Friday, August 26, 2011

Excerpts from grandfather's journals:



What is the composition of black powder ?

Composed of the following three solid ingredients:

· Saltpeter: KNO3 niter (or, more rarely, NaNO3 Chilean nitrate).

· Sulphur: S.

· Carbon: C. Often as charcoal from wood (willow).

However, simply mixing the ingredients produces a decidedly inferior powder... To obtain what I consider proper black powder, the ingredients must be "incorporated" in a damp state. This allows the application of great pressure to form a dense cake, ultimately broken down into dry grains.

Simple earlier recipes calling for equal weights of the three components... Such mixtures would only burn violently without exploding... Also, explosion cannot occur if raw saltpeter is used.

In the 6 pages of the Book of Fires, there are 35 incendiary recipes, including the one for black powder

1 lb of native sulfur, 2 lb of linden or willow charcoal, 6 lb of saltpeter, which three things are very finely powdered on a marble slab.

Other recipes call for 40% more saltpeter than either sulphur or carbon (7:5:5 formula by weight). less sulphur and more charcoal (6:1:2). The most commonly quoted modern gunpowder composition seems to date from around 1800 and calls for 75% saltpeter (niter) oxidizer, with 10% sulfur (S) and 15% charcoal (C) fuel:

The stoichiometry of the following oversimplified reaction would correspond to about 74.8% niter, 11.9% sulphur and 13.3% carbon (roughly 101:16:18):

2 KNO3 + 3 C + S ® K2S + 3 CO2 + N2 + 572 kJ (505.8 cal/g)

The potassium sulphide solid residue forms a thick white smoke, capable of obscuring entire fields. Newer propellants leave little or no such residue when properly exploded. They are thus collectively known as smokeless powders. The simplest idea for a smokeless dark powder is called ammonpulver (AP) and involves ammonium nitrate (AN) with 10% to 20% charcoal, although the stoichiometry of the following reactions translates into only 7% to 13% carbon, by weight:

2 NH4NO3 + C ® CO2 + 4 H2O + 2 N2 + 629.6 kJ (874.4 cal/g)
NH4NO3 + C
® CO + 2 H2O + N2 + 228.6 kJ (593.5 cal/g)

Sulfurless powder (12.93% carbon) yields 772.6 cal/g, with 60% smoke:

4 KNO3 + 5 C ® 2 K2CO3 + 3 CO2 + 2 N2 + 1501.4 kJ

It takes 92.9 g of this mix to release a mole of gas, whereas only 67.6 g of black powder would suffice (sulfur prevents wasteful carbonate production).



Thermite
Thermite brings about thermal destruction chemically.

Thermite is a mix of rust and powdered aluminum which can be ignited with a strip of magnesium to produce alumina and iron. This popular reaction is able to deliver molten iron at a very high temperature (about 2200°C).

Fe2O3 + 2 Al ® Al2O3 + 2 Fe + 851.5 kJ

The precise stoichiometry calls for 2.9 g of ferric oxide for 1 g of aluminum. An excess of aluminum helps prevent the formation of hercynite (FeAl2O4 ).

The usual recipe calls for 8 grams of iron oxide for 3 grams of aluminum.



Hot Ice (COMBAT USEFUL)
The crystallization of sodium acetate trihydrate is exothermic.

Here's the crystallization reaction for the hot ice found in the reusable PCM heating pads that have been widely available since 1978 (136.0796 g/mol).

Na+ + CH3COO- + 3 H2O ® (NaCH3COO, 3H2O) + 38 kJ

The data from the above table is equivalent to a latent heat of 280 J/g.

This solidification occurs (below 58°C) only when nucleation can be initiated by various impurities or, more reliably, by a little bit of already crystallized sodium acetate trihydrate.

Interestingly, the reaction can also be triggered mechanically by a special clicker (consisting of a slotted metallic disk) that I found out quite by accident. That device made possible a product known as a heat pack or hand warmer. I’ve found this to be quite useful and very popular here among the glaciers.

The thing consists of a permanently sealed soft transparent pouch containing a clicker and some hot ice (possibly with a very slight excess of water). The pack is stored or carried in its liquid form. When needed, a mere click turns it into a very warm solid object (which can later be returned to it metastable liquid form by heating the pouch in boiling water until all traces of the crystals have disappeared).

Ink Formulas
What is the composition of traditional inks ?

Natural Ink

Sepia is the most lasting of natural inks, but it's not lightfast. It is a dark brown liquid consisting of concentrated melanin, secreted by Mediterranean cuttlefish and other cephalopods (it's stored in ink sacs and ejected to confuse attackers).

Writing Ink

As early as 2500 BC, writing inks were carbon inks consisting of fine grains of carbon black [from soot] suspended in a liquid. A red version of this ink can be made which uses cinnabar (HgS) instead of carbon. The idea is simple: When the liquid dries out, the solid pigment (C or HgS) remains which leaves a permanent trace. Such inks are best used on semi-absorbent stuff, like paper or papyrus (not parchment).

The problem is to keep the grains in suspension long enough to apply the ink. In plain water, fine grains of carbon black would aggregate and form flakes large enough to fall quickly to the bottom of the container. This flocculation process can be prevented with a hydrophilic additive which minimizes interactions between the grains by coating them. Early ink recipes may thus have called for various plant juices instead of plain water. It turns out that gum arabic acts this way to stabilize the ink into a colloidal suspension for days or weeks...

Instead, ink is produced as needed by grinding an inkstick on an inkstone after adding a little water (the inkstone also acts as an inkwell). ink-sticks consist of a pigment (usually soot from pine, oil or lacquer) and a soluble resin which holds the dry stick together and plays a critical part in the colloidal ink suspension produced by wet grinding.

Iron-Gall Ink

Iron-gall ink normally includes a standard ink component, which provides both body (from gum arabic) and some initial coloring upon application of the ink. Otherwise, the main pigmentation of iron-gall ink comes paradoxically from water-soluble ferrous chemicals with little color of their own: When the ink dries in air, an oxidation occurs which turns these ferrous salts into insoluble ferric dark pigments. In addition, iron-gall ink may react with parchment collagen or paper cellulose, in a totally indelible way. Some poorly balanced iron-gall inks have even been observed to burn holes through paper.

It has been shown that an excess of ferrous salt in iron-gall ink leaves permanent traces of active soluble salts (not properly oxidized into inert pigments) which will catalyze the slow decomposition of cellulose, especially when acidity is present. This corrosion is reduced with a proper balance in the composition of the ink.

To prevent deterioration of historical iron-gall ink documents, I’ve found an interesting treatment: First, a saturated solution is applied which contains a calcium salt and its acid, namely:

· Calcium phytate: C6H6 (PO4Ca)6 (Phytic Acid Hexa Calcium Salt).

· Phytic acid: (CHOPOOHOH)6

The salt is soluble up to twice the molar concentration of the acid. This is an oxidation inhibitor which binds the metal ions. Then, acidity is neutralized with calcium bicarbonate, which creates an alkaline buffer and also leaves a phytate precipitate in the fibers, for continued oxidation protection.


Traditional Pigments
Chemicals traditionally used as coloring agents in paints, dyes or
inks.

Most of these substances are fairly harmless but some of them are too toxic for regular use, by modern standards at least...

At left is Blood ink, (the expensive dye behind the lake pigment used for red velvet) from bloodwood.

Pigments:

  • Carbon Black : Lampblack, from soot. C (12.01 g/mol)
  • Manganese Black : Manganese dioxide. MnO2 (86.937 g/mol)
  • Cinnabar : Called vermillion, or Chinese red. HgS (232.66 g/mol)
  • Red Ochre : Hematite. Ferric oxide. Fe2O3 (159.69 g/mol)
  • Brazilin : Natural Red 24. C16H14O5 (286.2794 g/mol).
    Turkey Red :
    Alizarin C14H8O4 (240.2109 g/mol).
  • Sepia : Natural sepiomelanin from sepia officinalis
  • Viridian : Chromium oxide dihydrate. Cr2O3 . 2 H2O
  • Green Malachite : Basic cupric carbonate. CuCO3-Cu(OH)2
  • Elven blue : Synthetic cuprorivaite. CaCuSi4O10
  • Indigo : "Indian Blue". CAS 482-89-3 C16H10N2O2
  • Blue : Palygorskite clay and indigo complex.
  • Lapis Lazuli : Lazurite (sodium aluminum silicate) not "lazulite" (Na,Ca) 8 (AlSiO4 )6 (S, SO4 , Cl 2 ) especially: Na 8 (AlSiO4 )6 S.
  • Nallic Blue : Ferric ferrocyanide. Ferric hexacyanoferrate. Fe4 [Fe (CN)6 ] 3 A chelating agent insoluble in water .

Wednesday, August 24, 2011

What an interesting turn of events...

Who knew, when I loaded my latest wares and hitched Charles to the wagon a few weeks ago , that I would end up halfway around the world?

Yeah it's been an eventful couple of weeks, and I've fallen in with an interesting group of companions.

What started out as a trip to the city to sell some potions and maybe do some research turned into quite an adventure. I set up my little corner shop, as I normally do, over on Potions Row. I had forgotten that it was time for the Games again, but wasn't really concerned with them other than to make sure I had enough to sell.

Then I get a customer who comes in, and practically buys everything I have on display.
He 's an interesting fellow, but he talks too much, and looks like he'd eaten one too many mushrooms. He inquired if I'd be interested in accompanying he and his party on a journey north, as they had need of a potion-maker.

Since grandfather died, one of my goals was to branch out a bit, so I agreed.

One good thing about the Autumn Games, is that I never keep a full stock for very long. I sold the rest of what I had brought with me, and made a list of all of the supplies, ingredients, and reagents that I needed to restock on.

During the games, I ended up having to heal one of the party members, a desert elf, from some rather severe burns. Don't ask me why, but the druid in the party ended up setting him on fire. I don't think it was deliberate. I think she may have been trying to actually heal him, but she seems rather accident prone when it comes to dealing with something other than plants and animals.

A curious note on healing the elf though, his skin has remained black. I wonder if that's a result of mixing so many potions together?

I normally don't attend the games, but the group I joined doesn't have a medic, and two of them were actually participating in the games. So I went with them. Specifically with the desert elf, who, for some unknown reason, insisted on being present and able to draw his bow.

Something about money I'm guessing. Some of the party members seem to have gotten themselves into a rather tight spot concerning money.

Anyways. The desert elf is going to try my patience, I'm sure of it. I did my best to try to impress upon him the need for rest. I even threatened to tie him to the bed! But he insisted. So I insisted on being there too. He actually finished the competition, stubborn elf, which surprised me. I was half-expecting him to fall over midway through the game.

I suppose it's a good thing I DID go with him to that final game.. there was a horrible accident where a stray arrow went into the crowd and struck an infant in the neck. I was only just able to get there in time. It was a terrible injury, but thanks to some quick help on the druid's part to break the arrow smoothly, we were able to save her. I've been monitoring her progress, and she's healing well. She'll have a small scar, and I'm afraid that her voice will be affected permanently, but she is very young, and with proper care, should be just fine. I've given the family a cache of the needed potions and poultices that they will need to continue her care after I've left; and their family doctor seems competent.

As thanks, they made me a part of their family, which I wasn't expecting at all. I'm honored. Brienne Na'lare Mambrosedóttir. I kind of like the sound of that. Maybe I can ask them to help me set up a place here. This city's not too bad.

We'll see where the travels take me though, I feel like I'm supposed to be with this group for a while. Gods know they need a medic with them. Someone with a cool head.

So far it's the druid, the ...cleric? (I'm not really sure what he is.. but apparently he can only talk to his god while he's high. Huh. To each their own I suppose.); the desert elf, and a bard and a mage have joined us now too.

Like I said, it's an interesting group.

Now that everyone is healed and mobile again, we're gearing up to travel south. To the desert.
Something about having to stop a demon goddess that mushroom-boy accidentally set loose.
I've never been to the desert before. I've been told that it's a lot like traveling across the glaciers here, except hot.

I'm looking forward to seeing where the road takes me.