COLORANTS

COLORANTS

 

The term colorant is a broad based word for materials to permanently color ceramics. These Include metallic oxides, carbonates, sulfates, and salts; raw stains; calcined stains (commercial or homemade); and some nonmetallic. Colorants can be used In clay, engobes, stains, overglaze, in the glaze, underglazes, decals, washes, lusters, ceramic screen printing inks, porcelain enamels (metal enameling), ceramic pencils, ceramic crayons, ceramic chalk, and crystal formers. The metallics are: bismuth, cobalt, nickel, chrome, copper, Iron, selenium, cadmium, uranium, manganese, zinc, and tin. The nonmetallics are: cerium, erbium, neodymium, zirconium, and sulfur. They are used as they are, but more often mixed with other colorants, mixed with and/or calcined with other ceramic minerals. The major methods of coloring ceramics include the following

 

Colored clay ‑ Colorants are mixed with the clay body.

 

Enoobe ‑ Colored fluxed slip (engobe) is applied as a design or to give color and/or cover the clay body. A glaze may be applied over.

 

Fuminc ‑ Metallic carbonates, sulfates, and nitrates are painted, sprayed, dipped on green or bisque ware for pit, saggar, or Raku firing. Like Egyptian paste the metallics migrate to the surface to give flashes of color and luster effects.

 

On the clay ‑ Colorants are applied by brush, spray, splatter, dip, pour, etc. to the surface of the clay. An antique effect Is obtained by having the colorant applied then washed off leaving the colorant in the recessed areas. A glaze may or may not be applied over.

 

On the glaze ‑ Colorants are mixed into base glaze for color. Some ceramic minerals that make up the glaze have metallics (barnard clay, Albany slip, ash, earthenware clay, etc.) that give glaze Its color (tenmoku, celadon).

 

Overglaze ‑ Colorants as stains and washes are painted, airbrushed, splattered, stenciled, etc. to the unfired or fired glaze. They fuse to the glaze once fired, but some will be matt and may need a clear glaze applied over to give a sheen or gloss.

 

Overolaze enamels ‑ Low temperature glazes containing colorants are applied to a glazed surface and fired at a low temperature to mature and fuse to the glaze.

 

Underglaze ‑ Colorants (commercial stains or preparations) or washes are painted on as allover color or designs. A transparent glazes Is applied over.

 

STAIN

 

A stain is used to give color to and/or mixed with coay, engobe, or glaze or used by Itself as a wash (over glazes, engobes, or clay body much like a watercolor), underglaze color, and overglaze color. It is conducive to application techniques of painting, spraying, screening, sponging, or used the same as the metallic oxides. Stains like metallics, If applied too thickly, may crawl or act as a flux or refractory..

 

A stain is composed of a mixture of metallic(s), filler, flux, and alumina. This mixture can ‑be used as Is (raw) or calcined. The purpose of calcination the mixture of metallics and materials Is that the heat fuse the materials to form a bond that is not affected by kiln temperature or atmosphere or the glaze the same way that the metallics alone would be affected. Metallics like cobalt, chrome, nickel, copper, Iron, etc. form colors in stains that by themselves would not be possible. Thus the use of stains vastly Increases the color palette and range. There are limitations and exceptions, particularly In the red, yellow, and orange spectrum beyond a limited temperature and glaze composition. Some stains are affected by the kiln's atmosphere and temperature.

 

There is no set percentage of the various materials to make up a stain. The following is averages of typical stains:

­

Materials                     Percentages                         Materials                     Percentages

Metallic oxides, carbonates                        4 to 85%                                   Alumina (china clay)                        5 to 50°%

Flux (borax, whiting, soda, etc.)                        5 to 70°,6                                  Silica                         0 to 50°ro

 

The following typical stain formulas show the colorant, filler, stabilizer, and *calcining temperature:

 

Blue Green Stain C/014*           Olive Green Stain C/014*            Leaf Green Stain C/014*

Silica                     32              Cobalt oxide              32              Silica               35

Borax              20              Chrome oxide              24                         Chrome oxide               20

Chrome oxide               18               Borax               14                          Zinc oxide               15

Zinc oxide               15               Zinc oxide               14                          Borax               18

Cobalt oxide               8               Silica               7                            Cobalt oxide               9

China clay               7               Nickle oxide               6                            Talc               3

               100               China clay               3                                           100

                                             100

 

Making and using one's own stains have the advantages of saving money and obtaining a variety of different colors. The disadvantages are time and extra equipment In making them. However, the variety, unusual colors, and textures are well worth It. See Commercial Stains In Appendix.

CALCINED STAIN can be individually made and will require a crucible, ball mill or mortar and pestle, 100 mesh screen, and kiln. Crucible are purchased or made. To make a crucible use fine Iron free grog (10 to 20 percent) wedged Into porcelain. Crucible forms are made by wheel or pinch formed. Before making a large batch of any stain, a testing should be done. The procedure for making stains are:

A.             Materials weighed, mixed, and 100 mesh screened

B. Some formulas recommend ball milling the materials wet or dry for 1 to 3 hours. Small amounts are done in a mortar and pestle for 1/4 to 1/2 hour.

C.     Wet materials are screened and washed twice then set out to dry. Dry materials are screened.

D.      Dry mixture Is placed In a porcelain crucible and fired in a kiln to the recommended tempera­ture, usually C/2 to C/11. In amounts of 5 pounds or more the melt will need to soak at the

peak temperature to make sure the entire mixture is heated evenly.

E. The heating the stain mix results in the mixture being hard like a glass rock (clinker), soft rock like sandstone, firm like dry clay, or powder consistencies. The soft will only need screening while the harder compound will break up with light hammering but the very hard need heavy blows to break the clinker into small pieces. These small pieces are ball milled for several hours to further break down the materials to finer consistency. Commercial companies dump the hot clinker Into water whereby the thermal shock shatters the clinker to speed up the hammering process.

F. The broken pieces are placed in a ball mill and wet ground for 4 or more hours until it will pass through a 100 or finer mesh screen. Some materials will need to have the water changed

several times during the grinding to wash out the soluble salt. Small amounts can be ground by hand in a mortar and pestle.

G. The wet stain Is screened (100 mesh or finer) and air dried. Commercial stains are screened 120 mesh and finer.

The benefits of making up raw stains are saving time, having a variety of colorants, and being able to develop new or different colors. The time saving of mixing up a large batch of raw stain so that it is available when smaller amounts are need to make a glaze, engobe, wash, and such. Making stains, washes, ceramic pencils, etc. requires time and preparation, however it is worth It. If a particular glaze Is used often and the glaze formula calls for several different metallics, making this colorant mix Into a large raw stain batch will save having to constantly weigh these out. When this glaze Is prepared, only the stain needs to be weighed Instead of several different metallics.

RAW STAINS are not calcined and often the same formula as calcined stains. The procedure Is the same (above A through C) as calcined stains. Even some commercial stains are not calcined, In particular browns and blacks. It saves time, ball milling, and kiln firing. Depending upon the firing temperature, In­gredients, and the glaze it is used in, the coloring power and color range of some yellow, red, and orange stains may be limited to low temperatures, while others will have the full temperature and glaze type range. Raw stains are easy to make, cheaper than commercial stains, and are an Interesting process. Unfortunately, the colors possible with raw stains are limited as compared to calcined stains.

COMMERCIAL STAINS Coral, pink, and certain yellow, orange, red, and purples can only be ob­tained by the use of stains. It Is very difficult to make these In one's studio without precise endeavor, ex­tensive equipment, and extended ceramic supplies. Heating the materials In a crucible, pouring the hot clinker Into water, grinding the fragments, ball milling, washing, and screening Is time consuming. Several companies make stains and provide a variety of colors. See Appendix for listing of stains.

 

The following table lists the possible colors, metallic oxide, and additive(s) used to obtain both raw and calcined stains.

 

FIGURE 9 ‑ STAIN COMPOSITION FOR METALLICS, AND ADDITIVES

 

Color Metallics Additives

Yellows Uranium Calcium

and oranges   Antimony Lead, tin, calcium

Vanadium Zrcopax, tin

Red Iron Alumina, zinc, calcium

Rutile Tin, alumina, zinc.

Reds Chrome Tin, calcium, silica

Selenium/cadmium Tin, calcium, alumina

Uranium Soda, tin, alumina

Gold Tin, alumina

Pinks Chrome T1n, calcium, lead, silica, zircopax

Manganese Alumina

Purples Chrome Tin, boron

and Ulacs Manganese Alumina, tin

Cobalt Tin, magnesia

Blues Cobalt Alumina, zinc

Cobalt/chrome Alumina, tin

Nickel Alumina

Copper/cobalt Tin, alumina

Grays Nickel/cobalVchrome Silica, calcium

Browns Iron Zinc, alumina

Chrome Zinc, tin, iron

Manganese Zinc, alumina, nickel

Blacks Iron/manganese/cobalVcopper          Alumina, silica

Iron/manganese/copper Alumina, silica

              (cobalVchrome free)

Iron/cobalVmanganese/chrome          Alumina, silica

              (copper free)

Greens Chrome/copper/nickel Alumina, silica

 

Rare earth elements (cerium oxide, neodymium oxide, praseodymium oxide, and yttrium oxide), produce some soft pastel colors as well as experimenting both for a stain and for unusual glaze effect such as crystal and crystalline glazes. See Appendix for more details on metallics.

 

METALLIC OXIDES AND OPACIFIERS

 

Metallics are the source of color, and in large amounts will opacity In a glaze. Often the metallics are oxides or carbonates but other forms are used Including carbides, chlorides, nitrates, phosphates, silicates, sulfides, and sulfates.

Color Is the absorption, reflection, and refraction of various light wavelengths that are detected by the eye and its associated nerves. Light reflected to the eye stimulates the various color cones of the retina, creating the basis for the brain's perception of color. Pigments and glaze colorants are both per­ceived in this matter, but there the similarity ends. Pigments, as in paints, produce easily predicted colors when mixed, (Le. yellow and blue make green). This Is not necessarily so In glazes, for there Is the chemistry of the glaze involved. In ceramics, unlike pigment, the color and color change are caused by chemistry. Examples are the abundance or scarcity of oxygen and metallic molecules and crystal and chemical structure. When blending of blue and yellow in ceramics, the result may be anything but green. This Is a chemical blending. The following Is a guide for the various colorants and opaciflers.

 

 

FIGURE 10 ‑ COLORANT AND RESULTING COLORS AS AFFECTED BY MAJOR FLUXES IN A GLAZE

 

Metallic                           Dominant Firing Atmosphere                    Resulting color(s)

Colorant Flux       Oxidation (OX) or Reduction (RD)

    CHROME

Alkaline  OX ‑ Yellow‑green, chrome.

           RD ‑ Pale green to browns‑green to almost yellow. Very refractory.

Lead                   OX ‑ C/010 to CI08 (high lead and low alumina) give brilliant orange to

                                   orange‑reds; soda and lead give bright yellow using 1 percent chrome, and

                                   with 4 to 5 percent In gives pink; temperature CI04 give chrome greens.

           RD ‑ Not reduced.

  Boron & Magnesia                                           Dull greens ail temperatures and atmospheres.

  High Zinc                                         Brown all temperatures and atmospheres.

  High Barium  OX ‑ In lower temperature, brilliant yellow‑greens to light green.

           RD ‑ Brown to pale green.

    COBALT

Alkaline                                           Powder blue, Intense blue to blue‑black at all temperatures and atmosphere

  Lead                                               Typical cobatt blues but less Intense than alkaline based at all temperatures

                                   and atmospheres.

  Boron                                              Rich blues of typical cobalt at all temperatures and atmospheres.

  High Magnesia    OX ‑ Purple.

           RD ‑ Pink, violet, to red‑blue.

  High Zinc                                         Strong green‑blues in all temperatures and atmospheres.

  High Barium                                     Gray‑blue in small amounts to Intense blue in all temperatures and atmo­

                                                  spheres.

         COPPER

Alkaline  OX ‑Intense blue to blue‑green, In low alumina a bright blue. (Usually

                                   runny)

           RD ‑ Gives blood reds.

  Lead                  OX ‑ Rich grass green yellow.‑green; with tin light grass green with deep rusty

                                   red when thin.

           RD ‑ Not reduced.

  Boron  OX ‑ Brilliant blue‑green and turquoise; with rutlle results in blue‑green

                                                  streaks; In reduction blood reds, purples to whitish reds In all tempera­

                                                  tures and atmospheres.

  High Magnesia    OX ‑ Purples.

           RD ‑ Liver to pale pink‑reds.

  High Zinc  OX ‑ Develops strong greens.

           RD ‑ Hinders copper reds In reduction.

  High Barium  OX ‑intense blue to blue‑green.

           RD ‑ Tomato reds; a mix of barium calcium, and soda gives blood reds.

         IRON

Alkaline  OX ‑ Straw yellow, yellow brown to brown.

           RD ‑ Cold colors; .5 to 1 percent gives Celadon blue to blue‑green.

  Lead   RD ‑ Warm yellow, amber, tan, honey, brown, reddish brown to deep red; saturate

                                                  iron; 7 to 10 percent in low alumina gives aventurine; with tin gives creams

                                                  and rusts.

           RD ‑ High leads not reduced.

  Boron  OX ‑ Dull tans and browns.

           RD ‑ Blue‑green celadons and red plum In saturated irons 8 to 12 %.

  High Magnesia    OX ‑ Usually browns.

           RD ‑ Small amounts gives gray‑green matts and yellow‑green at 10 %.

  High Zinc                                          Dull muddy browns in 10 to 18 percent zinc at all temperatures and

                                                  atmosphers.

  High Barium  OX ‑ Similar to the alkaline. Rich yellow‑green, yellow to effects, cold yellow to

                                                  greens; small percents for brown.

           RD ‑ High calcium and barium based transparent glazes give delicate blue‑green

                                                  to turquoise.

                                                         Metallic  Dominant Firing Atmosphere   Resulting color(s)

Colorant                          Flux                    Oxidation (OX) or Reduction (RD)

 

IRON CHROMATE

                                                       Used with all fluxing agents. In all conditions and temperatures produces

                                          grays, browns, and iron blues. Often a base for making black glazes and

                                          stains.

         MANGANESE

Alkaline         OX ‑ Violet, grape purple to red‑blue plum; some alkalines give browns or violet

                                          browns at all temperature and atmospheres.

Lead                          OX‑ Reddish brown to brownish violet (threaded with light and dark specks); In

                                          large amounts will blister.

                  RD‑ Not reduced.

Boron          OX ‑ Reddish purple‑brown to reddish brown at all temperatures and atmosphers.

High Magnesia                                  Lighter or pastel like effects of browns and violet‑browns at all temperatures

                                          and atmospheres.

High Zinc                                          Browns at ail temperatures and atmospheres.

High Barium         OX ‑ Delicate pink, violet, reddish violets, to red wine.

                  RD ‑ Violet, blue, to brown.

Barium and Alkaline                                        At low temperatures gives pink.

         NICKEL

Alkaline         OX ‑ Gray, brown, or greens; with barium gives violet to red‑brown. Refractory In

                                          large amounts.

Lead/Boron/or Magnesia ‑ Grays and browns at all temperatures and atmospheres.

High Zinc                Sometimes blue to violet; grays and browns at all temperatures and atmo­

                                spheres.

High Barium OX ‑ Gray‑browns.

         RD ‑ With a small amount of zinc will give red‑violet to blues.

         RUTILE

Alkaline OX ‑Iron type colors of pale tans or grays.

         RD ‑ Varies from tan, light blue straw to light brown to orange. Crystalline

                                effects.

Lead               OX ‑ Smooth and even colors of straw to tan.

         RD ‑ Not reduced.

Boron                    Very active streaking and mottling; tans to yellows at all temperatures and

                       atmospheres.

High Magnesia        Mottled and matt tans at all temperatures and atmospheres.

High Zinc                Low alumina and slow cooling for crystalline, crystal, and rutlie/zinc malts;

                                dull tans at all temperatures and atmospheres.

High Barium OX ‑ Tans to yellows.

         RD ‑ Pale blues.

         TIN

Chrome based OX/RD ‑ Pinks.

VANADIUM

Alkaline OX ‑ Various yellows; best at 8 to 10 percent at medium to low temperatures.

         RD ‑ Not reduced.

Lead               OX‑ Pasty pale yellow to bright yellow.

         RD‑ Not reduced.

Boron/Zinc/or

Magnesia               Pasty yellows or grays at medium to low temperatures.

         RD ‑ Not reduced.

High Barium OX ‑ Strong yellows at medium to low temperatures.

         RD ‑ Can be lightly reduced.

IRON based minerals

Clay minerals containing a high percentage of Iron including rutile, raw sienna, sienna, burnt sienna, raw umber, umber, burnt umber, and yellow ochre. These are forms of ochreous earth. Albany slip and barnard clay are more glaze/clay like. The result is translucent or opaque due to the clay Impurities and the Iron generates typical Iron colors of tans, browns, blacks, and iron blues in all the glaze conditions.

METALLICS

 

Color, as we know it, Is an effect produced on the eye and its associated nerves by various wave lengths. Light reflected or directed to the eye stimulate the different color cones of the retina creating the perception of the various colors. When light strikes an object, some of It Is absorbed and some Is re­flected while the color of a solid or transparent object Is determined by the wavelength of the light trans­mitted. Pigments (metallics) are mixed with the glaze, overglaze, engobe, enamel, and such to give color. Often times the metailica are oxides and carbonates, but other forms are used including carbides, chlo­rides, nitrates, phosphates, silicates, sulfides, and sulfates. It should be noted that paint pigments and ceramic colorants are different In that paint pigments respond to color mixing, while ceramic colorants respond to both heat and chemistry involved.

Examples of non pigment results of using metallics in ceramics follow. Iron of 1 percent of iron added to a glaze fired reduction = celadon and 14 percent = brick red‑black at C/11 and In oxidation, 4 percent = light tan, 6 percent = brown, and 10 percent = black; 4 percent iron and 6 percent rutile = blue. Copper at 1 percent in oxidation = light green but = bright blood red in reduction. Chrome at 2 percent chrome at C/OS = orange‑red but = dull green at C/8. These are not unusual examples for many factors affect the resulting color Including: temperature; acid/alkaline composition of glaze; type of flux; amount or lack of zinc, barium, magnesium, or tin; location In kiln; underfired or overfired; thickness of applica­tion; composition of clay body; atmosphere (oxidation, neutral, and reduction) control; other glaze over, next to, or adjacent; cooling cycle; length of firing; and whim of the kiln gods.

Opacify Is the state of being opaque and there are various levels starting with opaque (no light passing through), translucent (some light passing), to transparent (clear) with various in‑betweens. Dis­tinct levels of opacity is achieved by introducing differing amounts of opacifiers like zircon, zircopax, tin, zinc, and at low temperature antimony for white and/or metallics for colors. The following chart lists the mineral, use, color, and any remarks on metallics.

 

FIGURE 11 ‑ COLOR AND OPACIFIER CHART

 

Mineral   Use   Color   Remarks

Antimony oxide    Lead glaze   Yellow   Primarily an opacifier

   Sb203   Iron/lead glaze   Orange

      Stain   Yellow   With rutile or titanium

      Stain/glaze   Pale green   Chrome oxide and lead

 

Barium chromate            Overglaze   Lemon yellow   All low fire

   BaCr04   Borax glaze   Lemon yellow, pale green

      Alkaline glaze   Lemon yellow, pale green

Cadmium sulfide                Glaze colorant   Yellow, orange   Unreliable above C/010

   CdS   Borax glaze   Red   Used with 2096 selenium

      Stain   Yellow, orange, red   Up to 832oF with selenium and

                            sulfur

Chromium oxide                  Stain, underglaze,   Chrome green   Turns brown If zinc present

  Cr203             glaze, overglaze

    Tin glaze  Pink  Has blue cast If zinc is used

    Stain, glaze  Green‑blue, olive green        Addition of cobalt, nickel, Iron,

                                              and/or copper

    High lead, low  Chinese red  Low temperatures

                        alumina glaze

    High lead & sodium             Yellows  Low temperatures

    High zinc and/  Browns  All temperatures

                        potassium

Cobalt oxide      Stain, underglaze,       Blue, violet  Very powerful colorant

  co 03               glaze, overglaze

  Co 63   Underglaze  Black  With Iron chromate

    Boric glaze  Pink, pink‑violet  Low temperature with Mg0

    Sodium glaze  Green  C/15 glaze

 

COLOR AND OPACIFIER CHART

 

Mineral                        Use                        Color                        Remarks

Copper oxide                        Lead glaze                        Grass green                         Large amounts yield gun metal

  Cu0  Alkaline glaze  Turquoise  All temperatures

    Glaze  Red, purple, blue  Reducing atmosphere with 1% tin

    Tin glaze  Turquoise or robin's

                          egg blue

    Zinc glaze  Grass green  Zinc In glaze Increases brilliance

                            of color

    Stain  Green, blue  Low alumina stains

Gold  Paste, liquid, or  Gold  Low temperature

  Au  powder for overglaze

Gold chloride  Glaze  Gold luster  Low temperature, reduced

  AuCl3  Glaze  Purple, rose, red  Low temperature with tin

 

Iron chromate                       Underglaze                       Brown                        With manganese or zinc at low

FeCr04                                                                         temperature

                     Underglaze, body                     Black                     With Cu, Co, Mg0

                                          stain

                     Overglaze                     Dark pink                     Low temperature

                     Tin glaze                     Dirty pink, pink‑brown                     Low temperature

 

Iron oxide                       Lead glaze                       Straw yellow to light                        Oxidizing atmosphere

FeO                                   brown

                    Leadless glaze                    Brown to red‑brown

                    Borax                    Goldstone                    Saturated 12% plus

                    Opaque glaze                    Cream

                    Matt glaze                    Red‑orange                    With titanium C/11‑13

                    Body stain                    Red, yellow, brown

Celadon     Greens, blues, olives      Reducing atmospheres under 2%

Glaze     Blues     Glaze with lithium, barium,

          magnesium

Glazes, stains     Blacks      Saturated over 10% with Co, Cu, Mg

 

Lead chromate                      Basic flux in glaze                      Coral, red                       Low temperature

  PbCr04  Body stain  Green

    Acid flux In trans‑  Silver yellow  Low temperature

                        parent glaze

    Stain, glaze  Pink  With tin, low temperature

Manganese oxide Body stain  Red, purple, brown, black

  Mn02  Alkaline glaze  Plum

    Lead glaze  Light pink‑tan, dark

                       brown, red‑purple

    Glaze, stain  Black  Large amounts or with Co, Cu

    Underglaze  Brown  With iron chromate

    Glaze, stain  Intense black  With cobalt

    Glaze  Violet  Leadless alkaline glaze or zinc and

                         calcium glaze

Nickel oxide  Glaze  Blue, green, gray,

  NIO                brown, yellow  Unreliable, hard to handle

    Stain  Olive green  With cobalt and iron

    Glaze  Gray‑blue  High zinc (20%) over C/4

Stain, glaze    Yellow, blue, greenish     High zinc/barium base

 

COLOR AND OPACIFIER CHART (Continued)

 

Mlnerat                        Use                        Color                         Remarks

 

Platinum                        Glaze                        Steel gray luster                         Preferable to silver

Pt                     Overglaze, luster                     Silver                     Will not tarnish, available in liquid

                                                               form

 

Ruble                        Stain, glazes                        Ivory, yellow, brown                         A crude titanium and Iron

   TI02 (.2Fe0)      Glazes   Brown, blue

      Over 8 percent

      Glazes   Broken tans, opaque   2 to 8 percent

Selenium   Borax glazes   Pink or fire engine red   With cadmium

   Se                     Black   Over C/10

 

Silver                       Paste or powder                       Silver                       Tarnishes easily, not available in

Ag                       for overglaze                       liquid form

 

Silver chloride                       Glaze                       Yellow, purple, silver                        Low temperature, reducing

AgCl                      luster

 

Tin oxide                       Opaque glaze                       Pink‑maroon                        With chrome

Sn02                    Glaze                    White                    Opacifier, 2 to 10%

                    Glaze                    Yellow                     With vanadium

 

Titanium oxide                       Matt or crystalline                       Light cream to dark Ivory                        Oxidizing

1102                    Glaze                    Gray or blue                    Over 5%, reducing

                                                            atmosphere

 

Uranium dioxide Lead glaze                      Hot yellow, orange                       Low temperature

U02                    Alkaline                    Cool yellow, green

                    Glaze                    Yellow                    High temperature, 8%

                    Glaze                    Jet black or gray                    Reducing atmosphere

                    Lead glaze                    Red                     Pb, Zn, SI base no Ca, B

 

Vanadium oxide Glaze                      Yellow, bluish‑green                       A substitute for uranium, large

Va02                      amounts of tin or Zr

 

Zinc oxide                      Glaze                      Off white to cream                       Adds whiteness and brilliance to

  Zn02                 some colors

    Glaze  Matt, white  At 5 % or more

Zircon oxide  Glaze  White  Made up as a silicate frit

  Zr0  (Drcon G, Superpax, Zircopax, Opax)

 

COLORING CLAY BODIES

 

Coloring the clay body is a way to obtain a diversity to one's production assortment. Metallics as

well as stains are mixed in clay to give color but the range of color is less than glazes. Wedgwood pro­duced "marbleware" by mixing colored balls of clay together, slightly wedging it, and when scraped It after throwing to produce the agate, marble, or Zebra patterns. In slip casting two or more colored clays were poured at the same time resulting in similar types of patterns. Metlach's factory produced cameo by slip casting a basic shape in colored clay (blue, tan, brick, black) and sprig molded design and figures In contrasting colored clay (cream, white). These were placed on the basic shape In low relief producing cameo.

            In making of porcelain, white earthenware, and white stoneware, the purest of clays, fluxes, and silicas are used to avoid dirtying the whiteness of the clay. Commercial clay bodies that are colored use natural clays containing iron, or manganese to produce the gray, tan, brick red, brown, and chocc;ale colors. It Is cheaper to use natural colored clays rather than adding metallics. The metallics red Iron oxide, black Iron oxide, Iron chromate, magnesite, manganese dioxide, Ilmenite, and granular iron are the most common additives and are the cheapest colorants. Granular Iron, Ilmenite, and magneslte produces speckles while some sand and grog have traces of iron resulting In scant speckling. At lower temperature a colored clay may be brighter but darker at higher temperatures.

 

FIGURE 12 ‑ COLORANTS IN CLAY BODY

 

Metallics                        Percent                        Oxidation Firing                        Reduction Firing

Antimony oxide, sulfide                        2                                                                      ‑ 8%                        Off white                        Cream

Albany slip                        5                                                                      ‑ 15 %                        Cream to brown                        Cream to brown

Barnard clay                        5                                                                      ‑ 15 %                        Cream to chocolate                        Cream to chocolate

Brick, red (30 mesh)                        1                                                                      ‑ 10 %                        Light tan to dark specks                        Light tan to dark specks

Cerium oxide                        4                                                                      ‑ 10 %                        Warm pink                        Pinkish

Chrome oxide                        1                                                                      ‑ 5 %                        Light green to chrome green                        Grayed light green to gray olive

Copper oxide, carbonate                                  1                                              ‑ 5 %                        Light green to olive green                        Light green, red, green‑black

Cobalt oxide, carbonate                                  .6 ‑ 4 %                                    Light blue to dark blue                        Light blue to dark blue

Iimenite, powder                        1                                                                      ‑ 8 %                        Cream to light brown                        Buff to grayed brown

Ilmenite, granular                                    .5 ‑ 4 %                                    Few to heavy specks                        Few to heavy specks

iron red, black                        2                                                                      ‑ 10 %                        Pink to dark brick red                        Pinkish to medium brown

Iron chromate                        1                                                                      ‑ 8 %                        Light tan to medium brown                        Light grayed tan to grayed

brown

Magneslte, granular                                    .5 ‑ 4 %                                    Light to heavy specks                        Increased size of specks

Manganese dioxide                        1                                                                      ‑ 8 %                        Light tan with specks to                        Light grayed tan with medium

                                                                                                                        brown with specks                                      specks to grayed brown

Nickel oxide, carbonate                        1                                                                      ‑ 6 °/a                                Light tan to dark tan                        Light tan to grayed tan

Potassium carbonate                        2                                                                      ‑ 7 %                        Light green to medium olive                        Light green to dark green

Ochre, yellow                        1                                                                      ‑ 8 %                        Light tan to medium tan                        Light tan to cool medium tan

Rutlle, ground                        1                                                                      ‑ 8 %                        Light tan to medium brown                        Light grayed tan to grayed

brown

Rutlle, granular                          .5 ‑ 6 %                                    Few to heavy speckling                        Few to heavy speckling

Tin oxide                        2                                                                      ‑ 10 %                        White and opaque                        Whiter and opaque

Uranium oxide, sulfate                        2                                                                      ‑ 6 °/a                                Pink to tanish                        Light gray to gray

Vanadium pentoxide                        1                                                                      ‑ 5 %                        Slight tan to gray                        Slight tan to grayed olive green

Zirconium (commercial                        1                                                                      ‑ 10 %                        White and opaque                        Whiter and opaque

opaclfiers) ‑ Zircopax, Opax

 

COLORANTS USED AS WASHES FOR PIT FIRING,

SAGGAR, AND OPEN FIRING

 

Mixing colorants with water and then brushing, spraying, atomizing, spattering, or sponging to wet, damp, dry, bisque ware, and some cases over glazed ware giving random patterns on a pot will produce distinct effects. These effects range from matt black, luster, mother‑of‑pearl (unsmoked), rainbow, bright or metallic spots to subtle pastel colors. The colorants, mostly metaliics, are mixed with water (and small amount of glue), and screened In 80 to 100 mesh screen. The result depends upon the firing, amount of reduction, temperature, and thickness of application. The following is a basis for testing.

 

   A. Copper carbonate 50                D.                 Yellow ochre               70                G.        Potash dichromate             60

     Red Iron oxide        50                        Copper carbonate 30                         Copper carbonate 20

                              100                              100           Rutile             20

                                                                 100

    B. Copper carbonate 60    E. Copper carbonate 90

Red Iron oxide             30                      Cobalt carbonate             10                      H.             Red Iron oxide             70

Cobalt carbonate             10                                   100                                 Copper carbonate             30

             100                                                                        100

                          F.                       Copper sulfate*             100

C. Silver nitrate*                  100                  * Fumes are dangerous

 

COLORANTS IN GLAZES

 

Cobalt = green. chrome = green, tin = white, and the list goes on. By grouping several colorants to­gether the resulting color can be modified giving more interest, variety, and choices. In particular many glazes for electric firing are bland but they can be given more interesting effects by grouping. The fol­lowing colorants combinations are added to base glaze (white, translucent, or transparent) that can be further developed.

FIGURE 13 ‑ COLORANT GROUPINGS FOR GLAZES

 

Colorant   Percent   Colorant   Percent   Colorant   Percent

   Broken Blue                Broken Brown

Cobalt carbonate                .'                                Red Iron oxide                1.0                            Dark Broken Greens

Rutile                1.5                Manganese carbonate 4.0                            Manganese dioxide                2.0

Granular Ilmenlte .3   Rutile 2.0   Chrome oxide  1.0

                                     Copper carbonate   4.0

   Orange Brown          Speckled White

Red Iron oxide    2.5   Tin oxide   2.0            Black

Tin oxide   1.0   Granular magnetite   .5  Black Iron oxide   7.0

Rutile   2.0                      Cobalt oxide  1.0

Granular magnetite   .4             Broken Rust            Manganese dioxide   3.0

                   Red Iron oxide    8.0   Granular magnetite   .3

   Broken Greens         Manganese dioxide   1.0

Chrome oxide    1.0   Zircopax   4.0

Copper carbonate   3.0

Rutile  4.0

 

OPACIFIERS

 

Opacity occurs when a glaze contains suspended particles of a material that have a different refractive Index (the ability to bend light) from the glaze matrix. These particles cause the light rays to be diffused or the surface of the glaze has crystals that reflect the light causing the glaze to be opaque. One major way to render a glaze opaque Is to suspend undissolved particles or crystals on or In the glaze. Gas bubbles suspended In the glaze can also make the glaze opaque. The amount of opacifiers entered In the glaze will determine the degree of opacity. Often, too high a percent of opacifiers will render the surface rough or act as a refractory material.

Cost of materials Is a consideration for tin oxide is expensive and to make a glaze white requires about 5 percent. The same whiteness using zirconium based opacifiers takes 10 percent with the total cost cheaper for zirconium stain. The other factor Is that tin Is a warmer white compared to the stain a cooler white. A cheaper and good compromise is 2 percent tin and 5 percent zir­conium stain. Chun and other glazes rely on trapped minute bubbles for the translucent opalescence, but a too thin glaze application, prolonged glaze soaking, over firing, or refiring will cause the bubbles to dissipate.

The following chart shows various opacifiers, the resulting color, percentage, temperatures used, atmo­sphere, and a guide for the glaze (acid, neutral, alkaline), soaking period, and glaze thickness.

 

FIGURE 14 ‑ OPACIFIER CHART

 

Qpacifier                                   Color                        Percent                        Temperature                        Atmosphere

AIR BUBBLES                             Whitish                                     Any                        Either

                        Chun and similar glazes rely on trapped minute bubbles to produce translucent and

                        opalescence. Bone ash Is the major mineral us= ~ for this type of glaze.

ANTIMONY                        Weak yellow‑white                        8 ‑ 12 % Under C/1                        Oxidation

                        Low and medium temperatures, when used with lead, forms lead antimonate, a yellow

                        opaque color.

BONE ASH                        (see air bubbles)

 

CALCIUM FLUORIDE                                  Off white                        5 ‑ 8 % Up to C/11                        Either

                        Disadvantages ‑ May blister or pinhole in some glazes

COMMERCIAL FRITTED OPACIFIERS:

Calcium zircon silicate, magnesium zircon silicate, zinc zircon silicate, Zircopax, Uttrox, Superpax, Opax

Whites       4 ‑ 18 % Any        Either

 

RUTILE                                   Buff to brown                       1 ‑ 12 % Any                       Either

                       Advantages ‑ will produce crystal and crystalline finishes to glaze

                       Disadvantages ‑ may dissolve in melt; pulls out color from the clay body; has a ten­

                       dency to produce matt finish; may cause mottling of colors; subdues colors; gives

                       yellow color to the glaze.

TIN OXIDE                               Pure white                       3 ‑ 8 % Any                       Either

                       Advantages ‑ dependable, does not dissolve In melt, provides the whitest and

                       cleanliest colors.

                       Disadvantages ‑ pink tinge near chrome or copper In firing, expensive, in heavy

                       reduction gives gray cloudiness to the glaze and colors

TITANIUM                               Weak blue‑white                       8 ‑ 12 % Any                       Either

                       Advantages ‑ will produce crystal and crystalline finishes.

                       Disadvantages ‑ will dissolve In melt; precipitates out of the glaze during cooling,

                       thus must cool slowly; pulls out color from the clay body; has a tendency to produce

                       matt finish; may cause mottling of colors; subdues colors.

ZINC OXIDE                             Whitish to yellow                       4 ‑ 12 % Any                       Either

ZIRCONIUM                             White                       %‑ 12 % Any                       Either

                       Light gray‑white up to 750 C, then whiter over this temperature (Zircon G, Superpax,

                       Zircopax, Opax). Gray‑white color up to 1300° C, more white over this temperature.

                       Advantages ‑ Dependable, little dissolves in melt, provides white and clean colors,

                       does not accept pink tinges like tin oxide.

                       Disadvantages ‑ In heavy reduction gives slight gray cloudiness to the glaze and

                       colors.

                                              FIGURE 15 ‑ RELATIVE REFRACTIVE OPACIFIER INDEX

 

Opacifier                     Refractive Index                     Ocacifier                     Refractive Index                     Opaciner                      Refractive Index

Air                     1.00                     'Lead antimonate                     2.20                     Titanium oxide                     2.56

Antimony oxide                     2.10                     Rullite                     1.65                     Wollastonite                     1.61

Arsenic oxide                     2.20                     Quartz                     1.55                     Zircon                     1.96

Calcium phosphate                     1.63                     Sodium fluoride                     1.34                     Zircon based frit                     1.88

Cristobalite                     1.48                     Tin oxide                     2.00                     Zirconium oxide                     2.20