Figure 1 / Manufacturing Process of Gold Bronze Pigments
A new line of colorful effect pigments, based on gold bronze pigments, was recently developed for the coatings industry. The copper and copper-zinc pigments are encapsulated with a thin silica layer, using sol-gel coatings technology. The silica layer increases the stability in comparison to the uncoated pigments and leads the way for specific surface modifications to adjust and to tailor the wetting properties. These golden metallics can serve a wide range of coatings systems and open up new color styling possibilities.

Golden and shining colors were used thousands of years ago to provide added value to objects such as buildings or statues. Until the end of the 19th century, gold leaf was applied for these purposes, but the gilding process was very time-consuming and the raw material extremely expensive. At the beginning of the last century, owing to new manufacturing techniques, gold leaf was gradually replaced with metal-effect pigments based on copper zinc alloys. These gold bronze pigments have found widespread use in the printing, coatings and plastics industries whenever brilliance and metallic golden luster are required.

Table 1 / Color Shades of Gold Bronze Pigments

Manufacturing and Properties

Gold bronze pigments are made from cathodic copper and pure zinc. These metals are alloyed, atomized to small particles and ground to flakes in ball mills. Depending on the desired particle size, up to five grinding steps are necessary. Stearic acid is added as a lubricant to prevent cold-welding of the pigments. After a subsequent polishing and a final classifying step, the mill charges are homogenized and the resulting standardized pigment material is filled into drums (Figure 1).

Figure 2 / Position of Different Bronze Shades in the CIEL*a*b* Color Space
The different colors of the bronze pigments come from the different copper-zinc ratios: with increasing zinc content the color changes from a reddish copper to greenish gold. Color shades with higher chroma can be achieved by a controlled oxidation process, in which an extremely thin interference layer, mainly consisting of copper(I) oxide, is generated on the pigment's surface (Table 1, Figure 2).

Figure 3a / Leafing Pigments
Due to their manufacturing process, gold bronze pigments are covered with a hydrophobic layer of stearic acid, which has a significant influence on the wetting properties and may drive the pigments - especially in waterborne systems - towards the coating's surface ("leafing" effect, Figure 3a). This "surface-oriented" alignment gives excellent brilliance and chroma, but the pigments are not fully embedded into the coating's film. Consequently, they have poor rub-resistance and are very sensitive to corrosion. The use of surfactants or polar organic solvents provides better wetting, hence pigments turn out to be "non-leafing" (Figure 3b).

Figure 3b / Non-Leafing Pigments
As mentioned above, gold bronze pigments consist of copper and zinc (brass). The specific density (r) of brass is between 8.9 g/cm3 (copper) and 8.5 g/cm3 (CuZn30). Compared to aluminum flakes (r (Al)=2.7 g/cm3) gold bronze pigments need an increased pigmentation, by weight, to achieve similar hiding power.

Owing to the position of copper and zinc in the electrochemical series, different oxidation reactions can occur. Copper reacts with oxygen, especially at elevated temperatures, and black copper(II)oxide is formed (tarnishing). This oxide layer is soluble in water in the presence of acids or metal complex-forming compounds (e.g. amines, halides), and so provides no protection against further corrosion processes.

Zinc metal can be oxidized easily due to its electronegative character. Acidic as well as strong alkaline conditions lead to water-soluble Zn(II)-species.

These chemical reactions may take place in different coatings, printing and plastics application systems and may cause undesirable effects. Unprotected bronze pigments can tarnish, e.g. during the curing process of powder coating or during the extrusion process of thermoplastics. The resulting products lose their attractive metallic appearance. In both water- or solventborne liquid coating formulations, copper ions can be released and may then cause gelling effects (e.g. in nitrocellulose), or discoloration of binder systems (greening).

To reduce these undesirable effects two different approaches are possible.

1. Chemical inhibition via additives: special corrosion inhibitors are able to adsorb onto the metal surface and limit further attack and/or trap free metal ions, thus preventing their reactions with binder components.

2. Encapsulation of the pigment with a chemically inert and highly transparent barrier layer.

Figure 4 / Production Process of Silica-Coated Gold Bronze Pigments (Dorolan)

Encapsulation of Gold Bronze Pigments with Silica

The encapsulation of pigments with silica is well known. Silica-coated gold bronze pigments have been available for many years. Until recently, because of the manufacturing process, they have had less brilliance, color intensity and hiding power compared to uncoated pigments. These drawbacks have now been overcome using a new production technique (Figure 4).

Bronze flakes that have already been processed for color and particle size distribution are dispersed in a defined mixture of ethanol, water and the silica precursor tetraethoxysilane. The quantity of silane depends on the particle size of the pigment. A catalyst is added and the whole mixture is heated up to accelerate the reaction. The silane is hydrolyzed and reacts to form silica, which precipitates onto the surface of the metallic flake in the form of an ultra-thin vitreous layer (sol gel process).

When the reaction is completed, the mixture is filtered to remove undesirable by-products such as copper compounds, released lubricants (stearic acid) and the catalyst. In the final drying step, the residual solvent is evaporated and the coated gold bronze pigments are obtained in the form of a free flowing powder.

The silica layer itself can be altered by the reaction, for example, with bifunctional surface modifiers1, or other surfactants, leading to metal pigments with tailor-made wetting properties.

Figure 5 / SEM Image of a Silica-Coated Bronze Pigment

Properties of Silica-Coated Gold Bronze Pigments

The silica, approximately 3 to 5% of the metal flake weight, builds up a homogenous and highly transparent, but extremely thin, layer. The image from the scanning electron microscope, (Figure 5), shows the smoothness and homogeneity of the pigment surface, which has no silica side precipitations.

At present these pigments are available in eight different shades (natural as well as oxidized), and in a wide range of particle sizes (Table 2). The coarse grades give coatings a colorful metallic sparkle, whereas the finer grades provide excellent coverage. As indicated above, the amount of the silica depends on the particle size and, hence, the specific surface of the starting material. This is also the reason why very fine grades (D50 < 8 æm) are not yet commercially available.

Table 2 / Range of Silica-Coated Bronze Pigments
In contrast to uncoated gold bronze pigments, these new grades display a completely different wetting behavior, owing to their hydrophilic metal oxide surface. They are easily dispersible in solvent- or waterborne coating systems and are perfectly "non-leafing". The thin inorganic layer, while sealing the metallic surface, gives little reduction to the optical properties of the flake. A comparison of the appearance of coated vs. uncoated pigments demonstrates that, under appropriate conditions, the coated pigments offer (almost) the same superior optical properties as the uncoated ones.

Table 3 / Florida Weathering Test of Silica-Coated Copper Pigments
The color of brass comes from the reflection of light at the inorganic metal (oxide) surface, so gold bronze pigments show excellent light stability compared to many organic color pigments. As an example, silica-coated copper pigments (d50=17 æm) in an automotive coating system, with additional clear coat, were exposed to Florida weathering tests. After two years, no significant color change could be observed (Table 3).

Table 4 / L*C*h Values of Different Bronze Pigments in Powder Coating Applications
Although the silica layer has a thickness of around 30-50 nm, the barrier effect is sufficient to provide thermal stability during the manufacturing process of thermoplastics, or during the application of thermosetting (powder) coating systems. The following examples - powder coating applications of rich gold and copper pigments - clearly show superior color stability of the silica-coated pigments compared to the uncoated metal pigments, and improved optical properties (Table 4).

Bronze pigments are normally very sensitive to shear stress, owing to their shape (flakes) and the ductile nature of the alloy. The silica layer not only improves the thermal stability but also significantly enhances the resistance against mechanical damage. This has been proved using the high shear "Waring Blender Test". Both a coated and uncoated pigment grade, (pale gold, D50=17 æm), were mixed in a high-solid system (8 minutes, 13,500 rpm), followed by an optical characterization of the sheared vs. un-sheared coatings. According to the test procedure, when measured at 15¡, a DL* value < 5 is considered non-degrading, 5-10 semi-degrading and >10 degrading. The silica-coated bronze pigments passed the test with a DL* = -2.0. The uncoated pigments not only showed strong mechanical damage, (DL* = -20.2), but also were strongly corroded during the 1-day storage that follows the shear test (greening of the binder).

The barrier effect of the silica layer against thermal influences makes them non-flammable regardless of the particle size (tested according to Dir. 92/69/ECC). Consequently, these gold bronze pigments are not classified as "dangerous goods" for transportation. Additionally, samples of silica-coated pigments were investigated with respect to human health. Neither skin-patch tests nor in-vitro toxicity tests gave any indication of dermal or ophthalmic irritation, or allergic contact sensitization.

Figure 6 / Microscopic Images of Powder-Coated Panels (Cross Section) with a) Non-Leafing Bronze Pigments, b) Modified, Semi-Leafing Bronze Pigments

Semi-Leafing Gold Bronze Pigments for Powder Coatings

Silica-coated gold bronze pigments, due to their good wettability and non-leafing character, become uniformly distributed throughout the powder coating film and do not orientate parallel to the surface. Consequently, the coating has high gloss values (depending on the powder base), but relatively low color strength and metallic brilliance.

Figure 7 / Lightness (L*) and Chroma (C*) Values of Powder-Coated Panels with Semi-Leafing and Non-Leafing Silica-Coated Bronze Pigments (Rich Gold, D50=35æm)
The opposite effect can be achieved by using a specially modified pigment series. Starting with the Dorolan pigments previously described, a leafing-promoting compound is applied. This additive, creating a semi-leafing effect (see Figure 6b), gives no problem with respect to rub-resistance. The coatings produced are higher in lightness and chroma and exhibit an enhanced metallic effect (Figure 7). An additional benefit is the improved pigment transfer between the spray gun and the object.

Despite the fact that the pigments' location is at or near the surface, there is no significant decrease in stability in contrast to the embedded grades. Panels (5% pigmentation in a commercially available polyester resin) were exposed to humidity tests, (40 deg C, 1000 h, 100% rel. humidity). With both grades, only a slight reduction of lightness could be observed, whereas a comparative (silica-coated, "semi-leafing") bronze pigment of the prior pigment generation revealed a much higher corrosion rate (Figure 8). Unfortunately, in the presence of chloride (e.g. salt spray test according to ISO 9227), the stability of all tested pigments thus far is not sufficient. For exterior powder coatings, the application of a weather-stable clearcoat on top of the effect pigment coating is recommended.

Figure 8 / Color Drift During Humidity Test (100% with Condensation, 40 deg C)

Silica-Coated Gold Bronze Pigments for Direct Extrusion Into Powder Coatings

As described above, it is absolutely necessary to protect gold bronze pigments with a silica layer, against the curing temperature used in powder coating applications. Up to now it has not been possible to process state-of-the-art gold bronze pigments into powder coatings by direct extrusion. Their flake shape and shear-sensitive nature cause them to be damaged, especially during the grinding stage. In the following powder coating application process, the partly chopped and bent pigments did not orientate properly, and the appearance was merely dark brown, without any metallic effect. Metallic powder coatings, therefore, had to be produced by either a dry-blending process or an additional operation, bonding.

In the bonding process, an agitated mixture of base powder and effect pigments is gently warmed up above the softening point of the resin. The pigments are dispersed and stick evenly to the base particles. This method provides the best results with respect to optics and recovering of the oversprayed powder. Dry blending is cost saving, but as the "heavy" bronze pigment can separate from the base during spraying, the recovered and the sprayed powder tend to change in composition.

Recently, a new generation of metal-effect pigments was created to overcome these drawbacks. The basic bronze pigments are similar to the above-mentioned 17-æm grades, and the silica provides sufficient mechanical and thermal stability.

Figure 9 / Lightness (L*) and Chroma (C*) Values of Powder Coating Applications (Extruded) of Silica-Coated Copper Pigments (Dorolan) in Comparison to Pelletized Pigment Preparations (PowderSafe)
These pigments, available in dust-free pelletized form with 10-15% of wetting agents and wax, can be added at the premix stage, together with the other raw materials. They can be extruded and ground. No further production steps, like dry-blending or bonding, are necessary to yield metallic powder coatings. Considering the extreme shear stress the pigments are exposed to during the grinding step, the resulting applications show excellent metallic effects, chroma and brilliance.

In Figure 9, a comparison between a silica-coated metal pigment (e.g. Dorolan 17/0 Copper) and the new pelletized pigment preparation (e.g. PowderSafe 1790-01 Copper) is given. Before spraying, both pigments were processed via an extruder and a milling unit.

As the pigments orientate close to the surface of the coating, their corrosion protection through the binder is rather limited. For outdoor stability and whenever high chemical resistance of the finished powder coat is required, a UV-stable topcoat is still recommended. Stability has to be checked in customers' specific coating system to ensure that the product meets all application requirements.

Conclusion and Further Outlook

A new generation of gold bronze pigments, silica coated by a sol-gel process, was presented. This silica layer provides a short- to medium-term stability sufficient for many applications.

The results of our work give guidance on how to achieve brilliant metallic effects in the reddish to greenish-gold color range. The properties of coatings always result from the interaction between the pigments and all the other components. The possible variations are vast.

We, therefore, consider it unlikely that one kind of (gold bronze) pigment will satisfy all optical and stability requirements of the potential coating systems you may formulate. This fact however, creates the opportunity for further developments to satisfy more specific requirements as they arise.

Acknowledgments

I would like to thank my lab team (Mrs. Kupfer, Mrs. Meerstein and Mrs. Pickelmann) for most of the preparative work, and the colleagues from Technical Service Department (Mr. Korn, Mr. Schreiber and Mr. Wissling) for testing the new products. We are grateful to Klaus Greiwe, Ulrich-Andreas Hirth and Robert Lewis for valuable discussions and contributions.

For more information, contact Dr. Hans-Joerg Kremitzl, Eckart GmbH & Co. KG, Plant Guentersthal, D-91235, Velden, Germany; phone +49 9152 774850; or e-mail h.kremitzl@eckart.de.

This paper was presented at the 7th Nurnberg Congress, European Coatings Show, April 2003, Nurnberg, Germany.

References

1 Macromol. Symp. 187, 109-120 (2002)