1

Paint Pigments: From Chemicals to Masterpieces

by Jay Moore Chemistry 111 Section 407 November 19, 2013

Table of Contents Introduction Methodology Results Discussion References pages 3 - 5 pages 5 - 7 pages 7 - 11 pages 11 - 12 page 13

Introduction Pigments can be found all throughout the natural world. However, pigments can also be synthesized through introducing two or more chemicals together, and preserving the formed precipitate. No matter how the pigments are obtained, a medium must be added for the pigments to adhere to a surface and create a painting. By observing precipitation reactions both microscopically, and macroscopically, while understanding similar colored pigments are not always composed of the same compounds, one can synthesize various pigments to ultimately paint a work of art. History of Pigments The earliest pigment paintings are estimated to have been created between 350,000 and 400,000 years ago. Cave paintings and hunting rituals were some of the first forms of pigmented art (BBC News). The common colors of cave paintings consisted of earth pigments, such as: yellow earth, red earth, white chalk, and carbon black (Windsor & Newton). Much like technology, different eras and parts of the world have had great influence in shaping what pigments are as of today. Not only have different colors of pigments been introduced through worldly influences, but so have the ways of adhesion, known as mediums. The four known mediums are egg tempera, casein, gum Arabic, and acrylic polymer. History of Egg Tempera The word "tempera" derives from the medieval Latin "temperare," meaning blending or mixing. Today, the word indicates a medium bound with emulsions, combined with dry pigments and water (Brandywine Museum). With the introduction of oil paints, egg tempera became a method of the past. However, in the 19th and 20th century, artists became inspired by the painting methods of the past, and a revival of the technique began to emerge.

Egg Tempera Uses When tempera paint dries, the paint becomes insoluble. This is beneficial for the fact that the artist can paint with one pigment, then later paint over the same area with a different pigment, without fear of mixing the two colors. History of Casein Similar to egg tempera, the exhibition techniques were used by blending milk proteins, better known as casein, with dry pigments. Casein is also known as milk paint. Casein Uses An advantage of using casein tempera is that, unlike other paints, casein tempera tends to wear away, rather than flaking. This makes it much easier to repaint a surface without having to worry about chips from the previous coating. Casein is also a breathable paint, meaning it will adhere to surfaces easily, while leaving an attractive soft matt chalky finish (Tesh). History of Gum Arabic Gum Arabic is one of the earliest known mediums for pigments. The commercial use of it can be dated back as far as 2000 B.C. Gum Arabic is derived from one of several natural gums that ooze from trees and harden upon exposure to air. Gum Arabic Uses The technique of water-based painting dates to ancient times, and belongs to the history of many cultures in the world. In the West, European artists used watercolor to decorate illuminated manuscripts and to color maps in the Middle Ages (Barker). Although watercolors have the importance for decoration, they can also be used for play. Watercolors are one of the commonly used styles in paint kits for children.

History of Acrylic Polymer Discovered by Dr. Otto Rohm in the mid 1930s. Acrylic paint is made by combining water and acrylic resin binder. By the 1950s, acrylic paint was commercially being sold. Although oil paint was commonly used, acrylic painting became a new alternative to the painting market. Acrylic Polymer Uses Acrylic paints are able to be diluted in water, while still becoming water-resistant upon drying. This makes them an excellent paint for decorative pieces such as the interior of a house. Unlike oil based paints, acrylic paints are thinner, and dry much faster. Not only this, but acrylic paints also are easier to spread across a surface, and also high customizable by being able to water down the acrylic paint to look similar to water coloring. Methodology/Experimental Design Pigment Synthesis Barium white To synthesize barium while, 2mL of a saturated solution of sodium sulfate was poured into a test tube. After recording the color of the solution, 2 mL of a standard solution of Barium chloride was added to the test tube. The solution was then mixed well, and placed into a centrifuge for 3-5 minutes. This resulted in the separation of the white pigment and clear liquid. Upon decanting the clear liquid, the recovered white precipitate was placed onto a small square of filter paper to dry for the weeks to come. Chrome yellow To synthesize chrome yellow, 1mL of a 0.5M Sodium chromate solution was poured into a test tube, then 1mL of a 0.5 Zinc sulfate solution was added and mixed. After the pH level was tested with pH paper, and using the color guide to estimate the pH levels, 5-7 drops

of 6M NaOH, or Sodium hydroxide, was added to make the solution basic. The Zinc chromate precipitate was then filtered on filter paper, and set aside to dry. Synthetic Malachite After measuring out 5mL of a 0.5M solution of Copper sulfate into a beaker, 3.0g of solid Sodium bicarbonate was slowly added, little by little, into the beaker. The completed reaction was signified by the cessation of fizzing in the solution. After dividing the cloudy solution into two equal parts, half of the solution of basic Copper carbonate was filtered onto filter paper; however, the other half was placed directly onto filter paper. Both were then left to dry for the following week. Prussian Blue To synthesize Prussian Blue, 1.0mL of 0.5M solution of Iron (III) chloride was measured into a test tube, then adding 1.0 mL of 0.25M solution of Potassium ferrocyanide, and was mixed well. Later, the solution was filtered onto filter paper, and set aside to dry for the upcoming weeks. Identifying Unknown Pigments To identify the four unknown pigments, Hydrochloric Acid, or HCl, was added to four known pigments, to later compare to the four unknown pigments. The four known pigments were Zinc White, Chalk, Gypsum, and Titanium white. After adding a small amount of each of the known samples to different openings of the well plate, the properties of each pigment was observed. 1mL of HCl was then added to each pigment, noting the initial reaction of each pigment. After, allowing the HCl and pigments to react for fifteen minutes, a final observation was made of the substances. Knowing the differences of the initial reaction, and recording follow-up observations, the unknown pigments were able to be related, and later identified by conducting the same experiment with the unknown pigments.

Painting with Chemical Compounds Using the pigments that were prepared in the pigment synthesis experiment, unlocked the ability for the pigments to adhesively attach to a surface, through the use of a medium, and create a painting. For this experiment, casein was used as the medium. A very small amount (5-6 drops) of casein was added to 1-2 grams of pigment. Upon mixing the casein and pigment, a thick paste was formed, and was then ready for use. However, if the mixture was too thick, more casein could have been added to the pigment until the desirable consistency was formed. Also, if the casein paint began to dry, a few drops of water was added to dilute the paint. Results Pigment Synthesis Before obtaining the barium white pigment, the mixed solution of Barium chloride and Sodium sulfate was a white, cloudy solution. After the test tube was centrifuged, the mixture separated consisting of barium white precipitate and clear liquid. The chrome yellow pigment turned into a yellow-orange precipitate after mixing the Sodium chromate and Zinc sulfate together. By making the solution basic, through adding NaOH, the solution changed from yellow-orange to bright yellow. The synthetic malachite turned a light, soft blue color upon adding 3.0g of solid Sodium bicarbonate to the copper sulfate solution. This reaction required the most time due to the slow reaction of dissolving such a large quantity of Sodium bicarbonate. The Prussian blue was the quickest of the four reactions. The solution turned to a dark blue precipitate immediately upon mixing the potassium ferrocyanide with Iron (III) chloride. The balanced equations for the chemical reactions of each pigment are written in Table 1.

Table 1: Chemical Reactions of Pigments Chemical Reactions BaCl2 + Na2SO4 BaSO4 + 2NaCl Na2CrO4 + ZnSO4 ZnCrO4 + Na2SO4 [ZnCrO4 + NaOH ZnCrO4 + Zn(OH)2] CuSO4 + ZNaHCO3 CuCO3 + Na2SO4 + H2O + CO2 4FeCl3 + 3K4Fe(CN)6 Fe4(Fe(CN)6)3 + 12KCl

Barium White Chrome Yellow [After Adding NaOH] Synthetic Malachite Prussian Blue

Identifying Unknown Pigments In order to identify the unknown pigments and compare them with the known pigments, the reactions of the known pigments were recorded through chronological observations after adding HCl. Although the four white pigment looked the same initially, the reactions of each were slightly different. Chalk was the most reactive of the four pigments. Immediately after adding HCl, the solution began to fizz rapidly and turn into a cloudy solution. Zinc white was second most active due to a small amount of fizzing after adding HCl. On the other hand, Gypsum and Titanium white reacted slightly, and both had subtle differences between each other. The observations made before adding HCl, immediately after adding HCl, and 15 minutes after adding HCl, are written in Table 2. Table 2: Known White Pigments and Reactions to HCl

Zinc White (ZnO) Before Adding HCl

Chalk (CaCO3)

Gypsum (CaSO4)

Titanium White (TiO2)

Second most Thick

Semi-watery, White

Extremely watery, clear-ish white

Very thick, white

Immediately After Adding HCl 15 Minutes After Adding HCl

Dissolved slightly

Frothy white, cloudy

Stayed at bottom, solidified

Cloudy, white precipitate

Stayed at bottom, relatively clear

Second most cloudy, white precipitate around top

Stayed at bottom, most clear

White, cloudy, no real change

Understanding the reactions of the known pigments with HCl, the unknown pigments underwent the same experiment. Through comparing the unknown pigments with the known pigments, the reactions were able to be related to the results found in Table 2, and assist in identifying the unknown pigments. The unknown pigment reactions, along with their actual pigment name, are written in Table 3.

10

Table 3: Unknown White Pigments and their Reaction with HCl

Unknown 1 (ZnO) Before Adding HCl Immediately After Adding HCl 15 Minutes After Adding HCl

Unknown 2 (CaSO4)

Unknown 3 (TiO2)

Unknown 4 (CaCO3)

Liquid, white

Liquid, white, most watery

Liquid, white

Liquid, white, second most watery Very frothy, dissolved

Dissolved slightly, cloudy

Semi-cloudy, remained on bottom Cloudy, mixed precipitate

No real Change

Dissolved slightly further, second most clear

Stayed at bottom, most clear

White, cloudy, precipitate around top

Painting with Chemical Compounds After introducing casein to the pigments, the paint was ready to be used. An index card was used as the canvas. With each stroke of the brush, the pigment adhesively bonded with the index card; ultimately, creating a work of art. Although the casein dried very quickly, there was still a window of opportunity to blend the pigments together (Figure 1).

11

Figure 1: Using Pigments with Casein Medium Discussion Understanding the data, and the rate at which reactions occurs, is highly important. For example, if the 3.0g of solid sodium bicarbonate was added too quickly to the 5mL solution of copper sulfate, the reaction could potentially explode. Although it was assumed that through creating copper blue, the sample that was immediately set aside and filtered the following week would turn into malachite green; however, this was not the case. This may have been due to the prepared sample being added too quickly, or perhaps not allowing enough time to dry since the reaction to produce malachite green can take extensive time.

12

Also, it is highly important to have detailed observations when comparing pigments with their reaction with hydrochloric acid. Assuming there was going to be a wide range of reactions between the known white pigments and HCl, the differences between gypsum and titanium white were seldom to none. Although the samples of the known pigments were watery and significantly smaller compared to the unknown samples, the reaction with hydrochloric acid was still the same. Due to the non-specific unique written observations between gypsum and titanium white, determining the actual chemical compound of the unknown pigments became guess work. Through understanding the complexities of similar pigments being composed of different chemical compounds, and the reactions in which pigments are produced from, unlocks the potentials of the painting world; ultimately, being able to create unique details by using the four different mediums that have been used throughout history.

13

References Barker, E. E. (n.d.). Retrieved November 10, 2013 from http://www.metmuseum.org/toah/hd/bwtr/hd_bwtr.htm BBC News. . Retrieved November 10, 2013 from http://news.bbc.co.uk/2/hi/science/nature/733747.stm Brandywine River Museum. (n.d.). Retrieved November 10, 2013 from http://www.brandywinemuseum.org/news_print/news058_print.html Tesh, G. Retrieved November 10, 2013 from http://www.mikewye.co.uk/PaintsArticle.pdf Windsor & Newton. (n.d.). Retrieved November 10, 2013 from http://www.winsornewton.com/about-us/our-history/history-of-pigments/ Wye, Mike. Paints and Their History [PDF Document]. Retrieved November 10, 2013 from http://www.mikewye.co.uk/PaintsArticle.pdf