Tag: Glaze testing

Zinc Things

Zinc
Zinc

I got a lot of responses after my last post, where I made the claim that using zinc is hard on elements. I had some really interesting discussions with both John Britt and John Tilton on this subject, and I thought I’d share some of that info with you guys. Of particular interest was a tidbit from Britt where he mentioned that firing a zinc sample in oxidation leaves it unmelted (as the melting temp is 3500) while the zinc sample in reduction almost entirely goes away. Heres a fired sample from our glaze calc class, fired in cone 10 reduction. It was a thumbnail sized lump when it went in.

Zinc Oxide
Zinc Oxide

To make a long story short, the juries out on whether or not zinc directly reduces the life of kiln elements. What’s most likely is that it’s a combination of complex volatilizing compounds released during the firing coupled with high temperatures (especially if there are programmed holds). An often overlooked variable is water. It could very likely be that the extremely hard water at my current and previous studios is the culprit. If you’ve ever looked closely at old workhorse kilns, some of the deposits near the lids and spy ports are similar to calcite deposits. Its not hard to imagine Calcium and Flouride attacking the elements.

Another variable to consider is that the kilns that I’ve had access to for my entire career have been heavily used community kilns. At research universities there’s a huge range of clays and glazes that go through kilns. I’ve also heard that barium, cobalt, and copper are also hard on elements. Given all these extra variables, I suppose the only real way to quantify if and how much zinc affects elements would be to fire two brand new kilns side by side for a 100 or so firings and then compare. Let me know if you have two brand new kilns you need me to test. I’ll be happy to help you out!

On a related note, John Tilton had some great info on kiln elements. I hope he doesn’t mind me sharing the info – it seems very useful. From an email from Tilton:

The zinc thing is somewhat solved by using heavier elements. I have 11 gauge KA1s in my newest L&L, and after 104 firings they are still standing nicely. 12 gauge seems to give about 200 firings, and 13 gauge 80. Normal elements, the 16 gauge or so, give between 18 and 35 firings, not worth using. I also fire only one or two pots at a time so the total zinc load per firing is probably less than if you stacked tightly.

So it looks like 11 gauge might be the sweet spot, though they do require length to be resistant enough, and maybe that translates into coils of larger diameter.

Finally, I’ll leave you with the Material description from Digital Fire. I highly recommend consulting digital fire for material descriptions, and if you have the means, purchase access to the software. So worth it. From Digitalfire.com

Zinc Oxide

Pure Source Of Zinc

Formula: ZnO
Alternate Names: ZnO, Zincite

Oxide Analysis Formula
ZnO 100.00% 1.000
Oxide Weight 81.40
Formula Weight 81.40
Enter the formula and formula weight directly into the Insight MDT dialog (since it records materials as formulas).
Enter the analysis into an Insight recipe and enter the LOI using Override Calculated LOI (in the Calc menu). It will calculate the formula.
DENS – Density (Specific Gravity) 5.6

Zinc oxide is a fluffy white to yellow white powder having a very fine physical particle size (99.9% should pass a 325 mesh screen). It is made using one of two processes that produce different densities. The French process vaporizes and oxidizes zinc metal, the American process smelts a coal/zinc sulfide mix and oxidizes the zinc fumes.

Ceramic grades are calcined, they have a larger particle size and much lower surface area (e.g. 3 square meters per gram vs. less than 1; however 99.9% still passes 325 mesh). Calcined grades are said to produce less glaze surface defect problems (although many ceramists have used the raw grades for many years without serious issues). You can calcine zinc on your own in a bisque kiln, fire it at around 815C. Calcined zinc tends to rehydrate from atmospheric water (and get lumpy in the process, calcining a mix of zinc and kaolin produces a more workable powder). Alot of zinc is used in crystalline glazes (typically 25%), because these have no clay content, they bring out the best and worst of both the calcined and raw materials. The raw zinc suspends glazes much better (the calcined settles out much more). The raw zinc takes more water, but since the glaze can thin out over time it is better to add less than needed at mixing time and mix thoroughly. The raw zinc screens better (although it can be a challenge to get either slurry through an 80 mesh screen).

Zinc oxide is soluble in strong alkalies and acids.

It can be an active flux in smaller amounts. It generally promotes crystalline effects and matteness/softness in greater amounts. If too much is used the glaze surface can become dry and the heavily crystalline surface can present problems with cutlery marking. Other surface defects like pitting, pinholing, blistering and crawling can also occur (because its fine particle size contributes to glaze shrinkage during drying and it pulls the glaze together during fusion).

Zinc oxide is thermally stable on its own to high temperatures, however in glazes it readily dissolves and acts as a flux. Zinc oxide sublimes at 1800C but it reduces to Zn metal in reduction firing and then boils at around 900C (either causing glaze defects or volatilizing into the atmosphere; note that electric kilns with poor ventilation can have local reduction).

While it might seem that zinc would not be useful in reduction glazes, when zincless and zinc containing glazes are compared it is often clear that there is an effect (e.g. earlier melting). Thus some zinc has either remained or it has acted as a catalyst.

The use of zinc in standard glazes is limited by its price, its hostility to the development of certain colors and its tendency to make glazes more leachable in acids (although zinc itself is not considered a hazardous substance).

Zinc oxide is used in glass, frits, enamels and ferrites. Zinc oxide is also used in large quantities in the rubber and paint industries; in insulated wire, lubricants, and advanced ceramics.    Credit: Tony Hansen

Thanks to Tony, and John Tilton. Also a special thanks to John Britt for the feedback on my last post; the clarification on Feldspar (I was mistaking K200 for Minspar 200 – ignorant to the fact that K200 has been out of production for 20 years!) I’ve since edited my post on Cone 6 with this info.

Rainbow Iridescent OilSpot Glazes

Hello Again! It’s been quite some time since my last post. Gotta thank those of you who have contacted me with interest and suggestions! With so many summer projects and school stuff, it’s been very difficult to put my full efforts into any one thing… but life is what happens while you’re making plans.  Anyways, enough with the excuses.

Over the summer I had the time and energy to figure out an acceptable firing schedule in our new Blaauw kilns.  For as much as I love their sleek and sexy design, computer controllers, and top of the line hardware… you can’t look in the damn things while they’re firing. This poses several challenges for control freak oil spotters. Usually, the idea is to firein complete and total oxidation, going slowly through cone 7,8,and 9 to allow thermally reducing iron to bubble up through the glaze and cause the surface to crater or foam. By carefully monitoring the situation inside the kiln, and by pulling out glazed pull rings, the firer can increase the temperature slowly and fire until the glazes have significantly ‘healed over’. This isn’t really an option, so as a result a much more empirical approach was needed to find a good fit.

After 5 firings, I settled on a more or less acceptable firing schedule (the way this programming works is that the kiln starts at 0, take 1:30 to get to 200C, then 2:30 to get to 700C, etc). In Celcius;

time_temp 00:00 5

time_temp 01:30 200

time_temp 02:30 700

time_temp 03:00 1115

time_temp 02:00 1190

time_temp 02:30 1230

time_temp 02:30 1253

cooling

time_temp 02:00 1000

time_temp 02:00 500

time_temp 02:00 300

time_temp 02:00 50

time_temp 04:00 50

 

Once that was established, I began with some of my favorite tiles from my initial 2 rounds of oilspot base glaze recipes. My favorites:

 

NoCo OS:  (NC)

Dolomite 4.4

Whiting 4.4

K200 Feldspar 57.3

EPK 9.7

200m Silica 24.2

Spanish FeOx  10

 

Candace Black:  (CB)

Dolomite          5

Whiting           5

K200 Feldspar 60

EPK                       5

200m Silica  20

Spanish FeOx  8

Cobalt Carb       5

 

Loganspot: (LS)

Local Black Dolomite 10

K200        65

EPK          5

Silica     20

Cobalt      5

Red Iron  8

 

Fake Mashiko: (FM)

K200  37.6

Silica  9

Redart  8

Calcined Redart 35

Wollastonite   5.7

Talc    4.3

Bone Ash  .5

Red Iron   4

 

With these base glazes I began mixing, blending, and layering, and combining glazes with dipped, poured, and sprayed application.  On a whim I decided to experiment with some of my manganese saturate glazes, and that’s when things started to get really interesting. There is admittedly one glaze in particular that I’m not sharing, but with a little diligence and some wet blending, a seriously motivated glaze experimenter can discover this glaze by  looking at my old posting on my OSII series. Blend them all in 50/50 proportions and you’ll get the elusive but beautiful  GF glaze. Hell, it might even be on my blog somewhere. That’s all I’m saying for now – I’d hate to rob anyone of the learning experience… Hah! =)

 

Recently I was contacted by the British potter Allen Richards who has done some pretty extensive research into lustrous gold glazes. He suggested that I try small additions of Vanadium Pentoxide. These glazes feature 2 amended manganese saturate glazes in combinations with the usual oilspot suspects.

 

 

 

 

Here are some videos of some of my latest results. None of these particular tiles have Vanadium pentoxide.  As time goes by I’ll try to annotate the combinations MS corresponds to Manganese Saturate.

 

 

Iridescent Hare’s Fur Tenmoku

Telluride via Moab

Jeepster parked next to a clay bank with Mount Telluride in the background.
Jeepster parked next to a clay bank with Mount Telluride in the background.

 

 Back in the studio after a great trip over to Telluride, CO via Moab, UT. You better believe I scooped up some of this clay, ball-milled it, and made a slip. I also packed the jeep with a load of rocks and shit.  More on that as the story develops!

 

Red Siltstone and Clay, Telluride, CO
Red Siltstone and Clay, Telluride, CO
The San Juan Rocky Mountains.
The San Juan Rocky Mountains.
Moab Red Rocks
Moab Red Rocks

New Pots, New Recipes

#6, #5, #4 Manganese Saturate Crystalline Glazes
#6, #5, #4
Manganese Saturate Crystalline Glazes

#4 Recipe & Schedule

Fisker Bronze
Custer Feldspar.............     57.000  
  Alberta Slip................    7.000  
  Sil-co-sil..................    2.500  
  F-4 Feldspar................    1.500  
  Calcium Carbonate...........    0.500  
  Dolomite....................    0.500  
  OM #4 Ball Clay.............    2.000  
  MnO.........................   23.000  
  Copper Carbonate............    5.500  
  Iron Oxide Red..............    0.500  
                              =========
                                100.000

  Oxide   Formula  Analysis    Molar%
  CaO      0.043*   1.129%w   1.376%m
  MgO      0.019*   0.348%w   0.590%m
  K2O      0.143*   6.237%w   4.528%m
  Na2O     0.071*   2.052%w   2.264%m
  P2O5     0.000*   0.007%w   0.003%m
  TiO2     0.001    0.055%w   0.047%m
  Al2O3    0.252   11.952%w   8.013%m
  SiO2     1.783   49.756%w  56.619%m
  CuO      0.099    3.670%w   3.156%m
  Fe2O3    0.013    0.955%w   0.408%m
  MnO      0.724*  23.839%w  22.995%m

                        Cost:   0.273
              Calculated LOI:   3.521
                 Imposed LOI:        
                       Si:Al:   7.066
                      SiB:Al:   7.066
           Thermal Expansion:   6.848

Fired in Blaauw Reduction Schedule (in Celcius):

time_temp 00:00 5
time_temp 00:54 140
time_temp 01:12 260
time_temp 01:10 550
time_temp 00:30 600
time_temp 01:12 900
oxidation 83
time_temp 00:45 900
oxidation 93
time_temp 03:06 1210
oxidation 98
time_temp 01:24 1270
cooling
time_temp 02:15 1000
time_temp 01:00 900
time_temp 02:00 500
time_temp 01:00 300
time_temp 02:30 50
time_temp 04:00 50

#5 Recipe & Schedule

  Nepheline Syenite...........   65.500  
  MnO.........................   22.000  
  Silica......................   12.500  
                              =========
                                100.000

  Oxide   Formula  Analysis    Molar%
  CaO      0.018*   0.465%w   0.559%m
  MgO      0.004*   0.067%w   0.112%m
  K2O      0.071*   3.036%w   2.175%m
  Na2O     0.228*   6.461%w   7.033%m
  Al2O3    0.330   15.361%w  10.163%m
  SiO2     1.913   52.523%w  58.975%m
  Fe2O3    0.001    0.072%w   0.030%m
  MnO      0.680*  22.014%w  20.953%m

                        Cost:   0.312
              Calculated LOI:   0.065
                 Imposed LOI:        
                       Si:Al:   5.803
                      SiB:Al:   5.803
           Thermal Expansion:   7.492
              Formula Weight: 218.874

Strike Reduction Hold Firing Schedule 
in Small Test Gas Kiln in F

3:30 -> 1500F (^012)
Body Reduction
1:00 -> 1700F (^04)
Adjust to Moderate reduction, fast climb
3:30 -> 2300F (^9 flat, ^10 down)
Crash Cool
0:15 -> 1840F
Cut secondary air, minimize primary air, damp in, gas low to strong reduction and stalled holding temp
3:00 -> 1840F (Hold)
Off, Natural Cool
6:00 -> 300F

#6 Recipe & Firing Schedule

  Custer Feldspar.............   69.000  
  OM #4 Ball Clay.............    1.500  
  MnO.........................   27.500  
  Granular Manganese..........    2.000  
                              =========
                                100.000

  Oxide   Formula  Analysis    Molar%
  CaO      0.007*   0.210%w   0.256%m
  MgO      0.000*   0.006%w   0.010%m
  K2O      0.140*   6.961%w   5.057%m
  Na2O     0.064*   2.091%w   2.308%m
  TiO2     0.000    0.018%w   0.016%m
  Al2O3    0.226   12.223%w   8.201%m
  SiO2     1.533   48.751%w  55.512%m
  Fe2O3    0.001    0.123%w   0.053%m
  MnO      0.789*  29.617%w  28.588%m

                        Cost:   0.297
              Calculated LOI:        
                 Imposed LOI:        
                       Si:Al:   6.769
                      SiB:Al:   6.769
           Thermal Expansion:   7.120

Fired in Blaauw Reduction Schedule (in Celcius):

time_temp 00:00 5
time_temp 00:54 140
time_temp 01:12 260
time_temp 01:10 550
time_temp 00:30 600
time_temp 01:12 900
oxidation 83
time_temp 00:45 900
oxidation 93
time_temp 03:06 1210
oxidation 98
time_temp 01:24 1270
cooling
time_temp 02:15 1000
time_temp 01:00 900
time_temp 02:00 500
time_temp 01:00 300
time_temp 02:30 50
time_temp 04:00 50

Iridescent Glaze Research

Download the full PDF of my research Paper:

Iridescent Glazes

Download the full Powerpoint of my research Presentation:

Iridescent and Manganese Crystalline Glazes

 

 

 

Text From Paper:

 

Matt Fiske

Technology of Ceramics, Glaze Calc

April 24, 2014

Iridescent and Manganese Crystalline Glazes

Manganese crystalline glazes (high alkali, silica, and alumina) are usually created by saturating a feldspathic glaze with between 15-60% manganese dioxide. During the cooling cycle, manganese precipitates out of the molten glaze and crystallizes on the surface, producing lustrous, satiny surfaces.

UNDERSTATEMENT: Manganese Dioxide is extremely hazardous to your health!!!

 Breathing in Manganese dust when mixing these glazes or breathing the off-gassing vapor when firing WILL GIVE YOU PARKINSONS-LIKE SYMPTOMS BEFORE ULTIMATELY KILLING YOU, PAINFULLY. HEAVY GLOVES, DUST MASKS, AND VENTILLATION ARE CRITICAL.

 

Historical Information

            There is a long history of lustrous, metallic glazes. The first examples are thought to be from the early ninth century in an around what is modern day Iraq. Archeological evidence suggests that early examples originated from Mesopotamia in Fustat, which was then the capitol or Egypt. The oldest surviving examples were often multi-colored stains and iridescent sheens derived from copper and silver compounds. These compounds were usually manufactured by dissolving coins into acids and then mixing the resulting solution with earthenware clay. This mixture was then calcined and then finely ground. The resulting pigment was then mixed with a carrier (usually lavender oil) and applied to lead or tin glazed pots and re-fired to dull red heat. The pots were then held in an extremely smoky reduction environment at various temperatures and lengths of time, which resulted in surfaces ranging from olive-green, brown, amber, orange, yellow, crimson, and a very dark red which was sometimes so dark as to look almost black.[1]

Although the history and development of reduced-pigment lusters is long and storied, it was a more or less consistent sequence. It isn’t until the 19th century that one starts to find examples of resinate lusters. This resulted in the development of materials almost identical to modern ‘liquid gold’ and ‘platinum’ lusters. In Europe in the 1870s a revival in the technology and development of luster glazes saw a further refinement of reduced glaze lusters, most notably in the studios of William De Morgan, Massier, Kähler, and Zsolnay. This notable shift was the result of the use of higher firing clays, which French ceramicist Louis Franchet believed could offer the complete range of earlier pigment-lusters, but without a lot of the trouble.[2] Aside from the obvious temperature differences, the main difference between pigment and reduced glazes is that glaze lusters are generally less subtle, less mellow, and offers a wider, more brilliant range of color.

Abstract

I began research on this project in an attempt to find a brilliant, iridescent glaze similar to Zsolnay’s famous Eosin glaze, which has a very obvious bright reflective rainbow iridescent quality. Initial research suggested that Zsolnay’s effects were the result of the thin application of copper, silver or bismuth to a pre-fired glaze – firing to fusion point, and then reducing the kiln atmosphere during the cooling cycle. This method is documented extensively in Greg Daly’s book Lustre. Having had some glimmers of success with iron saturate glazes in reduction cooling environments, I proposed a solution that did not; 1.) involve expensive silver or bismuth oxides, or caustic salts such as stannous chloride or copper sulfate, and 2.) involve a postfiring or overly exotic and difficult to repeat firing schedule. In the end, a satisfactory solution was some combination of feldspathic glazes with 30-60% Manganese Dioxide, following closely in the steps of David Shaner, Lucie Rie, Hans Coper, John Tilton, and historical Rockingham ware.

Definitions

Reduced-pigment luster. Nearly all historical luster made before 1800 fits in this category. The result of calcining copper, silver, and bismuth oxides with earthenware or laterite clays, and applying the resulting mixture to a maturely fired lead or tin glaze surface. The piece is then refired and held in heavy reduction at dull red heat allowing for a thin layer or metallic oxide to fuse with the surface of the glaze. After the firing, the earthenware is wiped away, revealing a nano-thick layer of iridescent metal.

Resinate luster. Usually made with dissolved gold, platinum, or other noble metals and suspended in an organic binder. Generally fired to a low temperature, with the organic compounds burning out and fluxing a thin, even layer of metallic oxides with the surface of the work. Developed around 1800, very common in industry, very toxic.

Reduced Glaze Luster­. Generally higher porcelain and stoneware temperature. Usually cover the entire surface of a form. Relies on metallic saturated glazes precipitating out thin layers of reduced metallic oxides which deposit in a thin layer on the top of the glaze. Generally more brilliant and operate across a wider spectrum of interrupted light.

Technical Information

            Materials: I found that nearly all of my iridescent surfaces contained some percentage of manganese. The exception is a traditional Tenmoku glaze fired in standard reduction, and then ‘struck’ at 1840F for 1:20-2:00 hours. Strike firing, or striking the kiln is a glass term which refers to increasing the fuel supply and thus creating a reducing atmosphere around 1800F. Initial tests suggested that manganese saturated glazes promoted richer iridescent surfaces regardless of a strike firing. Additions of other oxides were often counterproductive to glossy surfaces and generally resulted in unpleasant black, rough surfaces. Copper, Iron, Chrome, Nickle, and Cobalt were all tested alone and in conjunction from .1 -> 20%. The character of the underlying glass matrix of was usually beer bottle brown, so I tested extensively to change the color of the glass without effecting the iridescent surface – to date I still don’t have a simple solution to this problem. Granular Manganese seemed to produce brighter colors as well as promoting streaking ‘hares-fur’ effects in faster cooling, and acting as ‘seeds’ to crystal formation on slower cooling cycles. My ideal concentration of granular manganese was 2% and fine manganese dioxide at about 27%.

Most recipes called for 50-70% feldspar, and after testing all of the available feldspars, I found that Nepheline syenite promoted a much smoother, regular iridescence. Custer feldspar promoted iridescence across a wider spectrum, but promoted intense crystallization as to appear almost pixellated. Kona f4 promoted a more matte, golden green/purple sheen. Other feldspars promoted a lustrous brown glass with varying degrees of light to moderate iridescence.

The addition of silica promoted a lightening of the glass matrix, as well as a sugary, semi- shiny sparkling satin luster. Silica beyond 15% eliminated iridescence. Alumina additions to the glaze produced a semi-matt honey colored glaze.

I found that the clay body had a huge impact on the color and quality of the iridescence. The most successful clay bodies were grolleg based porcelains, with only the highest percentages of manganese based glaze recipes showing even the slightest luster on stoneware recipes.

Finally, glaze thickness was perhaps the most critical aspect of obtaining iridescence at high temperature. This was complicated as these glazes are extremely runny. Even slight overfiring resulted in glazes running off the pot. There was a need to find a balance between adding clay and silica to the feldspar and manganese without diluting the concentration of available metal oxides and feldspar. It was also extremely difficult to apply these glazes consistently, and fire them in such a way as to reach maturity without overfiring.

Firing: All tests were fired in high temperature gas kilns. I usually fired to 1260C, or Orton cone 10. A majority of my testing was in standard cone 10 reduction firing, with a 1 hour body reduction at cone 012-> cone 08, and a 6-10 hour firing from cone 08-> cone 10. Recipes with 15% copper produced a striking gold color in oxidation environments, and glazes in oxidation firings bubbled and boiled up between cone 7-9, which suggests a similar thermal reduction similar to oil spot glazes.

Cooling: Most of my firings were in small soft brick or fiber kilns, so the possibility of extended cooling cycles was limited. I found that crash cooling seemed to promote smoother, less brilliant surfaces, and a moderately fast cool was ideal in creating a balance between bright color and reasonably smooth surface. Longer cooling promoted larger crystals to a point, and excessively long cooling cycles promoted a matte surface. Reduction cooling remains an exciting possibility which mostly extended beyond the scope of my research. A very interested mottled crystal growth was observed on bottle forms cooled with a 3 hour reduction hold at 1840F.

[1] Caiger-Smith, Alan. Lustre Pottery: Technique, Tradition, and Innovation in Islam and the Western World. London: Faber and Faber, 1985. Print. Pg. 21

[2] Caiger-Smith, 1985, Pg. 177

[3] “Iridescence in Lepidoptera”. Photonics in Nature (originally in Physics Review). University of Exeter. September 1998. Retrieved April 27, 2012.

Bibliography:

Britt, John. The Complete Guide to High-fire Glazes: Glazing & Firing at Cone 10. New York: Lark, 2004. Print.

Caiger-Smith, Alan. Lustre Pottery: Technique, Tradition, and Innovation in Islam and the Western World. London: Faber and Faber, 1985. Print.Pg 149

Conrad, John W. Black Pearl and Other Saturated Metallic Glazes. Santa Ana, CA: Falcon Division of Aardvark Clay, 2010. Print.

Currie, Ian. Revealing Glazes Using the Grid Method. Australia: Bootstrap, 2000. Print.

Daly, Greg. Lustre. London: A. & C. Black, 2012. Print.pg. 131

Hamer, Frank, and Janet Hamer. The Potter’s Dictionary of Materials and Techniques. London: & C Black, 1991. Print.

Raw Materials in Cone 10 Reduction

From Utah State University Ceramics Technology Glaze Calculation Class.

Thanks to Shasta Kruger for Photographing, Editing, and Compiling These Images!!!!