High Performance Pigments. Edited by Hugh M.

Smith 7
Copyright  2002 Wiley-VCH Verlag GmbH & Co. KGaA
ISBNs: 3-527-40307-8 (Hardback); 3-527-60049-3 (Electronic)

2
Bismuth Vanadates
Hartmut Endriss

2.1
Introduction

Bismuth vanadate pigments are a relatively new pigment class that has gained stea-
dily in importance over the last two decades. The pigments exhibit brilliant green-
ish-yellow to reddish-yellow shades, with compositions ranging from BiVO4 (CAS
No. 14059±33±7, EINECS No. 237±898-0) to the mixed pigment 4BiVO4 ”
3Bi2MoO6. They appear in the Colour Index as CI Pigment Yellow 184 without any
statement as to chemical composition. To improve the properties, including the ten-
dency to photochromism, bismuth vanadate pigments in paints contain several per-
cent of organic stabilizers.
Color changes may occur when these pigments are used to color plastics, because
of reduction of the vanadate ion in the polymer melt. Thermostable types suitable
for coloring plastics are therefore protected by a dense, glass-like, multilayer coating
composed of the oxides of aluminum, boron, silicon and zinc.
Bismuth vanadate pigments are lead- and chromate-free inorganic yellow pigments
used in the coatings industry to manufacture brilliant yellow, orange, red and green
shades with good gloss and hiding power. As thermostable types become more avail-
able, the plastics industry is also increasingly turning to these pigments. Bismuth
vanadate pigments have benefited from the decline in use of lead chromate and cad-
mium pigments, especially in the coatings and plastics industries.

2.2
Historical Background

Bismuth vanadate or orthovanadate, BiVO4, occurs naturally as tetragonal dreyerite

in Hirschhorn, Germany, as monoclinic clinobisvanite in Yinnietharra, Western
Australia, and as orthorhombic pucherite in Schneeberg, Germany. However, these
deposits are of no practical importance to the pigment industry.
Bismuth vanadate was first reported in a medical patent in 1924 and synthesized
as a solid substance in 1964. In 1976, Du Pont described the preparation and proper-
ties of ªbrilliant primrose yellowº monoclinic BiVO4. Montedison developed numer-
8 2 Bismuth Vanadates

ous pigment combinations based on BiVO4. Pigments containing other phases

besides BiVO4, for example Bi2XO6 (X = Mo or W) have been reported by BASF. In
addition, Bayer and Ciba have published methods for the manufacture of pigments
based on BiVO4. Today there are several manufacturers, producing ca. 900 tonnes
annually. The two leading producers are BASF AG and Ciba.
Bismuth vanadate pigments are high-quality yellow pigments. They lie in the
higher price range for inorganic pigments because the raw materials are relatively
expensive.

2.3
Manufacture

Bismuth vanadate pigments are obtained by a precipitation process in which caustic

soda or sodium hydroxide is added to a solution containing bismuth nitrate, sodium
or ammonium vanadate, sodium molybdate (where specified) and nitric acid. The
precipitate of oxides and hydroxides is washed until it is free of salt. To form better
crystals and hence improve the pigment properties, the intermediate product is tem-
pered at 200 to 700 C. Layers of stabilizer are then applied to the surface of the crys-
tals in subsequent precipitation steps, and are sometimes also calcined. In the case
of the thermostable type, these layers are dense, glass-like coatings composed
mainly of silicates. Further washing, drying and milling operations follow. To pro-
duce free-flowing, low-dusting fine granules, the pigment suspension is spray-dried
and automatically packed.
The wastewater from the production process is fed to a neutralization step in
which soluble heavy metals are precipitated, and suspended pigment particles
allowed to settle out. A denitrification step may be employed to lower the nitrate
content.

2.4
Properties and Applications

2.4.1
Chemical Properties

Bismuth vanadate pigments are insoluble in water and alkalies. Only in strongly
alkaline media, e.g. mixtures with cement, will they sometimes show instability and
undergo a change in shade. Acid media with a pH of less than 2 cause perceptible
solubilization, depending on how well the pigment has been stabilized.
 2.4 Properties and Applications 9

2.4.2
Physical Properties

The most important physical properties are:

Density 5±7 g/cm3
Mean particle size 0.4±0.8 lm
Specific surface area 12±4 m2/g
Oil absorption 30±10 g/100 g pigment
Compared with organic pigments, the density and particle size are relatively high
while the specific surface area and oil absorption are quite low. This means very
high pigment loading is possible. However, precautions must be taken to prevent
sedimentation in low-viscosity systems, due to the high density of the particles and
the fact that they readily settle out.

2.4.3
Coloristic Properties

Bismuth vanadate pigments are characterized by brilliant, greenish-yellow to red-

dish-yellow shades of high color strength, high gloss and good hiding power. When
they are compared with other inorganic yellow pigments, their coloristic properties
are seen to resemble those of cadmium yellow and lead chromate. Figure 2±1 shows
the reflectance curves of bismuth vanadate and other inorganic yellow pigments.

Figure 2±1: Reflectance curves of bismuth

vanadate and other yellow pigments (cad-
mium sulfide, nickel rutile yellow, yellow iron
oxide and chrome yellow).
10 2 Bismuth Vanadates

Bismuth vanadate pigments have a much higher chroma than yellow iron oxide and
nickel titanate pigments. In full shades and the palest tints, bismuth vanadate pig-
ments show superlative fastness to weathering.
Unstabilized types tend to undergo substantial reversible color changes (photochro-
mism) on exposure to intense radiation in the Suntest. Following additional stabili-
zation, this effect is substantially reduced or becomes barely perceptible.

2.4.4
Dispersibility

The excellent dispersibility is typical for inorganic pigments of this type and is far
superior to that of organic pigments.

2.4.5
Light Fastness and Weather Resistance

Bismuth vanadate pigments exhibit very good light fastness in both deep and pale
shades. They show excellent weather resistance in full shades, and are superior to
lead chromate in this respect. In full shades they are comparable with the best
organic pigments and have the greatest durability in deep reductions.

2.4.6
Chemical and Solvent Resistance

The resistance of these pigments to organic solvents is excellent. Their ionic charac-
ter may be a disadvantage with regard to acid/alkali resistance, but surface stabiliza-
tion improves this significantly (see Sec. 2.5.1).

2.5
Applications

About 95 % of the total volume of bismuth vanadate pigments is used in paint man-
ufacture and about 5 % in plastics processing. This ratio may change however in
the future in favor of plastics coloration.

2.5.1
Coatings

Bismuth vanadate pigments are used to obtain brilliantly colored lead-free standard
automotive finishes, automotive repair finishes and high-grade industrial paints.
They are equally suitable for pigmenting solvent-based and solvent-free paints. They
are of particular interest as a basis for brilliant, highly opaque orange, red and green
shades, for which they are combined with organic pigments.
 2.5 Applications 11

The chemistry of bismuth vanadate pigments makes them sensitive to acids. How-
ever, tests in which acids were applied to baking finishes under practical conditions
have shown that the acid resistance of these pigments is normally comparable to
that of a highly stabilized lead chromate. The application of bismuth vanadate pig-
ments in powder coatings and coil-coatings should be tested in customer material,
because in such cases ± more than in standard liquid paint systems ± the suitability
depends on the total formulation.

2.5.2
Plastics

2.5.2.1 Properties
Thermostable bismuth vanadate pigments are available today with a heat stability of
260 to 280 C. They exhibit very good fastness to light and weathering in plastics for
outdoor use. In weathering tests on plastics pigmented with 0.5 % cadmium yellow
or 1 % bismuth vanadate, the bismuth vanadate pigment was superior both under
artificial conditions (Xenotest, 4000 h) and outdoors (5 years).
The pigments have outstanding fastness to migration in plastics, and are readily
dispersible.

2.5.2.2 Applications
With their excellent heat stability, the thermostable types can be readily incorporated
into polyolefins and ABS at 260±280 C, and polyamide injection-molding materials
at 280±300 C. Even when they are applied in the manufacture of large injection-
molded and extruded plastic parts, the product obtained is dimensionally stable and
non-warping. Because of their excellent fastness to weathering, they are an ideal
substitute for pigments containing lead or cadmium in outdoor applications (bottle
crates, garden furniture, garbage bins, etc.)

2.5.2.3 Conformity of Pigments for Plastics Coloration to Food and Drug Regulations
The good insolubility of bismuth vanadate pigments is reflected in their fastness to
migration. They can be used in typical commercial concentrations for coloring plas-
tics for food packaging and other materials and articles in accordance with the purity
requirements of the following countries for colorants in food packaging: Germany
(RECOMMENDATION IX of the Federal Institute for Consumer Health Protection
and Veterinary Medicine, BgVV), Austria, Belgium, Italy, the Netherlands, Spain
and Switzerland. In addition, the purity requirements of European RESOLUTION
AP(89) I of September 1989 are met. However, they are not included in the French
and FDA positive lists (21 CFR, § 178.3297), nor have they yet been submitted for
inclusion.
12 2 Bismuth Vanadates

2.6
Toxicology

2.6.1
Acute Toxicity

No adverse toxicological effects were observed in animal tests involving oral and
inhalational intake of the pigments.
LD50 rat, oral > 5000 mg/kg
LC50 rat, inhalational > 5.15 mg/L/4 hours
Skin irritation Non-irritant (tested on rabbit)
Mucous-membrane irritation Non-irritant (tested on rabbit's eye)
Mutagenicity (Ames test) Negative (tested on five strains of bacteria with and
without enzymatic activation)
Sensitization Non-sensitizing (tested on guinea pig)

2.6.2
Chronic Toxicity

Animal trials with respirable dust gave some indication of inhalational toxicity, the
effects of which were reversible at low concentrations. To alleviate the associated
risk, some manufactures supply bismuth vanadate pigments in a free-flowing, low-
dusting form, making them inaccessible to the lungs. The safety of these pigments
is reinforced by their high density, which causes any airborne dust generated to set-
tle very quickly. Even so, the usual precautions and industrial hygiene rules neces-
sary for handling chemicals must be observed.

2.7
Ecology

Bismuth vanadate pigments exhibit low solubility in water. They can therefore be
removed from wastewater largely by mechanical means, for example in wastewater
treatment plants. An appreciable increase in water solubility occurs only at pH levels
of less than 2.
They exhibit practically no toxicity to fish, daphnia or bacteria, as evidenced by the
following values: fish (orfe, acute, 48 h, EC0 10 000 mg/L), daphnia (EC0 100 mg/L)
and bacteria (Pseudomonas pudita, EC0 10 000 mg/L).

References

1 H. Endriss, Inorganic Coloured Pigments Today, 3 H. Endriss, Farbe Lack 6 (1994) 397.
Vincentz, Hanover, Germany (1998). 4 H. Wienand, Ullmann's Encyclopedia of Indus-
2 L. Erkens, L. Vos, The Bulletin of the Bismuth trial Chemistry, Vol. A20, Sec. 3.3, VCH Pub-
Institute, Grimbergen, Belgium (1997). lishers Inc. (1992).