Tag: crystal

Rhyolite and Basalt Glazes

I was beyond excited to work with my newest found material, a rhyolite from Topaz Mountain, in Juab Country, Utah.  This time rather than choosing a handful of very large rock samples (to insure relative material consistency), I instead went to a wash and filled up a 5 gallon bucket with very fine material the size of course sand. My reasoning this time was that consistency is completely relative, and as long as I get materials from the same spots, it doesn’t matter – and I can grab material that has already been 99% processed for me. In the end I think this worked out, because I was able to run 5 gallons of sand through our ball mill with 2x 1 gal. ball mill jars in 10 batches. But I’m getting a bit ahead of myself, because I think it’s important to test fire a material before you go through the trouble of ball milling. So my new first step in dealing with materials (after identification of course) is to take a small chunk, put it in a small dish, and fire to cone 10 in reduction. Since this is my primary temperature range, that’s it, if there are chances I’ll also put similar samples into cone 6 oxidation as well as an oilspot firing schedule, which is about cone 12 oxidation. Here was the result at cone 10, in reduction:

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A small rhyolite pebble after being fired to cone 10, in reduction.

 

Looks a lot like a fired chunk of granite or feldspar. Onwards with the milling!

Someone asked me about my process for ball milling, and here it is: Fill a 1 gal ball mill jar 1/3 with mixed sized media (approx 50% 1/4″ balls, 25% 1/2″ balls, 25% 1″ balls) then fill the jar with 1/2 gallon of water, then fill the the rest of the container up with material until it’s about 2/3 full.) If I had more containers I wouldn’t exceed filling the jar 1/2 way, but my circumstances are what they are, and I haven’t needed to change anything yet, such as it is.

In reduction, this rhyolite material was surprisingly similar to my ice crackle glaze. I think with very little modification (a small addition of clay, bone ash, and maybe a bit of frit) I’m nearly positive this will look and feel like a Kuan, ice crackle glaze.

Rhyolite Glaze on a high Iron clay body. Fired to cone 10 in Reduction.
Rhyolite Glaze on a high Iron clay body. Fired to cone 10 in Reduction.

Once I had all of my material milled, I let it sit overnight and then drained off the excess water, leaving me with a glaze slurry with an SPG of 1.58 (That’s 79g of material in a 50cc syringe). That’s only important if you want to know how much material you have per given volume. Since I was going to blend this with a basalt material that was also in solution, I needed this info. After taking the SPG of my basalt material, which happened to be 1.54, I did a simple line blend. On both sides are the materials by themselves, in the middle a 50/50, and on the left and right middle 25/75.

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Rhyolite/Basalt line blend. Red stoneware (top row) and porcelaineous (bottom). Fired to cone 12, oxidation.

 

Pretty interesting results, I think. The big surprise was how sweet the 25% Basalt and 75% Rhyolite mix came out.

1 part Basalt, 3 parts Rhyolite. Fired to cone 12 oxidation.
1 part Basalt, 3 parts Rhyolite. Fired to cone 12 oxidation.

Finally, because I was looking for an oilspot/tenmoku type glaze with this research, I should also detail my firing schedule. Here’s my current Blaauw gas kiln firing schedule:

0 time_temp 00:00 5
1 time_temp 01:30 200
2 time_temp 07:00 1160
3 time_temp 01:30 1200
4 time_temp 01:00 1220
5 time_temp 02:00 1230
6 time_temp 01:15 1252
7 oxidation 80
8 time_temp 00:08 1252
9 oxidation 150
10 time_temp 00:30 1220
11 time_temp 01:30 1200
12 cooling
13 time_temp 02:00 1000
14 time_temp 02:00 800
15 time_temp 02:00 700
16 time_temp 02:00 500
17 time_temp 02:00 300
18 time_temp 02:00 50
19 time_temp 04:00 50

Blaauw kilns have the capability of firing in extremely oxidized conditions – blowing in somewhere to the tune of double the amount of air needed for complete combustion. The default, and maximum air value is 200. An neutral flame is around 100, and a smoky reduction is something like a 70.

Basically, this program fires up to cone 6 in about 9 hours, and then goes slowly up to 1252C, reduces for 8 minutes, and then goes back to oxidation, drops to 1220 over the course of 30 minutes, then drops to 1200 over the course of an hour and a half.  I’m still very much tweaking this schedule, which works very well for some glazes, and not so much for others.

Basalt

A Basalt Quarry near Paul, Idaho.
A Basalt Quarry near Paul, Idaho.

For a very long time now I’ve wanted to utilize some volcanic rock as glaze. In much of my research here at Utah State I’ve been looking at iridescent phenomena, both in glazes and in the natural world. It was quite fortuitous, then, when geology grad Doug Jones asked me to accompany him on an excursion just over the border into Idaho to look for Xenoliths, which at this site are very deep mantle rocks that have been blasted quickly to the surface in younger volcanic flows.

While we were poking around looking for Xenoliths, I started picking up some rather remarkable chunks of iridescent vesicular basalt. Vesicular basalt is characterized by it’s frothy, bubbly matrix… if you don’t know what I’m talking about, think red lava rock. It’s one in the same. Here’s an example:

Vesicular Basalt
Vesicular Basalt

After picking up a good pile of this stuff, we went on to find about 40 Xenoliths, as well as some other interesting stuff.

 

Basalt with Quartz Clusters
Basalt with Quartz Clusters

Once I got back to the studio it was time to figure out if this stuff was even viable. My standard go to for this is to break off a small chunk, put it in a dish, and fire away.

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After putting theses samples in a cone 10 reduction kiln and a cone 10 oxidation kiln, it became quite evident that I had something useful.

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Fired Samples

After deciding that this was a good road to go down, the hard work of crushing and processing this stuff began. I started by breaking the boulders down into gravel sized pieces. These then went into out ball mill. I could have shaved down the time it took to mill this stuff by using intermediate crushing equipment (an impact mill, or hammer mill) but I found it easier in the long run to load up our ball mill and run for about 24 hours, sieve out the useful material, add in more course material, and repeat. By the end of 4 days I’d run all the material through and was left with tumbled lava rock:

With my material milled down fine enough to pass easily through a 100mesh sieve, I then let it sit for a few days, pouring off the water each morning, until gradually the material became thicker and started to resemble a glaze. Because it was ball milled, the particles were quite small, and suspend really well.  The next step was to take this glaze material and see what happens in the kiln. I was quite pleased:

Basalt Material fired to 1250C in Reduction
Basalt Material fired to 1250C in Reduction
100 Basalt Glaze Material on Porcelain, fired to 1265C in Oxidation
100 Basalt Glaze Material on Porcelain, fired to 1265C in Oxidation

 

Now that I knew I was dealing with a viable glaze, I couldn’t wait to get this stuff in the kiln and firing it in a weird, experimental reduction cool cycle.  Last year I discovered some really incredible surfaces by cooling a kiln in reduction, and holding at certain temperatures. In this case, the geologists have told me that basalt solidifies at about 980C, so I’ve been crash cooling the kiln to around this temperature, holding in a reduced environment, and letting the metallic compounds crystallize in reduction. My speculation is that I can somewhat re-create the conditions in which iridescent phenomena occur. Lo and Behold:

Iridescent basalt Sample left, Iridescent Glaze right.
Iridescent basalt Sample left, Iridescent Glaze right.

This result is remarkably similar to effects you can achieve in Raku, or Lustre firing… but it’s a different phenomena, and relies on totally different elements; namely, Iron. Whereas raku usually derives rainbow iridescence from Copper and Cobalt, and lustres from Silver, and Bismuth, these colors are coming from Iron with trace amounts (less than .5% Manganese and Titanium). It’s very interesting on the ceramics side, and the geologists are quite interested too, because the phenomena is not wholly understood.  One of the perks of being a graduate student with STEM funding is that I have access to fancy analytical equipment.  This analysis has allowed me to build a material profile in Insight Glaze Software.

 

Insight Profile for this Basalt Material
Insight Profile for this Basalt Material

To that end, my future plans with this research will involve more experimentation with the firing process. In fact, I’m currently working on a piece that will exhibit between 10 and 20 wall hanging tiles that all feature the exact same clay and glaze with different firing schedules.  At the same time, I’ll also continue to tweak this material by adding other oxides to end up with brand new flavors of glaze.

 

80% Basalt Glaze Material + 20% Porcelain Clay Body
80% Basalt Glaze Material + 20% Porcelain Clay Body

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.

Adamite

From Wikipedia:

Adamite is a zinc arsenate hydroxide mineral, Zn2AsO4OH. It is a mineral that typically occurs in the oxidized or weathered zone above zinc ore occurrences. Pure adamite is colorless, but usually it possess yellow color due to Fe compounds admixture. Tints of green also occur and are connected with copper substitutions in the mineral structure. Olivenite is a copper arsenate that is isostructural with adamite and there is considerable substitution between zinc and copper resulting in an intermediate called cuproadamite. Zincolivenite is a recently discovered mineral being an intermediate mineral with formula CuZn(AsO4)(OH). Manganese, cobalt, and nickel also substitute in the structure. An analogous zinc phosphate, tarbuttite, is known.

Cuprian Adamite
Cuprian Adamite
Cuprian Adamite
Cuprian Adamite
Adamite
Adamite
Adamite
Adamite
FlouroAdamite from Tooele, Utah
FlouroAdamite from Tooele, Utah