colour and opacity, the NTP and
RTZ pigments have other desirable properties. They have excellent UV When exposed to UV light, the pigment’s high opacity protects sensitive
stability, weathering resistance in accelerated tests and acid/alkali resist- substrates and primers. At the same time, the UV light that it does ab-
ance. In addition they have a range of advantageous physical properties. sorb is not released as a free radical, rather it is dissipated by a vibration
The pigments are dense because of their inorganic metal-oxide structure mechanism (heat) that is negligible in a paint film exposed to sunlight.
and a particle size of around 1 micron. Like many inorganic pigments, The NTP yellow and improved RTZ Orange are still being tested in re-
they have low surface areas and oil absorption for easy incorporation as al-world situations. This will be reported in the future, but accelerated
well as the potential for high pigment loads for increased opacity or higher weathering results are already available.
loading levels in dispersion bases. The pigments have listed heat stabilities When NTP yellow is incorporated into a PVDF/acrylic film over a chro-
of 320 °C, however this is system dependant. The pigments themselves mate based primer on a steel substrate, excellent EMMAQUA weather-
do not react with molten resins in the way that pigments like BiV do. In ing results are obtained. Most notable feature of the masstone colour
change and gloss loss graphs in Figures 7 and 8 is that the PY 227 weath-
ers very similarly to the green-shade standard pigment for highly dura-
ble systems, PY 53 (nickel titanate). PY 227 also performs better than PY
Figures 7: Tint colour stability of various pigments 184 (bismuth vanadate) and PY 139 (isoindoline).
Using the above resin system and tinting with TiO2, the PY 227 performs
very well in the same accelerated weathering testing. It has excellent col-
our retention, especially compared to the organic pigment. It loses gloss,
but as can be seen in comparing the masstone and tint gloss change
data, the major driver in the gloss change is the TiO2, even though a
highly durable grade was used.
The new RTZ orange show excellent accelerated QUV masstone weath-
ering comparable to the red-shade standard, high-durability pigment
PBr 24(chromium titanate) –see Table 3.
CONCLUSION
Together the new NTP yellow and improved RTZ orange pigments pro-
vide high-performance, high durability colour envelope expanding tools
for the coatings chemist and paint formulator. Their high opacity and
chromaticity increase the colours that can be obtained in thin film coat-
ings while pushing the edge of the colour envelope in high durability
systems like coil and extrusion, pwoder, silicate-based paints and coat-
ings for the architectural, ACE, automotive, signage and corporate colour
Figure 8: Tint gloss change of various pigments marketplace. They also make alternatives to lead chromate pigments in
COLOUR CHART
Establishing the causes of colouring in iron oxide pigments. By Peter Köhler and Jürgen Kischkewitz (published in ECJ 01/2014)
Synthetic iron oxides are an important group of inorganic col- Fe2O9 double octahedra with common faces are present in the he-
our pigments, with annual consumption around one million matite lattice, with the Fe(III) ions occupying only 2/3 of the available
metric tonnes. But even though these products have been octahedron positions, while the oxygen lattice section is full. As a
used extensively their colouring mechanism (causes of colour- result of the unoccupied Fe(III) positions, a deficit in positive charge
ing) has not been described sufficiently to date. Detailed de- is produced that is compensated by moving the Fe(III) ions from the
scriptions of colouring for red, yellow, orange and black iron centre of the octahedra. This leads to pronounced distortion for the
oxides is provided and explained, using structural features of two individual octahedra (trigonal components). As a result, the Fe-O
each and findings from ligand field and molecular orbital (MO) distances vary greatly (3 x 2.12 Å and 3 x 1.95 Å in the respective indi-
theory. vidual octahedron) and the Fe(III)-O-Fe(III) angle is approximately 85°.
E U R O P E AN CO AT I NGS J O UR N AL 2018
I R O N O X I DE P I G MEN T S 75
For iron oxide yellow pigments, as a result of these different Chemical composi-
Structural
ligand field parameters, the high-intensity absorption bands III Pigment type* tion and oxidation Lattice type
features
to VI for α-FeOOH are positioned much more in the short-wave level of the iron
range, with the result that the rise in absorption that deter-
mines colour also undergoes a significant UV shift. Fe2O9 double
Iron oxide red -Fe2O3 Corundum
octahedra with
(hematite) (Fe(III) ions) ( -Al2O3)
For iron oxide orange pigments, the calculation of electron common faces
transitions I to IV provides a very good correlation with the
Edge-sharing
measured band positions I to IV, as shown in Figure 7, and thus Iron oxide yellow -FeOOH Diaspore
FeO3(OH)3
explains the colour change from yellow to orange. (goethite) (Fe(III) ions) ( -AlOOH)
octahedra
For iron oxide black pigments, at RT, the octahedrally co- Iron oxide
-FeOOH Boehmite
Edge-sharing
ordinated iron ions have an average valence of + 2.5, which orange FeO3(OH)3
(Fe(III) ions) ( -AlOOH)
Mössbauer spectroscopy also demonstrates with a signal split (lepidocrocite) octahedra
as a sextet, as the “Fe2.5+ ions” couple magnetically with the Fe(II)/Fe(III)
Fe3O4
tetrahedrally coordinated iron(III) ions. Iron oxide black octahedra
(Fe(II) Inverse spinel
(magnetite) Fe(III) tetrahe-
and Fe(III) ions)
drons
Figure 1: Single crystal absorption spectrum of α-Fe 2O 3 Figure 2: Absorption spectrum of iron oxide red III
Inflection points IP
Product Average Intensity i Intensity (L64,
Rise in absorption b*
name particle size (µm) Band II Rise in absorption pure tone)
(cm-1)
Yellow shift
Red II (yellowish cast) Approx. 0.15 0.30 17,300 2.25 23.7
Red IV
Approx. 0.70 0.50 16,700 8.3
(bluish cast)
Blue shift
Red V (strongly bluish
Approx. 1.0 0.50 Approx. 16,500 0.70 5.5
cast)
Figure 3: Absorption spectrum of α-Fe 2O 3 and comparison with a Figure 4: Absorption spectrum of α-FeOOH and comparison with
cadmium red pigment a cadmium yellow pigment
Figure 5: Absorption spectra of α-FeOOH and comparison with a Figure 6: Simplified electron structures of hematite and goethite
α-Fe 2O 3 pigment
E U R O P E AN CO AT I NGS J O UR N AL 2018
I R O N O X I DE P I G MEN T S 77
an intensity of around 10,000) is caused by a large number of other fineness, the colour shifts toward more yellowish products (red I and
electron transitions of the d5 multiple electron system. [3] red II). When the pigment particles are increased, a significant blue
The very high intensities are caused by the particular spin-spin inter- shift occurs (red IV and red V).
actions of the unpaired 3d electrons of two iron(III) ions in the double In the transition from red III to red pigments II and I (increasing fine-
octahedra by way of the bridging oxygen anions (Fe-O-Fe angle ap- ness), the profile of the absorption spectra is very similar (same posi-
proximately 85°). [4] tions for bands I and II). However, a difference exists for the intensities
The intensity of this absorption range is increased further by the rise of band II, as decreasing particle size is accompanied by a reduction,
to the first electron transfer band (transfer of an electron from the shown in Table 2, which results in the somewhat greater colour satura-
O2- ligand to the iron(III) central atom), which is widest in the range tion for the finer pigments. If we consider the rises in absorption, it is
from approximately 30,000 cm-1 to 35,000 cm-1 and also exhibits very possible to observe a shift toward the short wave from red III to red
high intensity. The precise band position can be calculated using MO II and red I (see inflection points in Table 2), which explains the yellow
theory. [5] tinge of the finer red. The intensities for the finer pigments are also
A quantitative evaluation of all electron transitions of Fe(III)O6 octa- slightly lower than for red III.
hedra is possible using ligand field theory and provides the electron In the transition from red III to the red pigments IV and V (increasing
structure of a-Fe2O3 in the d5 multiple electron system. Figure 6 shows particle size), the energy positions of bands I and II in the absorption
the simplified term structure with the measured (I and II) and calcu- spectra are also comparable to red III, while the intensities of band II
lated (III to VI) electron transitions in the visible spectral range. [6] are slightly higher, which Table 2 shows.
Unlike single crystals, both absorption and scattering properties need The rises in absorption become much less intense as particle size
to be taken into account to explain colouring for powder iron oxide increases, and the steepness is reduced. A slight shift toward lower
red pigments. When measuring pigment powders, the part of the wave numbers also occurs. These changes result in a distinct bluish
light that provides colour (red spectral range) is first scattered several cast and a dirtier colour impression compared to the red pigments
times on the pigment particles and then enters the spectrometer (in- I, II and III.
tegrating sphere) as diffused light.
To obtain the absorption spectrum from the remission spectrum thus IRON OXIDE YELLOW PIGMENTS
measured, the measured remission values R (υ, l) need to be con-
verted using the Kubelka-Munk equation Iron oxide yellow (goethite, a-FeOOH) has the crystal structure of dia-
spore (a-AlOOH) and contains only Fe(III) ions in an octahedral coordi-
K (1–R∞)2 nation. The pigments exhibit a needle-shaped habit, with a length-to-
–– = –––––––––––
S 2R∞ width ratio of around 5 : 1 predominating.
The smallest structural units for aFeOOH are FeO3(OH)3 octahedra,
and plotted against the wave number / wavelength as K/S. where the iron(III)-ion is coordinated asymmetrically by three oxygen
K is the absorption coefficient of the red pigment and correlates with (O2-) and three hydroxyl (OH-) ligands.
the extinction (absorbance) E of the single crystal through the rela- This distortion of the individual octahedra becomes clear if we look at
tionships the Fe-O and Fe-OH distances:
K = 2.302 ∙ e ∙ d and E = e ∙ d. Fe-O with 1 x 1.89 Å and 2 x 2.02 Å
With the exception of the factor 2.302, single crystal and pigment Fe-OH with 1 x 2.05 Å and 2 x 2.12 Å
powder have comparable dependencies in terms of absorption prop- In the crystal lattice of the goethite, these FeO3(OH)3 individual octa-
erties. hedra form double chains through shared edges and these chains are
S is a pigment’s scattering coefficient and is essentially dependent on linked to each other via corners, thus creating tunnel-like cavities [1].
particle size and the refractive index n. There are also hydrogen bonds between the double chains, with the
Figure 2 shows the absorption spectrum of a red pigment with an aver- hydrogen atoms being located essentially in the “tunnels” of the crystal.
age particle size of
approximately 0.25 µm (red III). Bands I and II have virtually the same ABSORPTION SPECTRUM AND COLOURING
energy positions as for measurement of the single crystal, as shown
in Figure 1. This is logical given the identical electron structure of the a- At 21,500 cm-1 (band III) and 24,000 cm-1 (band IV), the absorption
Fe2O3 materials. The correct magnitude of intensities is only obtained spectrum of a yellow pigment, shown in Figure 7, exhibits two intensive
by measurement of the a-Fe2O3 single crystal. absorption maximums that determine colouring.
The absorption spectrum of a saturated cadmium red pigment (Cd- The high intensity of the two bands is due to electron transitions with
SxSe1-x mixed phase), as shown in Figure 3, features a very steep, sud- particular spin-spin interactions of the five unpaired 3d electrons of
den rise in absorption that is caused by direct electron transitions two adjacent Fe(III) ions in the crystal lattice, with the rise in absorp-
from the valence band (VB) to the conduction band (CB). In the case of tion adding additional intensity to the first electron transfer band from
a-Fe2O3 pigments, the rise in absorption is less steep (angle of inclina- the O2-/OH- to the Fe(III) cation. A disadvantage for the saturation and
tion a at the turning point TP is approx. 80° compared to 85° for the colour purity of the a-FeOOH pigments is the relatively flat rise in the
cadmium red pigment) and the steepness is also reduced by band II range from 18,500 to 20,500 cm-1 (angle of inclination a at the turning
at approx. 15,500 cm-1. point TP of approx. 64°). In contrast, the rise in absorption of the bril-
These differences lead to the a-Fe2O3 pigments being much less satu- liant cadmium yellow pigment is much steeper (angle a approx. 84°,
rated and exhibiting much lower colour purity. as shown in Figure 4)
The influence of particle size on pigment colouring properties is well The two wide and low-intensity bands at 10,850 cm-1 (I) and 15,500
known. To also investigate this spectroscopically, red pigments of vari- cm-1 (II) have no significant impact on colouring of a-FeOOH pigments.
ous particle sizes from magnetite precursors were produced using Although the electron structures of red and yellow are very similar, a dis-
the Laux process (characterisation in line with Table 2.) and investi- tinct short-wave shift in the rise in absorption of around 2,100 cm-1 can
gated spectroscopically. be detected when comparing the absorption spectra, which is shown
If considering the red pigments I to V, red III represents the reference in Figure 5.
point (average particle size approximately. 0.25 µm). With increasing An explanation for this is provided by ligand field theory in conjunction
with the structural differences of the two pigments. Figure 7: Absorption spectra of α-FeOOH and γ-FeOOH compared
Fe2O9 double octahedra with common faces are present in the α-
Fe2O3, while edge-sharing FeO3(OH)3 individual octahedra can be ob-
served in the α-FeOOH.
In accordance with ligand field theory, the OH- ion is a stronger ligand
than the O2- ion [3,5], with the result that a much higher ligand field
strength ∆ is calculated for α-FeOOH than for α-Fe2O3 following evalu-
ation of the two absorption spectra (∆α-FeOOH = 13,600 cm-1 and ∆α-
Fe2O3= 11,300cm-1). The covalence parameter B was fixed at 580 cm-1
(α-Fe2O3) and 630 cm-1 (α-FeOOH), i.e. the Fe-O bonds in the α-Fe2O3
exhibit higher covalence components.
As a result of these different ligand field parameters, the high-intensi-
ty absorption bands III to VI for α-FeOOH are positioned much more
in the short-wave range [6], with the result that the rise in absorption
that determines colour also undergoes a significant UV shift.
The absorption spectrum of γ-FeOOH is very similar to that of α- the tetrahedrally coordinated iron(III) ions. Further evidence for the
FeOOH, which is shown in Figure 6. indistinguishability of iron ions in octahedron positions is provided by
The rise in absorption for band III exhibits a steepness that is compa- neutron diffraction with an Fe-O distance of only 2.06 Å. [7]
rable with that of band III for α-FeOOH, but the position of this rise for
γ-FeOOH has been shifted around 600 cm-1 in the long-wave direction,
shown in Figure 7, which causes the colour shift to orange. REFERENCES
This longer-wave position of bands III and IV for γ-FeOOH can be ex-
plained using ligand field theory if the differences in the hydrogen [1] Wells A. F., Structural Inorganic Chemistry, 1975, Oxford.
bonds are also taken into account. In the case of γ-FeOOH, these hy- [2] Single crystals were prepared and measured in the working group
drogen bonds are less pronounced due to the differing linking of the under Prof. R. Glaum, University of Bonn, Inorganic Institute.
octahedron chains, so that a somewhat stronger ligand field results [3] Schläfer H. L., Gliemann G., Einführung in die Ligandenfeldtheorie,
for the Fe(III) ions, which leads to a higher ∆ value (14,000 cm-1 as op- 1967, Akademische Verlagsgesellschaft, Frankfurt/Main.
posed to 13,600 cm-1 for α-FeOOH). The covalence of the Fe-O bonds [4] Sherman D. M., Physical Chemistry of Minerals, 1985, Vol. 12, p 161-175.
is comparable in the two pigments due to the calculated B values of [5] Duffy J. A., Bonding, Energy Levels and Bands in Inorganic Solids,
630 cm-1. 1990, John Wiley, New York.
On this basis, the calculation of electron transitions I to IV provides [6] Köhler P., Eigene Berechnungen mit den d5-Energiematrizen in Oh-
a very good correlation with the measured band positions I to IV, as Symmetrie.
shown in Figure 7, and thus explains the colour change from yellow to [7] Day P., Verbindungen mit gemischter Valenz, Endeavour, 1970, p
orange. [6] 45-49.
E U R O P E AN CO AT I NGS J O UR N AL 2018
Source: ShanePhoto - Fotolia.com W O R LD O F C O L O UR 79
ANCIENT PAINTS
Popular pigments used for
cave paintings were iron oxi-
de, maganese oxide and char-
coal, mixed with water, spit or
fat. Researchers assume that
other raw materials were ore,
feldspar, blood, limestone, re-
sin, milk and herbal juices.
FROM BRUSHES TO
SPRAY PAINTING
The paint was applied with
branches, stamps or
fingers. In addition to this,
paints were also spray
painted using pipes made
from bone.
Iron oxide pigments are used on a very large scale in many α-Fe2O3, α-FeOOH and γ-FeOOH is relatively well known, yet there re-
industries. The ways in which the structure of a major group mains a need to explain the absorption properties of these products.
of these pigments (the spinels) affects their colour is explored In particular, an answer is provided for the fundamental question of
in detail. The absorption spectrum of some of these pigments why α-Fe2O3 is red and why a colour shift to yellow or orange occurs
was studied and related to their crystal structure and the elec- for α-FeOOH and γ-FeOOH.
tron orbital transitions that can occur. These aspects are examined in detail based on structural and elec-
tronic properties of synthetic iron oxides and a relationship is estab-
E U R O P E AN CO AT I NGS J O UR N AL 2018
I R O N O X I DE P I G MEN T S 81
measured on powder at room temperature). Compared to Zn ferrite, visible region of the spectrum. An explanation of this band shift will be
two additional absorption bands with relatively higher intensity occur provided near the end of this paper.
at approximately 16,500 cm-1 (T1 = first d-d electron orbital transition These spectroscopic differences with respect to the Zn ferrite lead
of the Fe(III) tetrahedrons) and at approx. 19,500 cm-1 (T2 = second d-d to a significant colour change from a brownish yellow to a medium
transition of the Fe(III) tetrahedrons). brown in the case of the Mg ferrite.
The first high-intensity PE is located at around 19,500 cm-1 and, with
further d-d transitions of the FeO6 and FeO4 polyhedrons, contributes COLOURATION OF MAGHEMITE
to the rise in absorption with a maximum in the region of approx.
21,000 cm-1 (Table 3). The absorption spectrum of the γ-Fe2O3 (Figure 3b, measurement of
In addition, the O2 transition of the Mg ferrite is displaced to higher powder at room temperature) shows a similar curve to that of Mg
wavenumbers (13,800 cm-1 as opposed to 12,500 cm-1 in the case of ferrite, whereby all visible d-d transitions (O1 to O3 and T1 to T3 re-
Zn ferrite), which initiates the less steep increase in absorption in the spectively) and the first PE are displaced to a higher wavenumber in
comparison to the Mg ferrite (Table 3).
Due to the defects in the octahedral partial lattice of the γ-Fe2O3,
these sites offer greater scope for the FeO6 octahedrons to expand,
resulting in greater Fe-O distances. This leads to reduced ligand field
strength ∆ in the case of γ-Fe2O3 and causes the observed band shifts
Figure 2: Absorption spectrum of Zn ferrite (1:10 in BaSO 4) [8] to higher wavenumbers.
Figure 3a: Absorption spectrum of Mg ferrite [8]. Figure 3b: Absorption spectrum of γ-Fe 2O 3 (1 : 10 in BaSO 4) [8].
E U R O P E AN CO AT I NGS J O UR N AL 2018
I R O N O X I DE P I G MEN T S 83
cited states O1 to O5 for octahedral symmetry and T1 to T5 for tetrahe- the 1st to the 3rd PE in the absorption spectrum (Table 2).
dral symmetry [5]. The ground state is set to zero as a reference point As has already been briefly discussed, the relatively steep and high-in-
so that the excited states take on positive energy values (Figure 3). tensity rise in absorption in the region from 17,000 cm-1 to 20,000 cm-1
The d-d transitions in the excited states O1, O2 and O4 and T1, T2 and is responsible for the colouration of the Zn ferrite. The high intensi-
T4 depend on the ligand field strength ∆ and on the electronic inter- ties of the participating transitions (2nd PE, O3, O4 and O5) result from
action parameter B, and can be quantitatively characterised using the cooperative spin-spin interactions, which significantly increase the
energy equations. The transitions O3 and O5 and T3 and T5 are de- probability of these transitions. Furthermore, the rise to CT1, the first
pendent only on B and possess their own individual energy values, charge transfer transition, adds additional intensity.
i.e. the parameter B (a measure of the covalency of the Fe-O bonds) The 1st PE at approx. 17,500 cm-1, which as a pronounced shoulder
thus has the same values for Fe(III) octahedrons and for the Fe(III) in the adsorption spectrum prevents a steeper start to the rise of the
tetrahedrons. absorption, is disadvantageous in terms of colouration.
The edge coupling of the FeO6 octahedrons leads to a Fe-O-Fe an-
gularity of approximately 90 ° and permits cooperative interactions DIFFERING ELECTRON TRANSITIONS IN MAGNESIUM FERRITE
of the unpaired d electrons between adjacent Fe(III) ions via the O2-
ligands. This electronic coupling creates additional transitions in the The electron structure of the Mg ferrite is shown in Figure 4b and also
visible region of the spectrum, which are designated as PE [6] and are exhibits the d-d transitions T1 to T5 of the FeO4 tetrahedrons so that a
coupled with the d-d transitions of the FeO6 octahedron as follows: large number of electronic transitions of different intensities are reg-
1. PE = O1 + O1 istered in the region from 15,000 cm-1 to 25,000 cm-1. This does not
2. PE = O1 + O2 Increasing energy values
3. PE = O2 + O2
4. PE = O1 + O3
Charge transfer transitions, i.e. the transport of an electron from the
O2- ligand to the central Fe(III) atom within the Fe(III) oxygen polyhe- Table 2: Characterisation of absorption spectrum from Zn ferrite
dron, are a further aspect in understanding the electron structures of (octahedral sites).
Fe(III) materials.
O1 approx. 8,500 1st d-d transition (∆- and B-dependent)
The first high-intensity charge transfer transition (CT1), has a wide ab-
sorption maximum in the region of 35,000 cm-1 that can be calculated O2 approx. 12,500 2nd d-d transition (∆- and B-dependent)
using molecular orbital (MO) theory and is important for the coloura-
approx. 17,500
tion [7]. The rise to this absorption maximum lies partially in the vis- 1st PE
(shoulder)
1st pair excitation 2 x O1 = 17,000 cm-1
ible region of the spectrum and adds additional intensity to the d-d
transitions starting from 20,000 cm-1. 2nd pair excitation O1 + O2 =
2nd PE approx. 21,000
20,500 cm-1
ELECTRON TRANSITIONS IN ZINC FERRITE O3 approx. 21,250 3rd d-d transition (B-dependent)
approx. 23,500
The complete electron structure of the Zn ferrite is shown in Figure O4
(calculated)
4th d-d transition (B-dependent)
4a and is formed from the excited states O1 to O5 (d-d transitions)
and the four excited pairs (1st PE to 4th PE). The d-d transitions O1, approx. 24,500
O5 5th d-d transition (B-dependent)
(calculated)
O2 and O3 are clearly visible as bands in the absorption spectrum
(Figure 2) and, via the energy equations, provide the ligand field 3rd PE approx. 25,000 3rd pair excitation 2 x O2 = 25,000 cm-1
strength ∆ = 15,500 cm-1 (average of the calculations from O1 and O2)
O = octahedral sites, T = tetrahedral sites
and the electronic interaction parameter B with 600 cm-1 (calculation
from O3).
In the case of the pair excitations, the calculation used the absorption
bands of the d-d transitions O1 and O2 and confirms the energies of
Table 3: Ligand field parameters of the Fe(III) spinels (O = octa-
O1 (cm ) -1
8,500 9,500 11,300
O2 (cm ) -1
12,500 13,800 15,500
Dr Jürgen Kischkewitz
Contact:
3 questions to Dr Jürgen Kischkewitz Christoph Schmidt
Head of Global Brand Management
Iron(III) spinel pigments are discussed in depth. Please explain the pigment choice to the Lanxess AG
formulator and what must be considered when choosing them. christoph.schmidt1@lanxess.com
Spinel pigments basically behave comparably to pure iron oxide pigments during processing, as
these also undergo intensive grinding. There are differences in thermal stability. Zn-ferrite pigments
exhibit a much greater thermal stability than pure goethite pigments.
What does a formulator who wants to use these pigments have to consider?
Mg- and Zn-ferrite pigments exhibit a high thermal stability that is particularly well suited for the
coloration of plastics and for use in more thermally-demanding coating processes. Maghemite is not
as thermally stable and upon exposure to extreme heat can transform to the more stable hematite
modification and change colour. What makes maghemite special are its magnetic properties.
permit a rise in absorption as in the case of Zn ferrite, and causes the tetrahedral d-d transitions T1 and T2 only change by a moderate
change in colouration from yellow to brown. amount (Table 3), as the isolated FeO4 tetrahedrons in the spinel
The short-wave shift of the O1, O2 and 1st PE transitions relative to the lattice react less to the expansion effect.
Zn ferrite is noticeable, while the d-d- transition O3 (only dependent
on B) of the two spinels has the same energy (Table 3). REFERENCES
As Mg(II) and Fe(III) ions each occupy 50 % of the octahedral sites of
Mg ferrite and Mg(II) has an approximately 9 % larger ionic radius, [1] Eisenoxidpigmente – die Entstehung der Farbe [Iron Oxide Pigments
these sites are further apart than in the Zn ferrite, so that greater Fe-O – the creation of colour], focus theme, FARBE UND LACK, Jan. 2014.
bond lengths are possible. This leads to a smaller ligand field strength [2] Weiss A., Witte H., Kristallstruktur und chemische Bindung, Verlag Chemie,
∆ for an Mg ferrite (Table 3) giving the short-wave shift of O1, O2 and 1983.
the 1st PE (Table 3). [3] Wells A. F., Structural Inorganic Chemistry, Oxford, 1975.
The electron structure of the γ-Fe2O3 is in principle comparable to [4] Krebs H., Grundzüge der Anorganischen Kristallchemie, Enke Verlag,
that of the Mg ferrite; however, the octahedral d-d transitions O1 and Stuttgart, 1968.
O2 and the 1st PE are located at even shorter wavelengths (Table 3). [5] Own calculations with the d5 energy matrices for Oh and Td symmetry.
Due to the empty sites in the octahedral lattice, the FeO6 octahedrons [6] Sherman D. M., Physics and Chemistry of Minerals, 1985, Vol. 12, pp.
have even more space for expansion, which reduces the ligand field 161–175.
strength ∆ in γ-Fe2O3 even further (12,650 cm-1 as opposed to 13,850 [7] Duffy J. A., Bonding, Energy Levels and Bands in Inorganic Solids,
cm-1 in the case of Mg ferrite). John Wiley, New York, 1990.
As the B values for all spinel pigments are comparable (600 cm-1, cal- [8] The absorption spectra were measured by the research group of
culated from O3), the displacement of the transitions O1, O2 and 1st PE Prof. Glaum, University of Bonn.
are exclusively based on the different ∆ values. The positions of the
E U R O P E AN CO AT I NGS J O UR N AL 2018
W O R LD O F C O L O UR 85
SUBSTITUTES
During the early 20th century,
production decreased due to
exhaustion of the supply of
available mummies. Today,
the pigment is a mix of kao-
lin, quartz, goethite and he-
matite. It varies from yellow
to red and dark violet.
Copper phthalocyanine pigment blues show good light and ing of CuPC pigment in waterbased paints. Whereas exterior durability
weather fastness in exterior paints, but rapid fading has some- of the pigment has been extensively studied in scientific literature,
times been observed ininterior applications. Light levels, bind- researches on interior fastness are scarce.
er type and the photoactivity of titanium dioxide appeared to
have no significant effect. However, ozone in theair was shown TEST FORMULATIONS AND APPLICATION PROCEDURE
to degrade the chromophore groups in the pigment.
In order to determine the causes of the interior fading, an experi-
mental process was designed around six test paints made up using
E U R O P E AN CO AT I NGS J O UR N AL 2018
P HYT HA L O CYAN I N E P I G ME N T S 87
months.
ąą CIE L* a* b* data reveal that the major variation is in the ∆b*
value, signifying that the tints have become less blue.
ąą The b crystalline form (PB 15:3) shows better resistance than the
RESULTS AT A GLANCE others.
ąą The influence of the type of binder is negligible, though paints
űű Copper phthalocyanine blues are widely used in architec- with a lower PVC have better performance than those with a
tural coatings. Their exterior durability has been extensively higher PVC.
studied, showing good light and weather fastness. However, In conclusion, the tests show how different organic CuPC pigments,
there are few studies on interior durability, but on occasions considered in the present work, have slightly diverse behaviours
very rapid colour fading has been observed in interior water- and the binder type has no influence, but lower PVC leads to better
borne paints. resistance.
These initial results are in accordance with real paint applications:
űű The interior colour fading of waterbased paints containing that is, in a wide range of tints containing blue CuPC pigments, a rel-
phthalocyanine pigment blue was therefore investigated. Nei- atively fast degradation of the blue tone takes place. But what is the
ther light levels nor the photoactivity of titanium dioxide signifi- likely cause? There could be either endogenous causes (something
cantly affect fading. Although some dependence was found on reactive in the paint formula), or exogenous causes (something ex-
PVC, binder type also had little significant effect. ternal to the paint).
űű Fading was correlated to the presence of ozone in the am- LIGHT AND PHOTOACTIVITY OF TIO2 HAVE LITTLE EFFECT
bient air. An accelerated ozone test also showed rapid colour
fading, with a direct correlation between accelerated test and It is well known that titanium dioxide interacts with light and it
natural exposure. XPS analysis showed how ozone interacts shows photo-catalytic activity, depending on the metamorphic form
with the pigment leading to chromophore group depletion. of the TiO2 and treatment. It can form radicals able to react with
organic compounds [2]. So, instead of TiO2 (rutile), a reference paint
with barium sulphate white was prepared, coloured and exposed to
the same test conditions as before.
Even though the tints are altered by the pigment substitution, the
results, in terms of ∆E, are in accordance with what was verified in
the original test (see Figure 3). Thus, it appears that colour fading
does not depend on the photo-activity of titanium dioxide.
Even if the exposure takes place indoors, natural light itself should
be identified as a possible cause of degradation. Thus in order to
same as an ordinary room at home. Therefore panels were placed check the influence of light, two sets of equal test panels were pre-
vertically in a part of a building well lit by both natural and artificial pared following the previous procedure and exposed into two test
light, with a normal rate of indoor air exchange (test room). Then rooms, one lighted and the other completely dark.
the CIE L*a*b* data was collected regularly and the degradation After four months an equivalent degradation was observed (see Fig-
results after seven months of exposure are shown in Figure 2. ure 4). Therefore, ordinary interior illumination also has no influence
on the vanishing of the blue shade.
INITIAL RESULTS REVEAL SOME CLEAR TRENDS
SEALING THE TEST PANELS PREVENTS FADING
The initial results show a number of very clear trends.
ąą Firstly, only organic blue CuPC pigments show colour fading, Some reactive substances are present in ambient air, among them
while the inorganic cobalt blue pigment shows no significant vari- some radical species and mainly ozone (O3) [3] may react with pig-
ation. ments. Therefore two series of equal test panels were prepared
ąą All CuPC pigments have a large variation in terms of ∆E. The rate following the previous procedure and exposed into the test room,
of the phenomenon is relatively fast and can be observed in few one covered and carefully sealed by thick glass and one exposed
as usual.
After four months a remarkable difference in degradation was de-
Figure 1: An originally blue wall paint (colour still visible in tected (see Figure 4). In fact the glass-covered sample shows practi-
square areas originally covered up) has completely changed cally no colour change compared to the unprotected panel, sug-
colour after a few months gesting that air is responsible for the degradation.
After taking this into consideration, the behaviour of the same sam-
ple exposed in the same room in different seasons was analysed.
Figure 5 shows degradation in term of ΔE* of the same paint ex-
posed at different periods of the year, where degradation is higher
in summer than in winter season. This suggests that the likely cause
should be sought in some component of the air that increases in
concentration during the warm season.
Indeed, literature studies describe a kind of interaction between
ozone and copper phthalocyanine blue colorants as the cause of
fading [4]. In accordance with the current experimental results,
ozone has higher concentrations in summer than in winter and can
be correlated to the phenomenon.
Table 1: Formulas of waterborne paints with t wo different PVCs ACCELERATED OZONE TEST SHOWS RAPID COLOUR LOSS
Figure 4: Measures of ∆E after 4 months of exposure under dif- Figure 5: Measures of differential ∆E of test sample and rela-
ferent test conditions tionship with tropospheric ozone concentration
4
ΔE*
0
Test room Dark room Covered by glass
PVC 82 styrene-acrylic binder
15:1 b 15:1c 15 15:4
E U R O P E AN CO AT I NGS J O UR N AL 2018
P HYT HA L O CYAN I N E P I G ME N T S 89
sure of detecting a significant signal change, the analysis was car- ąą As copper blue phthalocyanine pigment is the only component in
ried out directly on pure colorant pastes. the colorant that contain nitrogen, an evident change and breakage
To do that, the 15:1 colorant was applied on a PVC sheet. Then, of the chromophore group of the pigment occurs when treated
when dry, it was divided into three: one piece represents the initial with ozone.
reference (t0), the second treated for 40 minutes into the ozone ąą The intermediate behaviour of the test room sample shows how
chamber (1 g/h O3) and the third exposed into the test room for one just 30 days of natural exposure causes
month, and finally all samples were analysed by XPS. an evident change of the chromophore group of the pigment,
The survey analysis was carried out between 0 - 1350 eV to identify explaining the fading phenomenon.
all detectable elements and a more detailed scan (multiplex analy- In conclusion, XPS analysis shows how oxidation occurs in both accel-
sis) was performed to collect the spectra of significant elements. erated and natural tests, and in addition the chemical shift of nitrogen
atoms leads to a substantially modified molecular arrangement in the
SPECTROSCOPY CONFIRMS DEGRADATION IS DUE TO OZONE chromophore groups, explaining the observed colour variation.
The key findings of the XPS analysis are shown in Figure 7 and can be
summarised as follows: REFERENCES
ąą An increase of the oxygen signal was found in the treated sample
compared to the untreated, as result of the oxidation reaction. [1] Herbst W., Hunger K., Industrial Organic Pigments, 2004, Wiley.
ąą A chemical shift of nitrogen, as shown by the considerable variation in [2] Kobayashi M., Kalriess W., Cosmetics & Toiletries magazine, 1997,
shape and position of peaks in the spectra, is due to the new chemi- Vol. 112, pp 83-85.
cal bonds built up among nitrogen and other more electronegative [3] Lee D. S., Holland M. R., Falla N., Atmospheric Environment, 1996,
species. Vol. 30 No. 7, pp 1053-1065.
[4] Fujie Y. et al, Fujifilm R&D, 2009, Vol. 54, pp 35-42.
[5] Hofmann S., Auger and X-Ray Photoelectron Spectroscopy in Mate-
Figure 6: CIE L*a*b* data of samples exposed in test room and rial Science, Springer, 2013
ozone chamber
ACKNOWLEDGEMENTS
This work has been carried out thanks to collaboration bet ween the San
Marco Group’s laboratory and the University of Padua. Special acknowl-
edgment is due to professors S. Mammi and R. Bertoncello of Padua de-
partment of Chemistry and to San Marco’s team: R. Nicoletti, M. Mazzari,
F. Toneatto, M. Pettenò, D. Minto, A. Cillotto, L. Piovesan and G. Bellato.
36000
Oxygen Nitrogen
30000 12000
24000
CPS
CPS
18000 9000
12000
6000 6000
Daylight fluorescent pigments (DFPs) have found wide use in eye-catching fashion designs and accessories, while magazines and
warning and safety applications, while, more recently, the advertising posters count on the impact of luminous signal colours.
packaging industry has turned to daylight fluorescent pig- The packaging industry has become increasingly interested in daylight
ments, as brands look for new ways to make their products fluorescent pigments, as more and more brands present their prod-
stand out on the shelf. However, solvent-resistant, strongly ucts in a striking manner, to stand out from the competition.
fluorescent pigments have been so far only available based on The vast majority – some 99 % – of DFPs are organic fluorescent dyes,
formaldehyde containing polymers. which are bound to a carrier resin or polymer and available as stir-
in pigments, where no grinding is needed and the compatibility with
other resins is optimal. Stability and resistance properties of the pig-
E U R O P E AN CO AT I NGS J O UR N AL 2018
FL U O R E S CENT P I G MEN T S 91
RESULTS AT A GLANCE
With the new technologies, the possibility of formaldehyde-
free production of fluorescent pigments is realistic.
"AC-103 "Ag-103
Solvent
orange" orange"
MEK: Xylene (50:50) 5 5
Methanol 5 5
Ethanol 5 5
Propanol 5 5
Ethyl acetate 4 5
Xylene 5 5
Acetone 3 5
Methyl-ethyl-ketone (MEK) 4 5
Cyclohexanone 3 5
3 % NaOH solution 5 5
Water + Ethanol 5 5
The formaldehyde containing (< 0,1 %) “Araco-10” (AC-10) series with its 1. Table 2 compares the reflection and the L*a*b* values that identify
pigments “AC-100 Lemon” to “AC-107 Magenta” is compared with the the saturation, brightness and chromaticity differences between the
formaldehyde-free pigments of the “Aragen-10” (AG-10) series (“AG-100 AC-10 (formaldehyde containing) and the AG-10 pigments (formalde-
Lemon” to “AG-107 Magenta”). hyde-free).
Precursors of AG-10 series are modifications based on polyester resins.
The polyester resins are the basis for the “Araco-60” (AC-60) pigments, A CLOSER LOOK AT LUMINOSITY
which have a low solvent resistance. Modifications of the polyester res-
ins by the addition of amide units have led to good reflection, accompa- To compare the fluorescence and thus the luminosity intensity, pig-
nied by a low resistance to solvents. ments are mixed into acrylic paint. The typical reflection curve of “AG-
Increasing the multifunctional parts in the polyester resin (pentaerythri- 103 Orange” compared with conventional pigments (here Pigment Or-
tol) led to improvement in the solvent resistance, but to the cost of the ange 73) is shown in Figure 1. Similar comparisons can be created for
reflection. all the bright colours of the AG-10 series with conventional pigments.
Similar results have been found by increasing the multifunctional The reflection of all colours is 2-3 times higher than with conventional
parts in polyamide or polyurethane resins. The traditional formalde- pigments. “AG-103 Orange” achieves in white pigment-free formula-
hyde-containing amine resins have been superior to other resins. tions, a reflection of 233 % or more, as shown in Table 2.
The AG-10 technology uses a hybrid polymer of the mentioned for-
maldehyde-free technologies. The solvent resistance is given in Table LIGHT FASTNESS AND HEAT RESISTANCE
Figure 4: Left: LDPE film with 1.35 % "AP-100 Lemon and a Figure 5: In extrusion blow molding process produced HDPE bot-
layer thickness of 150 microns. Right: LDPE film with 1.35 % AP- tles with a fluorescent outer skin layer and a white barrier inside
100 Lemon and a layer thickness of 100 microns mounted on a layer
white layer of 100 microns
Table 2: Comparison of the reflection maximums and the L*a*b*-values between AC-10 (formaldehyde containing) and AG-10 series (formaldehyde-free)
in Acryl resin
Product Colour max. refl. WL/nm L* a* b*
E U R O P E AN CO AT I NGS J O UR N AL 2018
FL U O R E S CENT P I G MEN T S 93
In addition to the solvent resistance of daylight fluorescent pigments, colouring of TPU and olefins (LLDPE, LDPE, HDPE, PP and cPP), while
light fastness and heat resistance are important application criteria. the applications in polystyrene, polycarbonate and PET are limited.
The new formaldehyde-free pigments exceed, even in these proper- The following properties are important for the colouring of thermo-
ties, their formaldehyde-containing counterparts. On the Blue Wool plastics:
Scale (BWS) “Araco-103” shows in orange acrylic paint (30 %), at a layer ąą No sticking on the extruder screws during the master batch pro-
thickness of 16 microns, a light fastness of 3, while “Aragen-103 Or- duction
ange” shows a light fastness of 4 on the BWS under the same condi- ąą No, or very low, plate-out on the tools of injection moulding ma-
tions. Experience shows that it is possible to use selected UV-absorb- chines
ers, a thickness of 100 microns and a pigment concentration of 30 % ąą High heat resistance and acceptable to good light fastness
to achieve light fastness of 6 in PVC. A topcoat with UV absorbers ąą Low odour
helps to achieve a better light fastness. ąą Low level of residual monomers for low migration (efflorescence)
Thanks to the good solvent resistance; light fastness and to the good and for enabling blow moulding of thin layers or sheets
reflection the door is open for the AG-10 series in luminous paints ąą Good fixation of the dyes to improve the migration properties of
and spray cans. the dyes
For applications on the PVC calendar or in injection and blow mould- ąą High compatibility of the polymers, in order to prevent subsequent
ing a good or heigh level of heat resistance is required. efflorescence or bleed. High polymer compatibility is also impor-
Mixtures of “AG-100 Lemon” respectively “AG-103 Orange” were test- tant for the production of thin layers, or films, by blow moulding or
ed in soft PVC formulations at 165 °C and 175 °C over a period of rolling.
20 minutes. The pigment concentration was increased from 5 to 10 %. Daylight fluorescent pigments in plastic packaging are used mainly for
The typical pigment concentration of 30 % was omitted in order to household cleaning products. Other methods, such as the blowing
better assess the effect of heat stress on the colour development. In of thin luminous PE films or bottles with fluorescent outer layer and
all tests, the colour development was uniform, and the fluorescence white inner barrier layer, have failed at production scale due to high
of the PVC films consistently high. Through the influence of heat, there residual monomer content and plate-out of daylight fluorescent pig-
were no odours or sticking of the mass on the roll, as shown in Figure ments and their limited compatibility with olefins. In this context, the
2. AP-10 & 20 technology should be evaluated.
To evaluate the heat resistance at higher temperatures, HDPE was A 45 % master batch was made with AP-100 Lemon in LDPE. In the
coloured with 1 % pigment and tested at various temperatures in an final product, the master batch was reduced with LDPE to a final con-
injection moulding machine. Injection moulded in olefins “AG-100 centration of 1.35 % “Araplast-100 Lemon” in LDPE (corresponding to
Lemon” remains stable up to 240 °C and loses only on colour strength 3 % master batch).
and brilliance to 280 °C. “AC-100 Lemon” loses stability above 220 °C First, a PE film was produced at 100 microns thickness and was then
and at 260 °C begins to show black combustion traces associated with mounted on a white sheet having a thickness of 100 microns. Another
an unpleasant odour. However, plastic parts that were coloured with film was produced with a layer thickness of 150 microns. The higher
“AG-100 Lemon” have been heated up to 280 °C without the genera- layer thickness is necessary because the fluorescence effect without
tion of odours and showed no traces of burning and up to 240 °C with the opaque, white background appears weaker. Film production went
the colour remaining stable. smoothly and the resulting films were homogeneous and without
Figure 3 provides a summary comparison of the main properties of shortcomings, as shown in Figure 4.
the traditional technologies of daylight fluorescent pigments with The high compatibility of the AP pigments with olefins, the very low
the properties of the new AG-10 series. The results of the tests show plate-out and the very low content of residual monomers have ena-
that daylight fluorescent pigments of the AG-10 series have multiva- bled the preparation of thin, fluorescent LDPE films. Previously, thin
lent uses. They are equally suitable for the colouring of aqueous and fluorescent plastic films were only available with PVC or PU as a carrier
solvent-containing concentrates, inks, paints and coatings. Moreover, polymer or by coating procedures.
they are suitable for the colouration of plastics such as PVC, PU, ole- In another test, the melting pigments were tested in extrusion blow
fins and some engineering plastics. The higher light resistance also moulding (EBM) process. Two extruders have produced two hoses,
allows for a greater range of outdoor applications, but not sufficient which were combined in the injection tool to a two-layer bottle with
for use in car or construction paints. fluorescent, thin outer skin layer of 250 microns and a white inner
barrier layer of 500 microns, as shown in Figure 5.
OTHER FORMALDEHYDE-FREE TECHNOLOGIES FOR DAYLIGHT In the course of the entire test, over 4000 bottles were produced.
FLUORESCENT PIGMENTS The combination of outer fluorescent skin layer and the opaque white
inner layer resulted in higher fluorescence visibility. This technique
In addition to the pigment series which retain their particle form in allows the use of daylight fluorescent pigments for new applications
the application, there are pigments which melt at a certain tempera- in packaging. The white barrier layer prevents any migration of colour
ture in the application, without being soluble in it. This leads to high towards the content and supports simultaneously the fluorescence
migration fastness and improved colour strength. Melting daylight and brilliance.
fluorescent pigments (MDFP) use such a technology. Both series
“Araplast-10” (AP-10) and “Araplast-20” (AP-20) are formaldehyde-free
polyester amide resins, coloured with fluorescent dyes. LITERATURE
The colouring of solventbased paints or coatings is not possible with
MDFP technology, this fails in such media due to the poorer solvent [1] I smael R., Schwander H., and Hendrix P., 2013 Fluorescent Dyes
resistance. and Pigments. Ullmann’s Encyclopedia of Industrial Chemistry. 1–22.
AP-10 & AP-20 pigments already begin to melt at 100 °C and are com-
pletely melted at 140 °C. For this reason, and because they are par-
tially soluble in PVC and PU, MDFP pigments are not suitable for the
colouration of these polymers. On the other hand a high migration
fastness makes the use of AP-10 & AP-20 pigments suitable for the
FORMULATION TRAINING
This series was developed exclusive-
ly for the European Coatings Jour-
nal. The articles are based on a long-
running successful course of project
work undertaken by trainee paint
technicians at Axalta. The first part
presents new tasks while you can
find the answers to the homework
of the last issue in the second part.
TASK QUESTION 2
Develop a conventional metallic basecoat for With which binders can you achieve elasti-
the decorative metal coating that meets the fication and an increase in the non-volatile
requirements set out below. Prepare a for- content of the metallic basecoat?
mulation and instructions for the coating and
use the questions to guide you. Take envi- QUESTION 3
Dr Roland Somborn ronmental protection factors and health and Which solvents are suitable for the prepara-
is head of the vocational training centre safety into account when selecting materials. tion of the metallic basecoat?
at Axalta’s Wuppertal site. Previously, he Prepare about 500g of the metallic base coat.
was responsible for production reliability Then prepare a test metal sheet with the cor- QUESTION 4
at DuPont Performance coatings. In addi- responding optical structure (surfacer, metal- a. Describe the differences between leafing
tion to education, his professional focus lic base paint, clear coat) and carry out the and non-leafing bronzes.
lies on the formulation and production of appropriate quality controls. Note: You can b. Compare the advantages and disadvan-
coating systems. also tint the metallic basecoat with suitable tages of the one-coat metallic with those of
pigment pastes. the two-coat metallic.
c. Describe the procedure involved in
PROFILE OF REQUIREMENTS bronze solubilisation.
Binder system: Cellulose acetate butyra- d. What has to be taken into account when
tenon-volatile matter (solids): w = ca. 17% formulating a water-thinnable metallic base-
Pigment-binder ratio 1:4 to 1:5 (mass) coat regarding to the choice of bronze?
Bronze type: Non-leafing bronzes
Flow type (flow cup to EN ISO 2431): QUESTION 5
25-30 s to processing: 21 s Which additives are mostly used when
Application: Spraying formulating the metallic basecoat? Name the
“Drying”: about 10 min at room groups of substances and their effect.
temperature
Adhesion: good adhesion on a surfacer QUESTION 6
Sagging: good non-sag properties on verti- What has to be taken into account in pro-
cal surfaces sag-free up to about 20 µm duction and application of metallic coatings?
Optical requirements: non-blooming
QUESTION 7
QUESTION 1 Define the following effects:
a. Give the chemical structure of cellulose Flop effect, DOJ effect and sparkle effect
acetate butyrate (CAB).
b. Describe the properties of CAB. QUESTION 8
c. What influence does the butyryl, acetyl Name factors which may be responsible for
and OH content have on CAB properties? blooming and give hints on how to avoid this.
E U R O P E AN CO AT I NGS J O UR N AL 2018
F O R MU LAT I O N T R AI N I N G 95
M0DEL ANSWERS
These are the model answers for the RE 3: ADDITIVES the water mountain can cause such a sharp
“Metallic basecoat (conventional)” task The following additives should be considered increase in viscosity that the mixer cannot
set as part of the “Formulation Train- when formulating water-borne metallic base- mix sufficiently to achieve good homogenisa-
ing” in the March issue of the European coats: tion and permit further processing.
Coatings Journal. ąą defoaming agents Water dilutable coating materials tend to
ąą wetting and dispersing agents produce foam which can cause problems
BASIC FORMULATION ąą anti-Sedimentation agents (e.g. development of specks and limits to fur-
A. Bronze reaction ąą rheology additives ther processing). Therefore the development
Provide and mix the following in the order ąą flow control agents of foam has to be prevented by adding de-
stated ąą antistatics (possibly with electrostatic ap- foaming agents and by making adjustments
ąą 3.5% glycol plication) to pumping and mixing capacity.
ąą 2.0% butyl alcohol Dispersions are not completely shear resist-
ąą 1.0% N-methyl pyrrolidone RE 4: “WATER MOUNTAIN” ant which should be taken into consideration
Whilst stirring slowly pour in and continue A peculiarity of water-based paints compared when dispersing.
stirring for 20 min. with conventional paints is the occurrence of
50% aluminium bronze for water-borne me- viscosity anomalies. When the paints with wa- RE 6: GASSING
tallics ter-dilutable binding agents are diluted with “Gassing” occurs with water-borne metallics
water there is no continuous decrease in as a result of the reaction of water and the al-
B. Basic coat production viscosity but a maximum viscosity is reached. uminium surface. In this reaction, which can
Provide and mix the following in the order This viscosity pattern is generally referred to arise in an acid or alkaline medium, hydrogen
stated as a “water mountain“ There are three dis- is accumulated. For this reason the alumini-
ąą 55.0 % polyurethane dispersion (20 %} tinct sections during dilution: um particles have to be stabilised (protected)
ąą 0.5% dimethyl ethanolamine solution 1. Decrease in viscosity (normal dilution ef- by “corrosion inhibitors” or by special protec-
Slowly pour the bronze reaction (A) into the fect). tive layers. The following possibilities can be
preparation (B) 2. Increase in viscosity to a maximum point. responsible for gassing:
Reason: The salt groups of the binding ąą inadequate or no protection of the alu-
Pour whilst stirring agents are dissociated by water and minium particles
ąą 1.0 % thickening agent this causes the polar molecules of the ąą mechanical or chemical destruction of the
ąą 15.0 % polyurethane dispersion (25 %) binding agent to associate (= increase in stabilisation.
viscosity ).
Adjust the pH-value from 7.6 to 7.9 with 3. Rapid decrease in viscosity due to com- RE 7: METAL EFFECT
DMEA solution. plete solvation of the polymer molecules The most decisive factor concerning the for-
=> no interaction between polymers. mation of the metallic effect is the alignment
Adjust for viscosity of the platelet-like metal effect pigments. In
17.0 % volume units in water “water-based paints” the rheology additives
Green pigment paste is used to obtain the viscosity cause a pseudoplasticity to form and result
water mountain
required colour. in the effect pigments aligning.
(2)
MODEL ANSWERS - KEY QUESTIONS RE 8: PARTICLE SIZE DISTRIBUTION
(1)
(3) The particle size distribution in dispersions
RE 1: POLYURETHANE DISPERSION can be determined by laser diffraction pro-
The structure of polyurethane dispersions viding that the dispersion is sufficiently trans-
is obtained by the polyaddition of diisocy- parent. This involves passing a laser beam
anates and diols using dimethylolpropionic additional water through the dispersion which is to be exam-
acid (hydroxycarboxylic acid). The polyure- ined. The laser beam is deviated and diffract-
thane chain thus gains a functionalisation ed at the particles depending on their size.
with a carboxylic acid group which can be The water mountain can be eliminated or at
transferred into water dilutable by means of least reduced by the following measures, for RE 9: DANGERS OF
neutralising with amines. instance: GASSING WITH METALLICS
Special emphasis should be placed on the ąą by adding water miscible co-solvents “Gassing“ metallics are potentially dangerous
following characteristics: ąą by varying the degree of neutralisation for two reasons. Firstly, the container can
ąą good optical characteristics ąą by lowering the concentration of ionic explode owing to the high pressure which
ąą good adhesion on various substrates groups in the polymer molecule the gassing can cause to build up. This can
ąą high water resistance lead to the material splashing into the eyes.
RE 5: SPECIAL FEATURES WHEN Secondly, the hydrogen produced presents a
RE 2: GREEN PIGMENTS PRODUCING THE COATING MATERIALS further danger since hydrogen forms an ex-
Green pigments which might be used in the When producing water dilutable coating plosive and easily inflammable mixture when
formulation of water-dilutable metallic must materials one must be careful about pos- combined with atmospheric oxygen. Contain-
be dispersible to transparency. sible reactions between water and iron. For ers of gassing material should therefore only
Copper phthalocyanines are particularly suit- this reason non-corroding materials such as be opened with the utmost care and using
able (= metal complex pigments). stainless steel must be used. Furthermore personal safety equipment.