PYRO3.TXT Stars, Flares, and Color Mixtures This is part of a series of files on pyrotechnics and explosives. It's serious stuff, and can be really dangerous if you don't treat it seriously. For you kids out there who watch too many cartoons, remember that if a part of your body gets blown away in the REAL world, it STAYS blown away. If you can't treat this stuff with respect, don't screw around with it. Each file will start with a set of safety rules. Don't skip over them. Read 'em and MEMORIZE 'em!! At the beginning, there will be a set of general rules that always apply. Then there will be some things that you HAVE TO KNOW about the materials you will be using and making this time. Read it thoroughly before starting anything. Pyrotechnic preparations and explosives are, by their very nature, unstable, and subject to ignition by explosion or heat, shock, or friction. A clear understanding of their dangerous properties and due care in the handling of ingredients or finished products is necessary if accidents are to be avoided. Always observe all possible precautions, particularly the following: 1. Mix only small batches at one time. This means a few grams, or at most, an ounce or so. Don't go for big mixes -- they only make for bigger accidents. The power of an explosive cubes itself with every ounce. (9 Ounces is 729 times as powerful as one ounce.) 2. When weighing chemicals, use a clean piece of paper on the scale pan for each item. Then discard the used paper into a bucket of water before weighing the next ingredient. 3. Be a safe worker. Dispose of any chemicals spilled on the workbench or equipment between weighings. Don't keep open containers of chemicals on your table, since accidental spillage or mixing may occur. When finished with a container, close it, and replace it on the storage shelf. Use only clean equipment. 4. Where chemicals are to be ground, grind them separately, NEVER TOGETHER. Thoroughly wash and clean equipment before grinding another ingredient. 5. Mixing of batches should be done outdoors, away from flammable structures, such as buildings, barns, garages, etc. Mixes should also be made in NON METALLIC containers to avoid sparks. Glass also should not be used since it will shatter in case of an accident. Handy small containers can be made by cutting off the top of a plastic bottle three or four inches from the bottom. Some mixes may most conveniently be made by placing the ingredients in a plastic bottle and rolling around until the mixture is uniform. In all cases, point the open end of the container away from yourself. Never hold your body or face over the container. Any stirring should be done with a wooden paddle or stick to avoid sparks or static. Powdered or ground materials may also be mixed by placing them on a large sheet of paper on a flat surface and then rolling them across the sheet by lifting the sides and corners one at a time. 6. Never ram or tamp mixes into paper or cardboard tubes. Pour the material in and gently tap or shake the tube to settle the contents down. 7. Store ingredients and finished mixes where they will not be a fire hazard away from heat and flame. Finished preparations may be stored in plastic bottles which will not shatter in case of an accident. Since many of the ingredients and mixes are poisonous, they should be stored out of reach of children or pets, preferably locked away. 8. Be sure threads of screw top containers and caps are thoroughly cleaned. This applies also to containers with stoppers of rubber or cork and to all other types of closures. Traces of mixture caught between the container and closure may be ignited by the friction of opening or closing the container. Throughout any procedure, WORK WITH CLEAN CONDITIONS. 9. ALWAYS WEAR A FACE SHIELD OR AT LEAST SHATTERPROOF SAFETY GLASSES. Any careful worker does when handling dangerous materials. Be sure lenses and frames are not flammable. 10. Always wear a dust respirator when handling chemicals in dust form. These small particles gather in your lungs and stay there. They may cause serious illnesses later on in life. 11. Always wear gloves when working with chemicals. 12. Always wear a waterproof lab apron. 13. If you must work indoors, have a good ventilation system. 14. Never smoke anywhere near where you are working. 15. Make sure there are NO open flames present, and NO MOTORS (they produce sparks inside.) No hot water heaters, furnaces, or pilot lights in stoves!! Sparks have been known to very readily explode dust floating in the air. 16. ALWAYS work with someone. Two heads are better than one. 17. Have a source of water READILY available. (Fire extinguisher, hose, etc.) 18. Never, under any circumstances, use any metal to load chemicals or put chemicals in. Fireworks with metal casings are worse to handle than a live hand grenade. Never use any metal container or can. This includes the very dangerous CO2 cartridges. Many people have been KILLED because of flying fragments from metal casings. Again, please do not use metal in any circumstance. 19. Always be thoroughly familiar with the chemicals you are using. Some information will be included in each file, but look for whatever extra information you can. Materials that were once thought to be safe can later be found out to be dangerous stuff. 20. Wash your hands and face thoroughly after using chemicals. Don't forget to wash your EARS AND YOUR NOSE. 21. If any device you've built fails to work, leave it alone. After a half hour or so, you may try to bury it, but never try to unload or reuse any dud. 22. If dust particles start to form in the air, stop what you are doing and leave until it settles. 23. Read the entire file before trying to do anything. 24. NEVER strike any mixture containing Chlorates, Nitrates, Perchlorates, Permanganates, Bichromates, or powdered metals don't drop them, or even handle them roughly. These rules may all look like a lot of silly nonsense, but let's look at one example. When the move "The Wizard of OZ" was made, the actress who played the good witch was severely burned when one of the exploding special effects got out of hand. The actress who played the bad witch got really messed up by the green coloring used on her face, and the original actor who played the Tin Man got his lungs destroyed by the aluminum dust used to color his face. The actor we know of as the tin man was actually a replacement. The point is, these chemicals were being used under the direction of people a lot more knowlegable of chemicals than you are, and terrible accidents still happened. Don't take this stuff lightly. We will be using the following materials this time. Get familiar with them. Some can be highly dangerous. Aluminum Dust (and powder) Al An element used for brilliancy in the fine powder form. It can be purchased as a fine silvery or gray powder. All grades from technical to superpure (99.9%) can be used. It is dangerous to inhale the dust. The dust is also flammable, by itself. In coarser forms, like powder, it is less dangerous. Antimony Sulfide Sb S 2 3 Also known as "Black" Antimony Sulfide. (There is also a "Red" form, which is useless to us.) This is used to sharpen the report of firecrackers, salutes, etc, or to add color to a fire. The technical, black, powder is suitable. Avoid contact with the skin. Dermatitis or worse will be the result. Barium Chlorate Ba(ClO ) * H O 3 2 2 Available as a white powder. It is poisonous, as are all Barium salts. It is used both as an oxidizer and color imparter. It is as powerful as Potassium Chlorate and should be handled with the same care. Melting point is 414 degrees. Barium Nitrate Ba(NO ) 3 2 Poisonous. Used as an oxidizer and colorizer. The uses and precautions are the same as with a mixture containing Potassium Nitrate. Charcoal C A form of the element carbon. Used in fireworks and explosives as a reducing agent. It can be purchased as a dust on up to a coarse powder. Use dust form, unless otherwise specified. The softwood variety is best, and it should be black, not brown. Copper Acetoarsenite (CuO) As O Cu(C H O ) 3 2 3 2 3 2 2 The popular name for this is Paris Green. It is also called King's Green or Vienna Green. It has been used as an insecticide, and is available as a technical grade, poisonous, emerald green powder. It is used in fireworks to add color. Careful with this stuff. It contains arsenic. Copper Chloride CuCl 2 A color imparter. As with all copper salts, this is poisonous. Copper Sulfate CuSO *5H O 4 2 Known as Blue Vitriol, this poisonous compound is available as blue crystals or blue powder. Can be purchased in some drugstores and some agricultural supply stores. Used as a colorizer. Dextrine This can be purchased as a white or yellow powder. It is a good cheap glue for binding cases and stars in fireworks. Lampblack C This is another form of the element carbon. It is a very finely powdered black dust (soot, actually) resulting from the burning of crude oils. It is used for special effects in fireworks. Lead Chloride PbCl 3 Available as a white, crystalline, poisonous powder, which melts at 501 degrees. As with all lead salts, it is not only poisonous, but the poison accumulates in the body, so a lot of small, otherwise harmless doses can be as bad as one large dose. Mercurous Chloride HgCl Also known as calomel or Mercury Monochloride. This powder will brighten an otherwise dull colored mixture. Sometimes it is replaced by Hexachlorobenzene for the same purpose. This is non poisonous ONLY if it is 100% pure. Never confuse this chemical with Mercuric Chloride, which is poisonous in any purity. Potassium Chlorate KClO 3 This, perhaps, is the most widely used chemical in fireworks. Before it was known, mixtures were never spectacular in performance. It opened the door to what fireworks are today. It is a poisonous, white powder that is used as an oxidizer. Never ram or strike a mixture containing Potassium Chlorate. Do not store mixtures containing this chemical for any length of time, as they may explode spontaneously. Potassium Dichromate K Cr O 2 2 7 Also known as Potassium Bichromate. The commercial grade is used in fireworks and matches. The bright orange crystals are poisonous. Potassium Nitrate KNO 3 Commonly called Saltpeter. This chemical is an oxidizer which decomposes at 400 degrees. It is well known as a component of gunpowder and is also used in other firework pieces. Available as a white powder. Potassium Perchlorate KClO 4 Much more stable than its chlorate brother, this chemical is a white or slightly pink powder. It can often substitute for Potassium Chlorate to make the mixture safer. It will not yield its oxygen as easily, but to make up for this, it gives off more oxygen. It is also poisonous. Red Gum Rosin similar to shellac and can often replace it in many fireworks formulas. Red Gum is obtained from barks of trees. Shellac Powder An organic rosin made from the secretions of insects which live in India. The exact effect it produces in fireworks is not obtainable from other gums. The common mixture of shellac and alcohol sold in hardware stores should be avoided. Purchase the powdered variety, which is orange in color. Sodium Oxalate Na C O 2 2 4 Used in making yellow fires. Available as a fine dust, which you should avoid breathing. Strontium Carbonate SrCO 3 Known in the natural state as Strontianite, this chemical is used for adding a red color to fires. It comes as a white powder, in a pure, technical, or natural state. Strontium Nitrate Sr(NO ) 3 2 By far the most common chemical used to produce red in flares, stars and fires. Available in the technical grade as a white powder. It does double duty as an oxidizer, but has a disadvantage in that it will absorb some water from the air. Strontium Sulfate SrSO 4 Since this chemical does not absorb water as readily as the nitrate, it is often used when the powder is to be stored. In its natural state it is known as Celestine, which is comparable to the technical grade used in fireworks. Sulfur S A yellow element that acts as a reducing agent. It burns at 250 degrees, giving off choking fumes. Purchase the yellow, finely powdered form only. Other forms are useless without a lot of extra and otherwise unnecessary effort to powder it. Zinc Dust Zn Of all the forms of zinc available, only the dust form is in any way suitable. As a dust, it has the fineness of flour. Should be either of the technical or high purity grade. Avoid breathing the dust, which can cause lung damage. Used in certain star mixtures, and with sulfur, as a rocket fuel. The Chemistry of Pyrotechnics Most pyrotechnic mixtures follow a very simple set of chemical rules. We'll go over those now. Most mixtures contain an oxidizing agent, which usually produces oxygen used to burn the mixture, and a reducing agent, which burns to produce hot gasses. In addition, there can be coloring agents to impart a color to the fire, binders, which hold the mixture in a solid lump, and regulators that speed up or slow down the speed at which the mixture burns. These are not all the possibilities, but they cover most all cases. Oxidizing agents, such as nitrates, chlorates, and perchlorates provide the oxygen. They usually consist of a metal ion and the actual oxidizing radical. For example, Potassium Nitrate contains a metal ion (Potassium) and the oxidizing radical (the Nitrate). Instead of potassium, we could instead substitute other metals, like sodium, barium, or strontium, and the chemical would still supply oxygen to the burning mixture. But some are less desirable. Sodium Nitrate, for example, will absorb moisture out of the air, and this will make it harder to control the speed at which the mixture will burn. In the following examples, we'll use the letter "X" to show the presence of a generic metal ion. Note that Nitrates are stingy with the oxygen that they give up. They only give one third of what they have. Some Some Nitrate Nitrite Oxygen 2XNO ---> 2XN0 + O 3 2 2 Chlorates are very generous, on the other hand. They give up all the oxygen they have. Furthermore, they give it up more easily. It takes less heat, or less shock to get that oxygen loose. Mixtures using chlorates burn more spectacularly, because a smaller volume of the mix needs to be wasted on the oxidizer, and the ease with which the oxygen is supplied makes it burn faster. But the mixture is also MUCH more sensitive to shock. Some Some Chlorate Chloride Oxygen 2XClO ---> 2XCl + 3O 3 2 Perchlorates round out our usual set of oxidizing tools. Perchlorates contain even more oxygen than Chlorates, and also give it all up. However, they are not as sensitive as the Chlorates, so they make mixtures that are "safer". That is, they're less likely to explode if you drop or strike them. Some Some Perchlorate Chloride Oxygen XClO ---> XCl + 2O 4 2 Reducing agents, like sulfur and charcoal (carbon) simply burn the oxygen to produce sulfur dioxide and carbon dioxide. It's usually best to include a mixture of the two in a pyrotechnic mixture, as they burn at different speeds and temperatures, and the proper combination will help control the speed of combustion. Also, when extra fast burning speed is needed, like in rockets and firecrackers, metal powder is often added. The finer the powder, the faster the burning rate. The proportions change the speed, as well. Magnesium powder or dust is often used for speed. Aluminum dust works, but not as well. Zinc dust is used in some cases. Powdered metal, (not dust) particularly aluminum or iron, are often used to produce a mixtire that shoots out sparks as it burns. In rare cases, it is desirable to slow down the burning speed. In this case, corn meal is often used. It burns, so acts as a reducing agent, but it doesn't burn very well. Coloring agents are very interesting. It's long been known that various metals produce different colored flames when burned in a fire. The reasons are buried in the realm of quantum physics, but the results are what matters, and we can present them here. Note that if we use an oxidizing agent that contains a colorizing metal, it can do a double job. It can produce oxygen and color. Barium -Barium salts give a pleasant green color. Barium Nitrate is most often used. Strontium -Strontium salts give a strong red color. Strontium Nitrate is a very convenient material for red. Sodium -Sodium salts give an intense yellow color. So intense in fact that any sodium compounds in a mixture will usually wash out other colorizers. As has been said, Sodium Nitrate absorbs moisture from the air, and so is not really suitable to impart color. Instead, Sodium Oxalate is usually used. This does not absorb lots of water, but has the disadvantage of being very poisonous. Copper -Copper salts are used to give a blue color. Blue is the most difficult color to produce, and it's usually not too spectacular. Usually Copper Acetoarsenite (Paris Green) is used. This compound contains arsenic, and is very poisonous. Since it still doesn't produce a very memorable blue, it's often used with mercurous chloride, which enhances the color, but is also poisonous, and expensive, to boot. Potassium -Potassium salts will give a delicate purple color, if they'e very pure. The cheaper lab grades of potassium nitrate often contain traces of sodium, which completely obscure the purple color. In order to get the purple coloring, very pure grades must be used, and you must be very careful to mix it in very clean vessels, and scoop it from the supply jar with a very clean scoop. The color is certainly worth the effort, if you can get it. Some mixtures that burn in colors also contain binders, that hold the mixture together in a solid lump. These lumps are usually referred to as stars. The balls fired from a roman candle or the colorful showers sprayed from aerial bombs are examples of stars. Depending on the mixture, the binder is either a starch called dextrine or finely powdered orange shellac. A shellac-like material called red gum is also used on occasion. In some mixtures, the shellac powder also helps produce a nice color. Shellac mixtures are moistened with alcohol to get them to stick together. Dextrine mixtures are moistened with water. If the colored mixture is to be used as a flare, it's just packed into a thin paper tube. If it's to be fired from a roman candle, it's usually extruded from a heavy tube by pushing it out with a dowel, and the pieces are cut off as the proper length pops out. Stars fired from an aerial bomb are usually made by rolling the moist mixture flat, and cutting it with a knife into small cubes. Stars that are extruded are often called "pumped stars" those that are rolled out are "cut stars". The following are formulas for mixtures that burn with various colors. Parts are by weight. Red Potassium Chlorate 9 Sulfur 2 Lampblack 1 Strontium Nitrate 9 bind with shellac dissolved in alcohol Blue Potassium Chlorate 9 This one is inferior Copper Acetoarsenite 2 Potassium Chlorate 12 Mercurous Chloride 1 Copper Sulfate 6 Sulfur 2 Lead Chloride 1 bind with dextrine Sulfur 4 in water bind with dextrin in water Green Barium Chlorate 8 Barium Nitrate 3 Lampblack 1 Potassium Chlorate 4 Shellac Powder 1 Shellac Powder 1 bind with alcohol Dextrine 1/4 Bind with alcohol Yellow Potassium Chlorate 8 Potassium Chlorate 8 Sodium Oxalate 3 Sodium Oxalate 4 Lampblack 2 Shellac Powder 2 Bind with shellac in Dextrine 1 alcohol or dextrine Bind with alcohol in water White Potassium Nitrate 6 Sulfur 1 Antimony Sulfide 2 bind with dextrine in water Orange Strontium Nitrate 36 Sodium Oxalate 8 Potassium Chlorate 5 Shellac Powder 5 Sulfur 3 Bind with alcohol Purple (ingredients must be very pure) Potassium Chlorate 36 This one has more of a lilac color Strontium Sulfate 10 Potassium Chlorate 38 Copper Sulfate 5 Strontium Carbonate 18 Lead Chloride 2 Copper Chloride 4 Charcoal 2 Lead Chloride 2 Sulfur 12 Sulfur 14 bind with dextrine in bind with dextrine in water water Brilliant White Potassium Perchlorate 12 Aluminum Dust 4 Dextrine 1 Bind with water Golden Twinkler Stars - Falls through the air and burns in an on and off manner. The effect is spectacular. A pumped or cut star. Potassium Nitrate 18 Sulfur 3 Lampblack 3 Aluminum Powder 3 Antimony Sulfide 3 Sodium Oxalate 4 Dextrine 2 Bind with water Zinc Spreader Stars - Shoot out pieces of burning zinc and charcoal. These stars are much heavier than usual, and require larger charges if they're to be fired from a tube. Zinc Dust 72 Potassium Chlorate 15 Potassium Dichromate 12 Granular Charcoal 12 Dextrine 2 bind with water Electric Stars - Stars that contain aluminum powder Potassium Nitrate 15 Potassium Chlorate 60 Aluminum, fine 2 Barium Nitrate 5 Aluminum, medium 1 Aluminum, fine 9 Black Powder 2 Aluminum, medium 4 Antimony Sulfide 3 Aluminum, coarse 3 Sulfur 4 Charcoal 2 bind with dextrine in Dextrin 5 water bind with red gum in water Potassium Perchlorate 6 Barium Nitrate 1 Potassium Perchlorate 4 Aluminum 20 Aluminum, medium 2 Dextrin 1 Dextrin 1 bind with shellac in bind with shellac in alcohol alcohol Simpler Zinc Spreaders Potassium Nitrate 14 Potassium Chlorate 5 Zinc Dust 40 Potassium Dichromate 4 Charcoal 7 Charcoal, medium 4 Sulfur 4 Zinc Dust 24 bind with dextrine in bind with dextrine in water water Willow Tree Stars - Use large amounts of lampblack -- too much to burn fully. Gives a willow tree effect. Potassium Chlorate 10 Potassium Nitrate 5 Sulfur 1 Lampblack 18 bind with dextrine in water In future files, we'll look at using these mixtures to produce roman candles, aerial bombs, and other effects. As always, don't forget that it's just plain stupid to go buying all these materials from one chemical supply house. When you buy it all as a group, they know what you plan to do with it, and they keep records. If anyone goes investigating the source of homemade fireworks and checks with your supplier, there will be a lead straight to you. Be sure to cover your tracks. 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