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Homegrown Oxidizers Part One WSM Not all of us live in an area friendly to fireworks. Access to these articles of celebration, let alone the materials to produce them may be extremely limited if not completely banned. Reliable information to produce fireworks raw materials is very difficult to find and even consulting professional chemists usually yields little useful information (unless they happen to work in the chlor-alkali industry). In these articles we’ll try to describe some workable methods of producing fireworks raw materials on a small (hobbyist) scale. The first material discussed is potassium chlorate. Industry typically produces potassium chlorate by starting with sodium chloride (table salt) and water from which is made sodium chlorate. The solution of sodium chlorate is mixed with a solution of potassium chloride and potassium chlorate (being much less soluble at room temperature) drops out of solution, is washed, dried, powdered and packaged. With a proper setup, it’s possible to make potassium chlorate directly from potassium chloride and completely avoid any sodium contamination. Fundamentals Pyrotechnists generally are concerned with the breakdown of molecules to get the required elements combined in the burning devices to produce the desired effects. To produce the raw materials desired, we need to build up the molecules. This is typically done industrially with electrochemistry. Electrochemistry uses direct current electricity in solutions of salts to create desired changes in the solutions. Examples of this are electroplating (depositing metals on other materials), electrowinning (getting pure metals from solutions), and anodizing (forming a strong protective oxide layer on aluminum). In our case we are starting with saltwater and producing an oxidizer salt. The mixture of salt and water (potassium chloride solution in this case) is changed by current through the electrodes by essentially breaking the water down to it’s elemental components, hydrogen and oxygen, driving the oxygen onto the chlorine ions (salts in solution become an ionic mixture) at the anode and the hydrogen collects at the cathode where it bubbles off and out of the solution. KCl + H2O + e- → K+ + Cl- + H+ + O- + e- → K+ + ClO- + ClO2- + H2↑ + e- → KClO3 (This is a very simplistic and unbalanced description of what happens in a chlorate cell) Many amateur chemists have made chlorates successfully using graphite for the anode (positive electrode) and iron or stainless steel for the cathode (negative electrode). Although graphite works, it has drawbacks and limitations to its use. One of the most notable is that it breaks down, leaving a black sludge in the chlorate cell that needs to be removed from the final product before it can be used. Graphite works best at lower temperatures or this breakdown is accelerated. The state of the art in industry for over 40 years uses a titanium anode coated with MMO, or Mixed Metal Oxides. MMO is a mixture of titanium dioxide and various precious metal oxides such as ruthenium dioxide, iridium dioxide and others in varying amounts to improve the electrical and physical characteristics of the coating. MMO has some distinct advantages over graphite as an anode: Though not physically tough, it is extremely electrically and chemically tough if certain contaminants are absent It can operate at much higher temperatures, improving current efficiency (CE) It produces a “clean” product requiring minimal processing to be ready for use It can operate in a cell for years, where graphite will only last for a month or so Though more expensive initially, MMO is more cost efficient due to its longevity Due to the wide use of MMO in industry, new material and surplus stock is available to the amateur electrochemist at reasonable cost. MMO on titanium anodes come in many shapes, configurations and sizes (as well as formulations). For the purpose of these articles we’ll ultimately discuss the use of an MMO coated titanium mesh anode and titanium sheet metal for the cathode (or cathodes) in the description of a workable amateur chlorate cell. Where Do We Start? Most budding electrochemists locate a source of electrodes and develop their system around them. I suggest a better approach is to locate an electric power supply and design the system around it. The best electrical practices dictate that the electrodes demand no more than 80% of the supply’s available current. Less is okay but more tends to overwork our power supply and can lead to premature failure. So what we suggest is get a power supply and tailor the entire system to it. Our power supply needs are: A steady source of “clean” DC power (little or no AC components, AKA ripple) Get as high a current output as you can afford (typically, the higher the current output, the more expensive the power supply) A variable DC power supply is excellent, especially for experimenting with various setups and conditions, but these tend to be very expensive unless a fortunate find on eBay or an electronics surplus house drops in your lap For chlorate a minimum voltage of 2.5 Vdc (volts direct current). Industry usually specifies 3.6 Vdc but we’ve successfully used up to 5 Vdc without problems Though we’re discussing voltage, the main component of power is the current. Current (measured in Amperes or Amps) is the main influence in our process and the real workhorse. The voltage only needs to be enough to keep the system working. More on the electrical theory later… Many amateur electrochemists have converted computer power supplies to the task and despite the universal availability of them; this author has never used one. Another option, if one has the electrical or electronic know how, is to rewire a microwave oven transformer to supply low voltage Vac (volts alternating current), rectify the output to Vdc and filter the output to remove AC components to yield the required clean DC power. As most computer power supplies output 12 Vdc and 5 Vdc (our interest is the 5 Vdc portion) and are capable of supplying 30 Amps we will discuss a simple chlorate cell using these parameters. The chlorate cell information shown can be scaled up or down but scaling up will get more complicated and require tighter control of the minute details of the system. To start, by all means, let’s keep it simple… Getting Started We have a power supply (5Vdc, 30 A), now we need the rest of our setup. At a minimum, we need a cell body and the electrodes. The cell body or reaction chamber needs to be compatible with the materials that it’ll be exposed to and secure enough to contain them without spilling or breaking. In the process of converting salt water to chlorate the steps include hypochlorite (bleach) and hypochlorous ions, with chlorate as the next step. The actual chemistry is quite complicated with many changes happening simultaneously and all affected by each other and a multitude of other factors. These processes have been the subject of scholarly doctoral dissertations but we’ll simplify it with descriptions of practical applications and rules of thumb to be successful (even if we don’t completely understand what’s happening we can still make it happen,… and optimize our yield). The Reaction Chamber (RC) Few materials are compatible with our cell but fortunately some of them are common and fairly inexpensive. Glass (some but not all will work) PVC plastic CPVC Teflon or PTFE Kynar or PVDF Viton rubber Typically these materials and similar are completely inert to the cell liquor we’ll create. Other materials can be used but may experience some degradation unless precautions are taken to prevent it (or they’re deemed to be acceptable losses). PE or polyethylene PP or polypropylene XLPE or cross-linked polyethylene Silicone rubber With few exceptions we’ll avoid metal containers. For example, some metals would be useful for one of the components but unsuitable for the intermediates. Glass is attractive because one can see what’s happening in the cell. Seeing is educational when starting out but not required for the process to function correctly (industry uses completely opaque cells, for example). If temperatures are kept in check, PVC is the least expensive option for a reaction chamber. We’ll discuss this more, later. The author’s first successful chlorate cell was a one gallon glass pickle jar with a 4” PVC pipe cap used for a lid and three holes drilled in the lid for 1) a vent, 2) the anode, and 3) the cathode. The setup was not ideal and a lot of lessons were learned in the process, but it made several kilos of potassium chlorate crystals that summer. The first run didn’t produce much chlorate but after recharging the depleted liquor with potassium chloride, subsequent runs produced a lot more. The reason the yield of the first run was small is the bulk of the energy went into creating the precursor ions (hypochlorite and hypochlorous, as well as chlorate) which stays in solution. Once the precursors are developed in the initial run and the liquor is charged with a new batch of chloride, the following runs produce more chlorate and right away. The anode was an MMO coated CP (commercially pure) titanium rod from a commercial source. The cathode was a CP titanium tube. The spacing wasn’t ideal, the vent was minimal and the power was low, all besides no controls and low efficiency (maybe 40%-50% at best), BUT… it made lots of potassium chlorate. It should be mentioned, only potassium chlorate was ever produced (the author has yet to bother with sodium chlorate since the potassium salt was the end goal). The whole notion of making potassium chlorate began with the discovery of the availability of potassium chloride water softener salt at the local hardware supply store. Several problems were noted during those initial runs many years ago: Lots of salt crust (salt creep) forming around the lid and around the electrode holes The electrode spacing was not optimized The electrode sizing wasn’t optimized either The power supply was under utilized Salt creep affected the electrical connections adversely The power connections to the electrode leads (alligator clips) were inadequate for the job No cell parameters were measured or controlled The whole thing was a rough attempt… but successful! Since that time, the author has come a long way and overcome these issues. We will show methods and techniques in an attempt to help the novice electrochemist bypass a lengthy and difficult learning curve to successfully build and operate an effective and efficient chlorate cell.

Homegrown Oxidizers Part Two WSM The Anode A key to modern chlorate production is the MMO anode. These were hard to come by many years ago, but now are so common that surplus material can be had at reasonable cost through careful searching. Part of the success of these MMO anodes is due to their large surface area (on a microscopic scale). The typical process of manufacture involves multiple coating and baking cycles that leave the microscopic surface looking like the cracked mud of a dry pond. These “cracked mud” layers provide much more surface area than a smooth surface would; so much so that an expanded metal mesh coated with MMO has about the same surface area as a solid sheet. This is important when calculating the size of anode required for a given power supply and cell size. A photomicrograph showing the “cracked mud” surface appearance of the acid-cleaned surplus MMO on titanium mesh (200x magnification). MMO on CP titanium mesh anode material. Surplus stock is shown on the left and new stock on the right. MMO anode material; Top on solid CP titanium wire, Middle on niobium with a copper core (the bulb on the end is epoxy resin, which didn’t hold up long in an active cell) and Bottom on a thin wall CP titanium tube. MMO anode material; Top Two: on CP titanium ribbon, roughly 1/4” wide by 0.025” thick, and Bottom: a CP titanium mesh anode, spot welded to a filled CP titanium tube for the electrical lead. The MMO coating is more electrically conductive than the titanium substrate under it, so there’s no need to remove the coating for making electrical connections. The surplus MMO anode mesh material is usually from industrial sources and may often be covered with contaminants. One sample had iron oxides on it (a brown smut on the surface), which was removed by soaking in hydrochloric acid (pool acid) for 15 to 60 minutes and then rinsed with water to remove the residual acid and air dried, leaving the surface clean and undamaged. If this condition exists on any MMO material found, avoid rubbing or abrading the surface with anything. Let the acid do the work; the MMO coating is not harmed by it. If there are scratches on the MMO surface, the exposed titanium is unharmed by exposure to the cell liquor (electrolytes). Titanium, being what is known as a valve metal, is prone to passivate or “self-heal” with an insulating oxide layer when scratched. Aluminum shows similar characteristics, but is unsuitable for exposure to the conditions in the cell. The Cathode Cathodes (the negative electrodes) can be made from many different materials, due to an effect called cathodic protection, as long as the current flows. The better materials to use are known as valve metals due to their physical and electric properties, but of these we’ve chosen CP titanium for its outstanding performance in our tests. The acronym CP stands for commercially pure and it works better than alloyed titanium for our purpose (and is unlikely to add unwanted metal ions to our electrolyte). CP titanium sheet metal stock for cathodes. Stainless steel is used by some electrochemists for a cathode, but we prefer to avoid contamination by nickel, chromium and a host of other alloying metals, especially when the electrodes are exposed to the electrolyte with the power off. If electrodes are left for long periods in the electrolyte without power they break down, not unlike a battery discharging, where irreversible damage can occur. Even with titanium electrodes, if the system powers down, remove, rinse with water and store the electrodes in a safe, dry place for the best care and longevity. Single or Double Cathodes, and Why? A pair of single electrodes with filled tubular titanium leads, offset for proper spacing of the PVDF compression fittings in the lid of the cell. PVDF nuts were added because the cell lid is thin plastic. Most beginners to electrochemistry use a single anode with a single cathode. The bulk of the work is done by the anode, and if coupled with a single cathode, the anode is used at half its full potential usefulness (one side instead of both). By surrounding the anode plate with cathodes, like a sandwich, the full potential of the anode can be utilized. An experiment where cathode plates surround the anode, and with close spacing for efficiency. PVDF (Kynar) compression fittings sealed the titanium tubing and prevented any “salt creep”, so there’s no damage to the electrical connections. The tubular leads were filled with lead-free solder and ran cool enough that no heat damage affected the plastic fittings. Are double cathodes always preferred? No, but more work can be accomplished in a smaller space this way and it’s a consideration. Most of the electrodes shown so far are somewhat rectangular in shape, and later research showed that longer and narrower electrodes which reach deeper into the cell tend to enhance the effect we call “hydrogen lift” which aids the mixing of ionic species in the cell plus prevent thermal layering, and thereby making a more efficient and effective system. Hydrogen lift is a convection-like current caused by the hydrogen bubbles rising from the cathodes as the cell runs. This fluid flow draws dissolved material from the lower parts of the cell and carries it upwards to the surface of the liquor, where it flows outward and cycles downward away from the electrodes. As it nears the bottom of the cell, it’s drawn toward the electrodes to continue the cycle. This physical circulation improves the efficiency of the cell and helps to promote (along with the pH) the “bulk reaction” spoken of in technical literature, where the chlorate ions are created throughout the cell rather than just at the anode by “brute force” of the electrical current. When we surround the anode with cathodes, the electrical stresses are more uniform on the anode, and almost the entire surface is working to produce the desired products. Sizing the Electrodes When we know the surface area of our anode, we can calculate the current demand of it. To calculate how much current our anode will use, we base it on the average demand of 0.3 Amps per square centimeter of surface area. Since one square inch is equal to 6.45 square centimeters we can figure our required current with this formula: A = In2(6.45)(0.3) Where A = maximum Amperage demand and In2 = surface area in square inches That is, if our anode measures 1.5 by 6 inches (9 square inches or 9 In2) and we’re using one cathode about the same size as the anode, plugging this figure into the formula above shows us the answer 17.415, or an expected current demand of 17.4 Amps, maximum. If we sandwich the anode between two cathodes, we double the current drawn and the formula is: A = In2(2)(6.45)(0.3) = 34.83 or nearly 35 Amps If we follow the best electrical practices, we load our power supply no more than 80% of its capacity, so we’ll need a power supply capable of supplying 44 Amps or more (or 22 Amps if a single cathode is used). Going the other way, if we have a power supply with a maximum output of 60 Amps, we want our anode to demand no more than 80% of that or 0.80 x 60 Amps = 48 Amps. If we want to determine the area (in square inches) of an anode that will demand 48 Amps we use the formula: ___48A___ In2 = (6.45)(0.3) for a single cathode, or 24.8 In2 ____48A____ In2 = (6.45)(0.3)(2) for double cathodes, or 12.4 In2 We then decide what width (in inches) our anode will be and dividing the square inches by that number will give us our anode length (again, in inches). Electrode Spacing This topic has been the subject of much debate among amateurs for many years. Some believe the anode and cathode should be as close as possible without touching each other, and others believe they should be as far apart as possible within the limits of the cell container. Most amateurs seem to compromise at somewhere in between these extremes. We’ve observed several of these techniques and see that they all work; the electrolyte is conductive and the current flows. The difference is in the efficiency. The further the electrodes are from each other, the higher the internal cell resistance seems to be. There is always some resistance which is normally exhibited as heat, or “wasted energy”; but in this case, heat actually improves the performance of the desired reactions so it’s not all bad. Higher heat is really a good thing here, but not too hot. Industry uses very close electrodes, but they control the temperature actively with water cooling, flowing through hollow electrodes. Almost all amateurs depend on passive cooling, where control of the cell temperature is by limiting the electrode size and the current supplied. If the temperature goes too high, the real concern is boiling the electrolyte and warping the electrodes till they touch each other, possibly shorting the power supply, which can destroy it. We never want to allow the electrodes to touch each other when power is applied. The effect on the power supply can be catastrophic. Temperatures should also be within the limitations of the cell’s structural materials. Our best performing tests using double cathodes show that a spacing of about 1/8” (or 3mm) seems very effective. The cell ran at 55°C (131°F) and performed quite well. Spacers made of compatible materials, with insulating properties, can be used between the electrodes to stabilize them and keep them from shorting out electrically. Meters Digital panel meters to display the voltage and current output from the power supply or as it enters the cell. To monitor the power used by our system, we use meters. Either analog or digital meters can be used. The voltmeter is wired parallel to the power supply output leads (minding the polarity, i.e., positive to positive and negative to negative) and the ammeter is wired in series with the negative lead through a device called a shunt. The shunt passes all of the current to the cell, except a tiny limited portion which the ammeter measures to display the actual current flowing though the leads. Temperature is another value worth measuring and displaying. If the thermal sensor is exposed to the cell liquor, it won’t last long, so it needs to be protected. Some sensors can be purchased that are Teflon coated and will hold up perfectly in the cell environment. Building a PVC Cell Tank (RC) The most common and least expensive material to fabricate our reaction chamber of is polyvinyl chloride, or PVC. It’s available in pipes and tubes, sheets and a host of other shapes and sizes. It also comes in different colors (including clear) for a price. The simplest tank is made from pipe and fittings, though in larger sizes the fittings can be very expensive. We’ve found that closing the bottom of the tank with PVC sheet material is much more cost effective, and when properly done, a permanent fix to the problem. Typically we look for sheet stock that is about the same thickness as the pipe wall. The pieces are cut and prepared to have the closest fit (without gaps or as close as possible; minor gaps can be filled) and then glued or cemented together. Companies that make PVC glues make them generally for three industries: pipe and plumbing, industrial and chemical. Our best results have been with the industrial or chemical grade glue. Thick walled plastic pipes glued to plastic plates for a reaction chamber. PVC and CPVC are about the same to bond and glue. The CPVC handles greater temperature extremes but costs many times more than PVC. Study and practice have shown us that smaller pieces are much easier to glue together than larger pieces. Large or thick pieces need to have several coatings of glue in a short space of time to soften both pieces before bonding them together. We recommend a heavy bodied cement with medium set for the best results. Weigh or clamp the pieces being bonded till they fully set. The bond is usually permanent in 24 hours at 70°F (21°C) or above. We’ve used additional cement to fill gaps and reinforce joints by applying with a disposable plastic dropper and drying for another 24 hours between every application. Care and patience makes for a neat job and a good bond. A technique we’ve used to seal the cell lid with pliable soft tubing to help alleviate “salt creep” at the lid’s edge. For the lid of the cell we use more sheet PVC. It’s useful to make the circular lid slightly larger in diameter than the outside diameter of the tank so it’s easier to grip. To create a soft seal on the cell lid (as shown in the photo), we first cut a thin ring of the same tube the tank is made from. Then cut the ring so the ends can overlap. Determine the amount of the ring to remove so when the ends touch, the ring will fit inside the tank with just enough of a gap for the seal to squeeze in and fill. Cut to remove that measured portion of the ring, leaving the ring in the shape of the letter “C”. Next we mold the prepared support ring by heating it gently with a heat gun till it softens and becomes pliable at 275°F (135°C). Form it into a ring with the ends touching and one edge as flat as possible (the one that will be glued to the lid). Be careful not to scorch the ring by keeping the heat gun moving in circular movements and avoiding getting the heat gun too close while doing this. This technique takes practice and patience (it may take between 5-10 minutes to do this procedure and it’s best not to rush), but good results are worth the effort. The formed ring can either be air cooled, or rags wet with cold water may be used to cool the PVC material till rigid again. Then center the support ring on the lid and glue it in place. The gasket is made from silicone tubing by cutting enough to make a ring that closely fits the OD (outside diameter) of the support ring on the lid. The ends of the tube are joined together by taking a short length of the same tubing, splitting it lengthwise, rolling it and inserting it in the ends of the seal to form a hollow O-ring. This O-ring seal can be bound to the cell lid with silicone caulk, which is left alone to fully cure. The caulk remains pliable in use and can be removed later to replace the seal if necessary. It’s a good idea to slightly chamfer the top inside edge of the tank so the seal will go in easier when the lid is closed on the cell. The Bucket Cell For simplicity and availability it’s hard to beat common 5 gallon buckets. When the bucket wears out, replace it for a few dollars and keep going. It’s prudent to place the polyethylene bucket in a secondary container, in case the bucket fails. A throw away plastic pan like those used to mix concrete for cement patching or post setting makes an excellent low-cost secondary containment. It should be large enough to hold the entire contents of the bucket. The bucket lid needs to be modified by adding a bucket cell adapter (or BCA) to hold the electrodes and other fittings. Usually the BCA is fabricated from PVC (polyvinyl chloride) plate or sheet. Various holes are drilled and tapped in the BCA for standard pipe fittings (NPT, National Pipe Taper) and either plugged or filled with the appropriate fittings. To attach the BCA to the bucket lid, compatible machine screws can be used. It’s useful to put a gasket between the lid and the BCA to prevent salt creep getting through. A bucket cell custom fabricated for a fellow enthusiast using 3/8” thick clear PVC plate for the BCA (bucket cell adaptor) with several ports drilled and tapped with common pipe threads and plugged. The BCA (shown above) has the PVC plate mounted below the lid with a Viton rubber gasket (which is compatible with the electrolyte) between the lid and the BCA, in hopes of sealing them. The bolts and washers are stainless steel, and they’re mounted to threaded holes halfway through the PVC plate (so the metal isn’t exposed to the cell liquor). The BCA is made from clear PVC only because that’s what we had on hand (the typical opaque grey or white PVC works just as well and costs less), and we’re hoping it helps In observing what’s going on inside the cell, though it’ll likely be clouded with condensation from the warm cell liquor. To cut the bucket lid we simply used a pocket knife and followed the edge of the ridge molded in the plastic, till the knife cut through. The BCA is sized to be a tight fit inside the larger ring in the bucket lid. If your bucket lid is flat, a square BCA would work also. Generally, one should put in as many tapped holes of the appropriate sizes as possible. There are always more things to add, measure or monitor as our experience grows. Tubular Electrode Leads, a Boon to Amateurs Most sellers of ready-to-use electrodes sell them with flat straps for the electrical connections. These are convenient if the cell top is open, but sealing them into the lid is a major chore, and often leaks appear when the cell is in use. The solution to this problem first appeared in the APC forum blogs by the individual known as “Swede”, in the blog site called, “You'll put your eye out...”. In there, Swede shows the techniques of how he built electrodes with tubular leads, with complete descriptions and a lot of photos. Tubular leads have the distinct advantage of being able to be securely sealed in compression fittings, which will eliminate the problem of “salt creep”. We recommend using Kynar (PVDF) compression fittings, which are as compatible in our system as is Teflon, but at about one fifth of the expense. The fittings need modifying to function this way but simply drilling through them (without the seals and nut in place) with a drill close to the size of the titanium tube works. Then replace the seals and nut. Tubular leads can be connected to the electrodes by several methods, but the most effective means we’ve used is by resistance welding (also called spot welding). The most afford-able equipment we’ve found to do this was purchased from Harbor Freight Tools Company when they had a sale (about $160). The leads can also be attached by riveting or screws, if the fasteners are also CP titanium (but they’re hard to find and may need to be fabricated). Electrical connections to the electrodes are made by either tapping the top end of the titanium tube to accept machine screws (to hold the ring terminal terminated leads from the power supply) or by inserting brass or stainless steel “all-thread” (threaded rod) into tapped holes in the metal filler (solder in the titanium tube leads) and attaching the power by ring terminals on these leads (held in place between washers and a machine nut) as seen in the photos above. Electrolyte Preparation To prepare the electrolyte we need to dissolve the salt crystals and nuggets in water. Due to impurities and additives in tap water, it’s best to use either distilled water or water purified by reverse osmosis (RO) to make our electrolyte. Filtered rain water can also be used. It’s a fact that moving water dissolves the salt seven times faster than still water. Whether moving the water by stirring or by pump, the effect is the same. Heating also works, but take care not to dissolve too much salt in the water; about 350g/liter maximum is ideal at room temperature (a bit less is okay). The following solubility charts will give you the optimal amount of salt in solution for a given temperature. Some Solubilities in grams per 100 ml water Compound--------------------------- 0°C 100°C KCl or potassium chloride---------- 238 567 NaCl or sodium chloride------------ 357 391 Solubilities of salts in grams per liter We should use starting materials as pure as we can find. Even if our salt is impure, it’s better to use pure water to make our electrolyte to limit the variables in our final product. Impure salt can be dissolved, filtered and recrystallized to purify it. We still use the potassium chloride (KCl) water softener salt for our salt source but there exists agricultural sources as well (muriate of potash), which definitely need purification before use in our electrochemical cells due to impurities naturally occurring or added to it. Again, any impure salt can be dissolved, filtered and recrystallized to purify it. Bibliography, Where to Learn More… - APC (Amateur Pyrotechnics and Chemistry Forum), http://www.amateurpyro.com/ especially the Chemistry section and Swede’s blogs - Science madness, http://www.sciencemadness.org/ especially the Technochemistry section - CHLORATES AND PERCHLORATES: THEIR PRODUCTION, by James Finckbone American Pyrotechnist Fireworks News Volume 7, Number 6 June, 1974 - Industrial Electrochemistry by C.L.Mantell, 1931 - Electrochemistry, Theoretical Principles and Practical Applications, by G. Milazzo 1963 - The Encyclopedia of Electrochemistry by C.A. Hampel 1964 - Industrial Electrochemistry by D. Pletcher 1982 - Electrochemistry in Industry by Brett 1994 - Electrode Reactions in the Chlorate Process (Doctoral Thesis) by A. Cornell 2003 - Influence of the Electrolyte on the Electrode Reactions in the Chlorate Process (Doctoral Thesis) by L. Nylen 2008 A Few Sources of Supply: - U.S. Plastics Corp. - http://www.usplastic.com/ 1390 Neubrecht Rd. Lima, OH 45801 USA (800) 809-4217 - Ozone Solutions, Inc. - http://www.ozonesolutions.com/products/Ozone-Compatible-Fittings 451 Black Forrest Rd. Hull, IA 51239 USA (712) 439-6880 - McMaster-Carr - http://www.mcmaster.com/ 600 N County Line Rd. Elmhurst, IL 60126 (630) 833-0300 or check for local listing

Flying Fountain -Uron Tubri (local name)

New design, new body, a bit advanced fuel. Turn up the volume!!! slight issues with the start that I have to figure out - but could not be happier - almost everything worked. By gps, 1km distance was travelled. Next test - will improve launch platform and will use slightly smaller diameter stainless steel tube + integrate camera.

Homegrown Oxidizers Part Three WSM The Power Supply Our power supply (5Vdc, 30A) The name plate, showing the input and output power Since the power supply has a voltage adjust trimmer, we can adjust the output voltage slightly above or below the 5V rating. To save energy we adjust it downward as the cell needs less than 4 volts to operate. Since this supply has multiple positive and negative output terminals, combining the positive wires to the anode and likewise the negative wires to the cathode will allow us to carry higher current with smaller gauge wires. The same technique is applied when a modified computer power supply is used (gather all the +5V leads to a bus for the anode and gather all the negative or ground leads to a bus for the cathode) to power the cell. A larger size and type of power supply with variable outputs. This power supply has variable outputs and can supply 0-40V and 0-75A, but costs many times as much as the simple supply shown above. An additional feature is it’s capable of constant voltage (CV) or constant current (CC) operation. The CC operation allows for simple current efficiency (or CE) calculations which allow us to know how well our setup is performing (industry usually works at above 95% CE, where with even the most advanced amateur setup, we’re lucky to break the 90% barrier). Setting the Cell up to Run We’ve got all our various parts gathered together, so let’s start our cell. Before we begin, we need to decide about the details: Where to run the cell (Indoors or Outdoors)? How much electrolyte is needed (fluid levels?) Where do we want to place the electrodes? Vent sizing and placement When do I “Pull the Plug”?! Electrode Care and Storage Where to run the cell Indoors (not to mean any inhabited area, which is too risky), your system is protected from the elements and unwanted approach by those unfamiliar with the hazards present. A big downside of running the system indoors is the effects of chlorine on any metal (or living organism) nearby. A good (non-sparking) ventilation system is advised if running a system indoors. We’ve normally elected to run our systems outdoors, for safety. That said, it’s still good to protect it from the elements and curious pets or people. A small lockable shed or other structure, tailor made for the purpose, is a good idea. The ideal structure should have a strong roof designed to shed any rain or contaminants but still allow proper ventilation to safely remove the hydrogen and any chlorine gas that may be generated. Protecting the components from direct sunlight is another function of a good roof. The walls of the structure can either be solid, screen material or a mixture. There are advantages and drawbacks to either one. Fluid Levels We have our cell but how much salt solution do we put in it? Most amateurs want the cell to be as full as possible, and this tends to cause (or encourage) more salt creep on the cell lid. Since the running cell generates heat and lots of very tiny hydrogen bubbles, a good friend and fellow enthusiast suggested keeping the fluid level well below the cell lid (up to 6” or 150mm below) to allow the space for those bubbles to pop, keeping any resulting spray away from the lid and minimize the salt creep problem. Though this will reduce the total volume of the cell liquor, the cell will run better overall. Electrolyte preparation by simply dissolving the salt in distilled water Electrode Placement Where one places the electrodes is a matter of choice, but we tend to place them off-center in the cell to promote more fluid flow, as discussed earlier. This is especially important if your cell has anything like a dome shaped lid (even slightly dome shaped), where the highest point is where the hydrogen vent should be. Don’t hesitate to experiment with electrode placement and see which spot is optimal for your system. The current usage and temperatures reached are a couple of the indicators showing how well the system is running based on electrode placement. A “bucket cell” showing offset electrodes and a large barb fitting for the vent (upper left side of the adaptor) Vent Size and Placement We’ve already mentioned placement (the highest point in the cell), but what size vent is required? As the cell runs it breaks down water. The oxygen is pushed onto the salt component ions, but the hydrogen ions combine with each other in a covalent bond and bubble out of the liquid. The amount of hydrogen gas formed at the cathode is dependent on the surface area and current demand of the system (in other words, every situation with its myriad variables is different) but the need to safely vent that hydrogen is the same. Making the vent oversized is better than making it undersized, so go larger rather than smaller with vent tubing. Hydrogen is very explosive, and in venting it, make sure to avoid any source of sparks or ignition to prevent a dangerous hazard. The material the vent is made of is not as critical as the cell structure itself, so polyethylene (PE), polypropylene (PP), or polyvinyl chloride (PVC) should work just fine. A piece of used garden hose (for example) attached to a barb fitting in the lid would work fine. Whether hard pipe or flexible tubing doesn’t matter, but it should rise straight up (or nearly so) so it won’t close off with collected condensed vapors and pressurize the cell (making the salt creep problem worse) as it will in a vertically coiled tube. If chlorine gas is generated by your cell, a scrubber consisting of a glass or compatible polymer jar containing sodium hydroxide (lye) in line with the vent, will eliminate any escape of the gas by binding it safely as salt. How Long to Run the Cell Most beginners to electrochemistry face this question. In the changes going on in an active cell, we start with high chlorides and transition to low chlorides, high precursors and chlorate. The process efficiency is not a straight line but an arc with a sharp drop off at a certain point [during the run]. Many beginners want to run the cell to completion, but converting the last bits of chloride uses much more power than the earlier parts of the run, and efficiency drops off greatly (diminishing returns). Practice has shown us that when the initial chloride level (maybe up to 16% chloride in solution) drops much below 10% KCl, the efficiency drops dramatically, and rather than use a lot more power to gain slightly more product; we stop the run, harvest the chlorate, resaturate the depleted liquor with chloride and start another run. Lacking the ability to simply or cheaply measure the chloride level in our liquor, we use the “rule of Thumb” and keep an eye on the current draw of our system. When the amperage demand of our cell (using the power supply above and without pH control) draws roughly half of the highest current level observed, we end the run, harvest the crystals and set up to run the next batch. We don’t worry about squeezing every bit of dissolved chlorate out of the depleted liquor because that chlorate and the precursor ions with it will help the cell to yield more chlorate much more quickly in subsequent runs, after replenishing it with fresh chloride. Electrode Care and Storage Our electrodes are chemically and electrically tough… as long as the power is on. Once the current stops flowing, the cathodic protection ceases and at this point it’s advisable to remove and wash the electrodes with fresh water, air dry and store them till the next run. Doing so will protect the working surfaces and lengthen the life of the electrodes. Other things can negatively affect the life of the electrodes, too. One reason we recommend using deionized or distilled water (or rain water, filtered to remove particles) to make up our electrolyte is that several dissolved minerals in tap water can either cover the working surfaces or attack the titanium substrate of the MMO anodes, shortening their life and efficiency. This is especially true if your tap water is fluoridated (fluorine ions can etch and destroy titanium fairly quickly and can dramatically reduce the electrode life). There are other elements in tap water that can cause problems too, depending on the water sources and quality in your area. Running the Cell Due to the nature of these cells, it’s best to run them without interruption. Once set up and running properly, they do their work most effectively when we leave them alone. Even just taking a look might reward you with a whiff of chlorine, so avoid doing that and maintain good ventilation where your cell is run. If your area is prone to power outages, an automatic power transfer system (ATS) might need to be considered for the health and life of your electrodes (let alone other vital services you depend on). A “bucket cell” powered by a modified computer power supply with a digital ammeter added Harvesting the Crystals Now that our cell is loaded with chlorate crystals, how do we recover them from the liquor without ruining our clothing or leaving our hands stinking of bleach? Wearing rubber or nitrile gloves helps (along with other common PPE’s or Personal Protective Equipment, such as goggles and face shield, rubber or vinyl apron, etc.). Even with such protective equipment it’s not advisable to reach into the cell liquor (essentially bleach) to recover the crystals. A friend uses an inexpensive aquarium fishnet to remove the crystals from his system. If the crystals are caked together (a common occurrence if the crystals sit for much time in the solution), a length of clean PVC pipe can be used to break them up, with or without a small square piece of flat PVC sheet glued on the end for a type of scraper or spatula. Purifying the Product Now that we’ve removed our wet crystals from the cell, we need to prepare them for actual use. The first step is removing the residual liquor. This is most effectively done with a process called vacuum filtration, with the side benefit of making washing any impurities off the crystals a simple task. Some examples of a vacuum filtration setup (many variations of this are possible) After the mother liquor is separated from the crystals we wash the crystals with chilled deionized water (to minimize dissolving our chlorate) in the same setup. The depleted liquor and wash water is recharged with salt and then added to the cell for another run. If further purification is required, the crystals can be dissolved in pure water and recrystallized. The moist crystals then are dried, powdered and stored for later use. How to Measure Total Yield To measure the yield we first weigh the dry crystals from our run. Next we determine the volume of the remaining liquor. Once we have the volume, we measure the temperature of the liquor. Compare the volume and temperature to the “Relative Solubilities” chart (published in part two of this series) and calculate the amount of dissolved chlorate and add that amount to our dry weight and we have a close approximation of the total yield of the run. Bibliography, Continued “Chloric Acid and Chlorates” section of Encyclopedia of Chemical Technology by Kirk-Othmer, published by Wiley and Sons, Inc., 4th and 5th Editions plus others. “Effects of Electrolyte Impurities in Chlorate Cells” by Richard A. Kus, Senior Research Chemist for ELTECH Systems Corporation at the 16th Annual Chlorine/Chlorate Seminar.

Large Case Formers! Do you really want one? Well, if you do and don't have a big lathe maybe these ideas can help you. I had a smaller cheapy lathe that I bought from a big box store. They don't sell them anymore and I burned mine up trying to make a former that is larger than an 8 inch'er. I contemplated what to do about this and I came up with a solution that went sideways...literally. Instead of laminating blocks of wood and machining them round I decided to take flat sheets and cut them round. Doesn't make much sense does it? Well it was actually a pretty nice project and the formers work really well. So I'll do a little explaining on how I did this pretty cheaply. My first decision was to use MDF board that is 3/4" thick. I sawed a bunch of MDF into round discs. Then I lightened them up a bit and finally glued all the sections together. So one section looks like the pic below and you can make and glue as many as you want for the length desired. I bought the material new but you could maybe find cheap furniture made of this stuff to use as a donor. This is one section of my 12" former. Maybe now you are getting my meaning! Keep reading to see how I made these formers. The smallest former below is an 8" that I made on a lathe. The other 2 are an 8" and a 10" that I made using the MDF material in this blog. First of all I had to come up with some inexpensive tools to do the job. I found a band saw on Craigs List for $25. I gave it a little attention by getting a couple of new blades for it and adjusting the guides pretty tight. I also changed the table top so that I could clamp a fixture board where ever I needed to. For the fixture I merely cut some material out of a board in kind of a rounded slot. Then I strategically drilled a 1/4" hole so that I could cut the radius I needed. Clamping the fixture to the table top gave me adjustability. Not really an ideal setup but it worked. Be sure to take your time with a new blade to cut the discs. Any forcing of any kind will not cut nice round discs! So what I did was I bought the MDF and I cut the sheets down to square pieces that are pretty close to the finish size of the former. For my 10" I believe I cut the MDF into squares that were 9-3/8" which is an 1/8" over a standard 9-1/4" former dimension for making a nominal 10" firework cylinder case. Then I took a straight edge and drew a line from corner to corner in both directions to find the center of each square. The next photo is a practice piece to see how well this project might work. I used the piece above for a top and another for a bottom. The build was looking pretty good so kept cutting. Before I got a bunch cut I used the center mark to swing an arc to find 3 evenly spaced points where I continued to hole saw out 3 holes from each disc for weight reduction. What I don't have a picture of is when I glued all the discs together. Take great care in this step to keep the discs clean for final assembly. If the discs have debris between them they might have air gaps between the joints. The center hole that I used is 1/4". After applying Titebond glue or similar to each disc I threaded them onto a 1/4" round dowel. Once all of the discs were thread together I put the stack in a press and applied light pressure to laminate them together without air gaps between discs. Take care to keep well away from the center hole with dowel when applying glue. The dowel hole can act as a vent when done. The catch is that you need to be able to remove the dowel after the glue sets. When I made both my formers I was able to remove the dowel from the center hole. After the glue dried I sanded to a slight taper and tried the former. Once I was happy with how they functioned I stained them with what ever I had on hand. Then I finished them with spar varnish which is a marine application. Spar varnish also has a little bit a flex to it for expansion and contract for when the MDF gets wet and dries. I never get my large formers that wet so they have not deteriorated in any way. After a several years of use I never regretted making them. Pics of the finished formers:

Homegrown Oxidizers Part Four WSM A fellow enthusiast has offered this method: When is a batch finished? For maximum anode life, one should end a batch run when the potassium chloride concentration drops to about 10% by weight. Without expensive analytical equipment the easiest way to infer the concentration is by measuring the specific gravity, which falls as the chloride is converted to the chlorate that largely drops out of solution. This can be done by carefully weighing a known volume of liquid in a small graduated cylinder. More convenient, however, is measuring the s.g. (specific gravity) with a battery acid hygrometer (or a more-expensive scientific one). You need the type with a large floating bulb with numerical values on the float. Any other type is useless for our purpose. This process is most conveniently done at 20°C (68°F). Lange’s Handbook has tables of solubilities for salts, including potassium chloride and potassium chlorate. It also has specific gravities. If we ignore the solubility of the chlorate as a first approximation, the specific gravity of a 10% solution of KCl at 20°C is found to be 1.0633. That for a 24% solution is 1.1623. Now, extrapolating (using other table values) for the s.g. at the solubility limit (25.4% KCl), we get a value of 1.1727. Thus, we would easily know the concentration of pure KCl solution based on a density measurement. We do have some potassium chlorate in our solution (after the first run). Lange’s Handbook tells us the solubility of KClO3 at 20°C is 7.4 grams per 100 grams water. That’s a 6.89% solution. Using the same process as above yields 1.0435 for its s.g. at that solubility limit. The above values are fairly accurate for the two pure salts separately in water. Now here’s where we have to make some assumptions for our actual solution. We assume the solubility of potassium chlorate in a KCl solution is about the same as that in pure water and further, that the actual specific gravity is given by adding the chloride’s specific gravity to the chlorate solution’s specific gravity minus 1. So we have 1.1727 + 0.0435 = 1.2162. Now, the mutual solubilities of the salts are somewhat less than in pure water, so it’s probably closer to 1.20. This is for a solution saturated with both salts. This is approximately the density of the second (and succeeding) batch starting solution after re-saturation with KCl. Finally, the density of the stopping point solution, if 10% KCl is desired, will be: 1.0633 + 0.0435 = 1.1068, or 1.10, rounded down with the same assumption as above. After all this complication, the final procedure is fairly simple. Our starting specific gravity will be near 1.20 (for the second and later batches saturated with chlorate; less for the first batch starting with pure potassium chloride). Its actual value may be less, but it doesn’t really matter. The ending specific gravity at 10% KCl will be about 1.10, so to ascertain the end point of a batch run, a sample from the cell is taken and cooled in an ice bath to 20°C (ignore the bit of crystallization which takes place). The supernatant liquid is checked for specific gravity, aiming for about 1.10. The solutions can be easily measured with enough accuracy for our purposes, and the actual stopping value doesn’t have to be very precise unless you’re trying to accurately measure your electrical current efficiency. A few more thoughts about oxidizer harvesting Before we continue, another fellow enthusiast shares a method he uses of harvesting chlorate crystals from his bucket cell: Harvesting the crystals may be done with a set of 100 micron screens (available from Duda Diesel at www.dudadiesel.com/) made to fit a 5 gallon bucket. The screens are strong and have held from 5 to 10 pounds of wet product without failing. They should be rinsed clean after each use. The mass of crystals is left in the cell bucket, and the warm liquor is poured off carefully through a screen into a catch bucket, not disturbing the crystals. The screen is then switched to a third bucket for removing and washing the crystals. This allows the rinsing (of the raw chlorate crystals) to be done without cooling down the mother liquor (which, at this point, will take up renewal salt quickly, with some stirring). Two things can be accomplished at the same time: The cold water rinse can be allowed to sit and drain while stirring the recharged bucket. Then back to a cold wash when the first quantity of cold water has gone through. A harvesting setup using multiple buckets and bucket screens. The description immediately above is useful for operating a single bucket cell fairly consistently and is capable of producing hundreds of pounds of oxidizer a year, with diligent effort. Turning the Product into a “Pyro Ready” Oxidizer We’ve harvested the crystals, but how do we prepare them for use in pyrotechnics? Once the chlorate crystals are rinsed with chilled, pure water in a vacuum filtration setup, they need to be dried. Drying can be as simple as spreading the crystals in a half inch layer on a cookie sheet and letting them dry in an oven set to 150°F (66°C) for an hour or so. For thick layers of crystals (up to 1.5”), use up to 250°F for a lot longer and with occasional stirring to break up the lumps. Another option is to leave the crystals on a polymer screen, tilted up slightly on one edge (for airflow) with a fan gently blowing across them until they’re fully dry. This may take a day or longer. Chlorate crystals drying in a tray lined with plastic foam wrapping sheets. The next step is to reduce them to powder. There are various means to accomplish this task, but the most common is ball milling. Also, small amounts of crystals can be milled in a high speed, rotary blade type coffee mill. This is perfectly safe if done without any type of fuel present. However it’s accomplished, once the chlorate crystals are reduced to a fine powder, they should be stored in an air tight container (preferably with a desiccant pack to keep them free flowing) and stored in a cool, dry (and secure) place. Setting up for Subsequent Runs The used electrolyte is a better starting point than the salt solution we originally began with. The reason for this is that the used electrolyte is full of precursor ions as well as dissolved chlorate from previous runs. The advantage of this is that subsequent runs produce chlorate right away. In storing used electrolyte, the best thing to do is keep it at room temperature in a covered container. A normal 5 gallon (20 liter) bucket with a secure lid will work, but any compatible, clean container will do. To recharge the used electrolyte, several methods will work. One of the easiest is to simply add the potassium chloride nuggets or crystals to the solution and let them dissolve till they reach equilibrium (no more salt dissolves at room temperature). Once that’s accomplished (from a few hours to a couple days, depending on the temperature of the liquid), the recharged electrolyte is ready to use for the next run. It’s usually best to use the recharged solution in the cell without any un-dissolved salt crystals included (use just the liquid portion). This way, you know your starting concentration and can calculate the current efficiency when the run is finished. Recharging the warm electrolyte by simply dissolving in more chloride crystals with either manual or mechanical stirring (for efficiency). Improving Yields As mentioned in an earlier section, higher temperatures increase the cell efficiency (and activity). However the greatest improvement comes with pH control. The pH is a number that represents the acidity or alkalinity of a solution. Neutral pH is represented by 7.0, lower pH numbers are acidic and higher pH numbers are alkaline. The further away from neutral, the stronger the acidity or alkalinity is. Left uncontrolled, the chlorate cell runs moderately to strongly alkaline. The greatest current efficiency (CE) is achieved when the pH of the cell is at or near 6.8 (slightly acid, since neutral is 7.0), where the ideal precursor ratio of 2:1, HOCl:ClO- (hypochlorous acid to hypochlorite) strongly favors the production of chlorate ions with the minimum of electrons (6 per chlorate ion as opposed to 9 without pH control). The end result of good pH control is more chlorate faster while using less current! The proper pH for peak current efficiency of chlorate cells. How do we control the pH? We add acid to the cell as it runs. Our acid of choice is hydrochloric acid (HCl or pool acid), which lowers the pH by adding atoms already present in our electrolyte. By using equipment and materials made to handle acids, and using careful assembly, this task can be greatly simplified. Some have suggested using an “off the shelf” pH controller. Unfortunately, using an active pH controller (like those used for saltwater aquariums or in laboratories) is impractical because the “ionic soup” our electrolyte is composed of, poisons most of the common pH sensors available. How much acid is required? Fortunately, industry has determined the quantity of acid required for the given current consumed per time unit (in milliliters HCl per amp, per hour) to achieve the ideal pH for the best CE of the cells. One number for a batch system like ours, as shared by Swede, is: 0.057 ml of concentrated (32%) HCl per ampere, per hour, with the HCl delivery cut by 33% after the chlorate crystals begin to form. Now since our system consumes water as it runs, we find it convenient to dilute the acid. If we dilute the acid to one fourth the concentrated strength (from about 32% to 8%), we use four times the volume to get the required amount (i.e. 0.228 ml 8% acid per ampere per hour to start) to optimize our CE. Note that the above recommendation is only an approximation. The actual usage in practice will depend on the individual operating conditions of your setup. Furthermore, it’s recommended to carefully calibrate your own pH control system to make it fail-safe, to avoid accidentally dropping the pH much below 6, where copious chlorine fumes will start to generate. Obviously, this is very undesirable. How is the acid added? Carefully! The best way to introduce the acid is slowly, low enough under the surface of the liquor that the chlorine stays in solution and does its work without escaping the cell. If acid is dumped on the surface of the electrolyte in the cell, the usual result is the release of toxic chlorine gas! Swede came up with an elegant solution to this problem. He plumbed a tube from the lid of the cell to plunge deep into the electrolyte and cross drilled it with many small holes, well below the liquid surface. As the acid is added to the cell in this dispersal tube, it slowly diffuses into the electrolyte which helps keep the chlorine in solution, where it benefits the chlorate producing system, instead of producing a noxious cloud. One example of an acid dispersal tube. Enter our pH control system! Our first thoughts of a system to add dilute acid to the cell involved an accurate timer controlling a pump to move the acid from its reservoir to the dispersal tube. Our friend Swede noticed a problem with this scheme, where the fluids would retract in the tubing between doses and cause inaccuracies in the amount of acid delivered. His simple and elegant solution to this dilemma is to place the acid reservoir at a higher level than the cell and let the additional head pressure gravity feed the acid injection, rather than pump it. A minimum acid reservoir height of one or two feet (±1/2 meter) above the cell is usually adequate to supply enough pressure for such a system, and more is stronger. A timer, PTFE solenoid valve and PTFE needle valve with PVDF fittings for our gravity-fed pH control system. Parts needed for our system include (acid compatible): Liquid tight, vented reservoir with a fill port and drain, including a shutoff valve Tubing and fittings An accurate timer system to control doses A solenoid valve for acid delivery and shutoff A needle valve for fine tuning the dose volume The fabricated acid dispersal tube running inside the cell The timer is the heart of this system. An ideal timer is sold by Auber Instruments on eBay and is fully programmable and accurate to less than one second per day. It has a range from 0.01 seconds to 9999 days. To test the setup we programmed it for quarter hour dosing for 5 seconds. As seen in the photo below, the lower number is set for 14 minutes and 55 seconds (5 seconds short of fifteen minutes), and when that time runs out, the internal relay switches on for 5 seconds, then resets the cycle and continues the next timed interval. For actual use with the cell, the timer is programmed for hourly injections of dilute acid, and the needle valve is adjusted to deliver the required volume, determined by testing (between the timer interval and needle valve setting, running water into a graduated cylinder) until the correct dose is achieved. Our timer module, shown below (mounted in a PVC electrical box), is wired to feed power to the duplex outlet through a solid state relay. The timer’s internal relay switches on 9Vdc (from an auxiliary terminal on the timer module itself) to the control side of the solid state relay, switching on the 120Vac power to the outlet, which in turn opens the solenoid valve (powered by the 12Vdc adapter shown, plugged into the outlet), allowing the acid to feed into the dispersal tube in the cell. The “dry test” of a gravity fed pH control system set for 15 minute intervals. The tubing shown in the photo above is a rubber material designed to be used with peristaltic pumps and is listed as compatible with dilute HCl (hydrochloric acid). The acid reservoir tank is a modified laboratory pipette cleaner made of cross-linked polyethylene (XLPE), listed as impervious to HCl. The acid reservoir shown below was fabricated from PVC pipe and fittings by a fellow enthusiast, and is also compatible with HCl. If building your own from PVC, be sure it’s liquid tight (leaking even small amounts of dilute acid can amount to a serious hazard over time). A partially completed PVC acid reservoir. The cutoff valve is mounted, but the fill port and vent fitting (toward the top) haven’t been installed yet. This is a closed system, so by venting the upper part of the reservoir to the cell, any vacuum created (when the fluid level drops) is broken and the acid will freely flow when the valves are open. By including two more tapped holes (to the top and bottom sides of the reservoir) a compatible and clear sight glass can be added to monitor the fluid level inside. Testing the pH of the electrolyte This can be a tricky proposition since our electrolyte is a very potent bleach mixture. If using standard pH paper, the paper tends to bleach almost instantly. However, if we dip and quickly observe the color before it disappears, we can get a close estimate of the pH level of our cell. Some experimenters like to use the relatively inexpensive electronic pH pens available, but they don’t last long in practice, since the element is poisoned by the cell liquor. If it’s tried, the best approach would be to quickly test and then rinse the element in distilled water and store the pen tip in 3M (3 times molar) potassium chloride storage solution, for the best chance of survival for a pH pen. Never store pH sensors in water (which will eventually ruin them); store the sensor bulb in 3M KCl solution, either purchased or made up by the user. Greater efficiency and production In the next article, we’ll describe continuous chlorate cells and things to consider when setting them up and running them.

Testing flash powders (for homemade firecrackers) from the most known ingredients at home. Sulfur, Sb2S3 as catalyst increased performance highly in all cases. In the case of sulfur, 10% catalyst was ideal. KClO4 Al 70/30 and KClO4 Mg/Al 50:50 they operated with significantly worse efficiency without a catalyst. Close metal powder and oxidizer ratios they operated with much better efficiency than higher oxidizer an lower metal powder combinations. The winner was Potassium Perchlorate Aluminum Sulfur 50/40/10% (3-7 micron aluminum for small firecrackers). And 50:50 mixed 30 micron Blue aluminim or another aluminum under 40 micron with 3-7 micron dark aluminum powder for bigger salutes (above 10g). It has unimportant advantages over other flash powders. This flash powder is the king of firecrackers and ground salutes after 10 year research. 1. The best proven flash powders what I recommend best. Extreme: KClO4 Al S 50/40/10 3-7 micron dark aluminum required for small firecrackers and 50:50 30-40 micron Blue Aluminum and 3-7 micron dark mixture for bigger salutes (above 10g) to get a huge effect. The best flash powder for firecrackers I've ever seen. Does not need to protect the aluminum with boric acid in this composition. It can be made safely, for friction not particularly sensitive and have a good storage stability. The voice is very sharp and extremely loud, the effect bright white gloss. For bigger salutes are important to use 30-40 micron aluminum and 3-7 micron dark 50:50 mixture to get huge explosion effects. Sulfur significantly increases performance, and the high proportion of aluminum for the effect. The ratio brings the best efficiency with both ultra-fine and coarser like homemade aluminum. I use this the best flash powder I know. Ba(NO3)2 KClO4 Al S 30/30/30/10 with 30-40 micron aluminum (Blue) and 3-7 micron (Dark) 50:50 mixture (above 10g). Here need to coat the aluminum with 2% boric acid (what dissolved in water and the Al dried later) important! This was the stun grenade formula How to Build Flash/Stun Grenades By George Dmitrieff and a photoflash powder with sulfur. Barium nitrate with aluminum are much more brighter than magesium or magnalium. Brighter than the previous version, have the same sound but less powerful. In small firecrackers have no advantage compared to KClO4/Al/S 50 40 10. Moderate: NaNO3 Mg S 50/40/10 with 400 mesh fine magnesium powder. Here need to coat the Mg with 4% boiled linseed oil and dry it to get a hard strength coat before use or the chemicals will attack the Mg! And the NANO3 must be dried after grinded and before use at 150-200°C to get free from moisture. Moderate loud composition have a characteristic yellow bright effect (this flash effect are not white). Slightly stronger than KNO3 but much more weaker than Ba(NO3)2, or Sr(NO3)2. The brightest flash after Ba(NO3)2 and Sr(NO3)2. NaNO3 are hygroscopic, this is disadvantageous to storage. Moderate: KNO3 Mg S 50/40/10 with 400 mesh fine magnesium powder. Here need to coat the Mg with 4% boiled linseed oil and dry it to get a hard strength coat before use or the chemicals will attack the Mg! Default flash powder with moderate sound bright effect nothing extra. Ba(NO3)2, Sr(NO3)2 much more stronger than this flash powder. Extreme white bright effect with powerful sound: Ba(NO3)2 Mg S 50/40/10 with 400 mesh fine magnesium powder. Here need to coat the Mg with 4% boiled linseed oil and dry it to get a hard strength coat before use or the chemicals will attack the Mg! Extreme white bright flash powder with powerful but not extreme sound. The brightest nitrate based flash powder i know. It's much better worth it than KNO3 for the extreme light, and the power. The best nitrate based flash powder for firecrackers, ground salutes. Much more stronger than KNO3 and NaNO3 versions. Strontium white powerful: Sr(NO3)2 Mg S 50/40/10 with 400 mesh fine magnesium powder. Here need to coat the Mg with 4% boiled linseed oil and dry it to get a hard strength coat before use or the chemicals will attack the Mg! Slightly stronger than Ba(NO3)2 but Ba(NO3)2 are better for firecrackers. It has a stable white effect the best Ba(NO3)2 Mg S alternative. From Sr(NO3)2 you can not make Glusatz. All nitrates worked properly with magnesium, each is significantly weaker with aluminum or does not work for firecrackers. KNO3, Ba(NO3)2, NaNO3, Sr(NO3)2, they all require magnesium (except Ba(NO3)2 with KClO4!). Aluminum based flash powders are much more brighter than magnesium or magnalium versions. Ba(NO3)2 with KClO4 using aluminum works the best magnalium 50:50 alloy are less effective. Magnalium with only nitrates are weak for firecrackers. The used -400mesh magnesium powder current mesh size in the tests: ballmilled, 40 μm / 400 mesh, fraction 40-4μm - 0,2%, fraction 20-40μm - 67%, fraction <20μm - 32,8%. At 40 microns -400 mesh, the finer the particle size the better, the ideal Mg particle size would be around 20 microns. The grain size reached a maximum of 40 microns, but the factory metal powder contained a much finer grain size. Before you buy metal powder, check exactly what size particles it contains. The used Blue Aluminum powder current mesh size in the tests: 99,5% Aluminum: > 250 μm: 0.6 %, 150 - 250 μm: 1.7 %, 74 - 150 μm: 5.1%, 37 – 74 μm: 7.5 %, 20 – 37 μm: 25.0 %, 10 – 19 μm: 29.0 %, 4 – 10 μm: 26.0 %, 1 – 3 μm: 6.0 % Extreme: KClO4 Mg:Al (50:50) alloy (325-400 mesh) S 50/40/10. Here need to coat the Magnalium with 4% boiled linseed oil and dry it to get a hard strength coat before use or the chemicals will attack the Mg! Not stronger than the KClO4/Al/S 5/4/1 version light is less bright and smaller effects can be achieved with it if the metal powder is too fine. More sensitive to friction than aluminum. The advantage is that the 50:50 Mg/Al alloy easy to grinded, powdered at home unlike Magnesium or Aluminum powder. In larger salutes if the KClO4 mixed with Ba(NO3)2 using magnalium a 30 Ba(NO3)2 30 KClO4 30 Mg/Al (not finer than 325-400 mesh 40-45 micron) 10 Sulfur are much more effective or using Sr(NO3)2 than the pure KClO4 version! Similar to KClO4 Al S and Ba(NO3)2 KClO4 Al S versions but only with the nitrate. Extreme: KClO3 Al 70/30 (3-7 micron under 10g salutes and 60/40 ratio for 30 micron blue+2-7 micron dark aluminum 50:50 above 10g salutes) This is a KClO4/Al/S alternative and almost have the same power but much weaker. Much more powerful than the non KClO4 based flash powders. Much more sensitive than KClO4/Al/S have similar sensitivity like KClO4/Mg/S. The friction sensitivity of the KClO3 was reduced by heating after grinding to 250-300°C to be free of moisture and chloric acid temporarily and added 5% KHCO3 potassium-bicarbonate! Excelent for firecrackers and booster too with 3-7 micron aluminum. KClO3 with MgAl, Mg, Sulfur, Sb2S3 are extremely sensitive for friction. I couldn't find any other KClO4 alternative what have similar power. Does not need and not recommended using boric acid to the aluminum! This flash powder power cannot be increased with sulfur or Sb2S3, or much more reactive metal powders because with those will be unstable and extremely sensitive for friction the composition! For large salutes the KClO3 (or KClO4) 70/30 the sound was OK, but the visual effect with 3-7 micron dark Al was poor. When KClO3/Al 60/40 ratio and 1:1 Dark+Blue aluminum mixture are used in the composition this improved the quality of the visual effect size and brightness in large salutes. For bigger salutes (above 10g): Only with KClO4 40-45 micron magnalium 50:50, 3-7 micron+ 30-40 micron 50:50 mixed Aluminum (Blue, atomized), 40 micron magnesium+ 30-40 micron aluminum (Blue, atomized) 50:50 mixture make huge stable flash effects. For small firecrackers (under 10g): 40 micron Mg/Al, 3-7 micron Al, 40 micron 325 mesh Mg, working the best with KClO4. Too fine metal powders with KClO4 spectacularly reduce the flash effect in bigger salutes especially with 325-400 mesh (and much finer) Mg, and 3-7 micron Dark Aluminum. Too coarse or of an inappropriate proportion of fineness metal powders mixtures are weak, slow for flash powder. The aluminum in the aluminum mixture must kept under 40 micron, and must be not firefly bright flake, i used atomized or 30 micron Blue Aluminum are ideal. 2. What I don't recommend did not work: KClO4 Mg S 50/40/10 Here need to coat the Magnesium with 4% boiled linseed oil and dry it to get a hard stregh coat before use or the chemicals will highly attack the Mg! The effect is unimaginably weak, you will see absolutely nothing in larger firecrackers if the Mg are too fine. For friction very sensitive compared to other written above flash powders. In firecracker not stronger than KClO4 Al S 5 4 1 with 3-7 micron dark aluminum. Sulfur minimally increases the sensitivity to friction here, It is almost the same sensitive without sulfur. Which were very weak for firecrackers: BaSO4 Mg and KNO3 Al S I find them very weak for firecrackers. Antimony trisulfide Sb2S3 based flash powders: 60 KClO4 30 Al (dark 3-7 micron) 10 Sb2S3 for boosters are much more powerful, brisant than the classic KClO4/Al 70 30. In homemade setup much more worth it than the classic 70/30. This KClO4 Al Sb2S3 composition are used in high quality extreme loud and bright mini and 0,3g (maximum 0,5g) match crackers by the factory setup. Used in another compositions where 50/40/10 ratio are used this can changed to 50/35/15. In 60/30/10 ratios do not change the composition. KClO4/Al/S 50/40/10 are same good for booster. Compared to sulfur powder Sb2S3 are costly, in the case of using KClO4 it does not increase performance much more than sulfur. Does not cool down the flash powder like sulfur this way burning higher temperature. When sulfur are used 10% are not reduces the burning speed, when Sb2S3 this can be 15% when the metal powder and Sb2S3 ratio are not too close each other 35% metal powder 15% Sb2S3, or 30% metal powder 10% Sb2S3. For flash powder Sb2S3 are too costly the price are 3X higher and not worth it compared to sulfur. Highly recommended to use sulfur in all flash powder what used in ground salutes, firecrackers, booster. Without it are much weaker the flash powders. In the factory setup in high quality extreme bright, and extreme loud European mini firecrackers, match crackers (0,5g and under) Sb2S3 or sulfur always used for the flash powder! Which were dangerous, unstable and non professional: Ba(ClO3)2 Al S extremely sensitive to friction and greenish (half with Ba(NO3)2, or Sr(NO3)2 reduces sensitivity but not too much). KClO3/Al/S Even the most reliable of the most dangerous flash powders. Very sensitive to minor friction (extremely powerful have the same sound and effect than the KClO4 version performance is theoretically weaker but technically you will se nothing difference in sound and effect). KClO3/Al 70/30 much more weaker and much less sensitive without sulfur. KClO3/Mg very sensitive for friction, Na2S2O8 and K2S2O8 Mg with moderate sound absolute a non professional flash powder self-ignition may occur very easily during storage. Na and K persulfate are worse oxidizers than nitrates like KNO3. KMnO4 Al S (60/30/10) with moderate sound and power absolute not have a storage stability. Potassium permanganate stronger oxidizer than nitrates. And louder flash powder can be made from it with aluminum powder than from nitrates with magnesium. After KClO3 and chlorates (Ba(ClO3)2) this was the most strongest flash powder. The friction sensitivity of the KClO3 was reduced by heating after grinding to 250-300°C to be free of moisture and chloric acid temporarily and added 5% KHCO3 potassium-bicarbonate! And added 1/4 KHCO3 to sulfur when tested! The tested chlorates with aluminum much less sensitive than magnesium. Magnesium with sulfur without oxidizer give a fast flash too this makes it even more dangerous! The power of flash powders for firecrackers: The Nintrate/Magnesium/Sulfur flash powders in power are almost same in power. High-powered firecrackers cannot be made from them. They are working in firecrakers, but compared with KClO4 their performance and voice are below average and weak. The most spectacular was Ba(NO3)2 what have a extreme bright light and a good sound, alternative for this are Sr(NO3)2 with the similar power and quality bright white effect. For quality salutes and firecrackers i recommending to use minimum Sr(NO3)2, or Ba(NO3)2, firecrackers with KNO3 and NaNO3 are a lower quality category. In Normal, Larger, Black Powder, sized firecracker paper tubes the Ba(NO3)2 Mg S flash powder produced exceptionally good quality in terms of absolute bright white light and sound what are similar to KClO4. If i didn't have KClO4, I would choose this for bright loud firecrackers. For safe high-powered firecrackers required KClO4 with (Sb2S3 or sulfur), aluminum. KClO4 with Mg, Al, MgAl gives a relative almost same power in presence of sulfur, and the safe choice are aluminum. KClO4 with Mg/Al alloy 50:50 and pure magnesium are much more sensitive than aluminum. I did not find a safe KClO4 alternative, for extremely strong firecrackers. The paper tubes: The paper tubes made from copy paper, glued with 40% water glass (Sodium Silicate solution). The wall thickness are calculated from the tube internal diameter and used 8-10% paper thickness from the internal diameter. Example in a 40mm internal diameter tube are used 3,2-4mm paper wall thickness. The sodium silicate gluing made strength, rigid, hard paper tubes which proved to be very ideal for firecrackers. Thicker but not overly thick hard, solid tubes are ideal for firecrackers. The wall should be more thicker rather than thinner when we make it, and uniform thickness with deep end plugging or the firecracker will be quarter as strong. The cylindrical shape works with the best efficiency because the paper tears evenly. With the triangular shape, for example, where the paper distribution is not uniform, I experienced a significant difference in performance. Through the mini (milligram) firecrackers the medium and bigger firecrackers the water glass+copy paper combination it works very well. For bigger paper tubes (masking paper from paint shop), kraft paper with wood glue (Wood Glue/Water 3:1 dilution ratio) very good paper tubes could also be made. The exact paper size was calculated for the current product. I experienced it at factory paper tubes that the paper does not tear evenly, the wall thickness is not correct, and weaker, in many cases I achieved much lower efficiencies with factory made paper tubes. Especially with them, they break in a spiral. My blog with more description (Hungarian): https://mx5-kevin.blogspot.com or https://sufnipiro.wordpress.com Tether USDT and BNB BEP20 or (Matic Polygon) small amount donation to support projects: 0x16829457123552A574441bf38Eeaf93B46105A1d BTC Bitcoin donation: 16aiyTMQDagpcD1za5yoVLCMssym52QLnf Testing flash powders for firecrackers from the popular most know oxidizers: https://www.bitchute.com/video/9yAJCFMwMsmv or https://odysee.com/@mx5kevin:a/Testing-flash-powders-for-firecrackers-from-the-popular-most-know-oxidizers:3 Tests: https://www.bitchute.com/channel/X6adxEKbK8Ky/ The flash powder (with tests): https://www.bitchute.com/video/aElYEUtifJZB/ or https://odysee.com/@mx5kevin:a/How-to-make-powerful-firecracker-flash-powders-and-fine-magnesium-aluminium-powder:e The flash powder (ball mill process): https://www.bitchute.com/video/Uapx1fZZdyJx/ or https://odysee.com/@mx5kevin:a/How-To-make-Flash-Powder-with-ball-mill:c Testing the KClO4/Al/S 50/40/10% (with 3-5 micron Dark Aluminum powder) in homemade mini match crackers: https://www.bitchute.com/video/jVTqaAhMONRL/ or https://odysee.com/@mx5kevin:a/dorzsfejespetarda:c Simple ID 7mm (made the tube by wrapped on the pencil). The firecrackers tube made from 2x(70mm wide x210mm long) copy paper, gypsum 20mm, visco fuse 80mm long 2mm wide, glued with 40% sodium silicate solution. Filled with sifted loose texture flash powder. Tube parameters for firecrackers: From copy paper glued with 40% sodium silicate solution Normal: ID: 5mm tube made 2 piece W:70mmx L:145mm paper gypsum 20mm Visco fuse 2mmx80mm (cc ≈0,9g Flash power) Larger: ID: 7mm tube made 2 piece W:70mmx L:209mm paper gypsum 20mm Visco fuse 2mmx80mm (cc ≈1,2g Flash powder) Black Powder or mega (2mm granular willow ideal): ID 15mm tube made 6 piece W: 105mmx L:150mm paper gypsum 30mm Visco fuse 2mmx100mm (8g Fash powder if FP are used instead of BP). Or from a 1mx25m masking paper (craft paper) 1 meter total paper length are required. Ground Salute: ID: 25mm tube wall 3-4mm, gypsum 30mm, length 150mm tube wall calculated (the wall thickness must be much more thicker than 2,5mm or the sound will be reduced, but not thicker less than 5mm maximum +2mm (5-7mm when 1mx25m masking paper (craft paper) are used instead of copy paper) or the visual effect will be reduced and a wall thicker than this does not increase the sound volume further). Flash powder 30g (Visco Fuse 500mm length (50sec delay) from 2mm visco 1cm/sec burning rate for KClO4 based FP protective distance: 50m 164 feet). For this tube 2m masking paper are used or 10 full piece copy paper what cutted half to 150mm. Above 40mm tubes IDx0,08mm minimum IDx0,10mm maximum wall thickness calculated. KClO4/Al/S 50/40/10 in ID: 5mm Normal tube cc ≈0,9g Flash powder (extreme loud old version from aluminum foil) KClO4/Al/S 50/40/10 Extreme loud Ground Salute 25g (aluminum foil version from cc 20 micron aluminum) mega effect with mixed aluminum or homemade aluminum from aluminum foil. The record holder are made from 30g flash 3 meter large flash effect (Dark 3-7 micron+Blue 30 micron 50:50 mixture). The mixture are worked under 40 micron aluminum. The KClO4 Ba(NO3)2 Al S 30/30/30/10 version similar with the same aluminum mixture, the magnitude of the effect is smaller but brighter. The flash powder must be loosely textured filled in the paper tube without any compression. It must be sifted through a sieve before loading to get a lose texture. If it is not made at the same time, it must be mixed because the burning rate a little bit is always different. Must be avoided for the powder to be denser at one point of the tube, or the burning speed to be different.

The homemade chlorate and perchlorate project The video from the process: or https://www.bitchute.com/video/JsRryZQmK3Rv/ or https://odysee.com/@mx5kevin:a/Make-potassium-perchlorate-KCLO4-from-sodium-perclorate-Naclo4-with-electrolysis:8 KClO3 Vs KClO4 tests: https://www.bitchute.com/video/rkfx0mcotRcb/ or https://odysee.com/@mx5kevin:a/KCLO3-VS-KCLO4-important-differences-and-tests:c or My website with more Hungarian description and documents: https://mx5-kevin.blogspot.com or https://sufnipiro.wordpress.com My BitChute chanel with more videos and tests: https://www.bitchute.com/channel/X6adxEKbK8Ky/ Tether USDT and BNB BEP20 or (Matic Polygon) small amount donation to support projects: 0x16829457123552A574441bf38Eeaf93B46105A1d BTC Bitcoin donation: 16aiyTMQDagpcD1za5yoVLCMssym52QLnf More documents: https://odysee.com/@mx5kevin:a or https://drive.google.com/drive/folders/0BwXIGQD4ku3hfjc0NXZYV2ZydnlvTXR1RkxoV09nVGgydFloWUdReVNCeXV5aThoSHlrRTQ The setup: Sprinkler connection module Soft PVC Pipe Tube 6m plastic jar lid 500ml glas jar 6V 4A car battery charger Cathode 8mm carbon welding rood Cathode 2: Titanium the best Calculation: For the double displacement reaction calculated using a periodic table from relative mass the ratios (KCl+NaClO4). In a electric balance calculated 1kg water to 1000ml 1l. Protecting the tools: The beaker: Use a Wire Gauze Heat Shield with Ceramic Center to protect the beaker from thermal shock or will be cracked or use a sand bath this is important. Do not heat directly intensive way in hot plate because this will crack the beaker. Hotplate: Protect it with aluminum foil from corrosion. Stainless steel saucepan: Do not heat it in wet NaCl, KCl, NaClO4, NaClO3 crystals in it this will rusted the saucepan immediately and contaminated the product. Do not boil HCl acidic solution in it. Use 18/10 stainless steel. Possible to heat in it wet KClO3 and KClO4 crystals without erosion. The electrodes: Only use few micron platinum or PbO2 in perchlorate cells and make the chlorate with MMO anode. Keep the pH 6-7 or 7-8 to protect the MMO and PbO2 anode from too alkali or acidic solutions using a digital pH meter. Digital pH meter: Need to calibrate with pH buffers, and always wash it with NaHCO3 solution after used in the chlorate perchlorate cell. Aluminum saucepan, ceramic pans, in oven, gas stove: In pure aluminum possible to heat wet KCl, NaCl, NaClO4, NaClO3 crystals and the pan not get rusted using a hotplate or gas stove. But pure aluminum not tolerate alkali or acidic solutions! Protective gears: The cell must run and the processes must make in outdoor. Use a M3 protective mask, protective glasses from chlorine, protective plastic gloves! The platinum anode and graphite 8mm welding carbon rod cathode for NaClO4 and KClO3 KClO3 from KCl after 1 week Platinum anode parameters for KClO3 and NaClO4 Silver 70mm x 3mm pure platinum 0,2mm (200micron platinum) fully coated the silver. For 400-1500ml cells max 6V 4-6A. Anode materials one step chloride to perchlorate setup: Platinum (thickly coated): For a 0,5l cell a 70mm long 3mm wide silver rod what is fully coated with 0,2mm (200micron platinum) thick pure platinum so that they are not attacked by chemicals a choice for life for chlorate and perchlorate production in one step. It must be made individually. For using 400-1500ml small cells are excellent. Using plastic champagne cork and silicon inside cell with less corrosion possible to connect it from the copper wire. This anode required only a cheap 6V 4-6 A car battery charger, maximum of 2 Amps will actually pass through the cell (if a 10mm carbon cathode are used) this power supply can handle this comfortably. Anode materials two step chloride to chlorate and chlorate to perchlorate setup: MMO anodes RuO2, IrO2, TiO2 mesh in a titan base for chloride to chlorate production. And chlorate to perchlorate production strong beta PbO2 in titanium base, or few micron platinum in titanium base. For thin platinum on a titan base or PbO2 making the NaClO3 first with MMO, than the NaClO3->NaClO4 conversion with Pt, PbO2 are the best. Multiply by many the lifetime a few microns platinum coated anode. In the case of strong beta lead dioxide anodes, this is only allowed in the two MMO/PbO2 step. For thin platinum on a titan base or PbO2 making the NaClO3 first with MMO, than the NaClO3->NaClO4 conversion with Pt, PbO2 are the best. Multiply by many the lifetime a few microns platinum coated anode. In the case of strong beta lead dioxide anodes, this is only allowed in the two MMO/PbO2 step. 5 micron platinum coating on a titanium anode all platinized titanium anodes are poor quality. Such electrodes are destroyed quickly. Everyone who bought such electrodes this anodes are quickly damaged. These are the electrodes that multiple costumer are say that people shouldn't buy. Avoid all platinum electrode where the platinum layer are thinner than 100 micron, 200 micron platinum layer are ideal and costumer specific dimensions. Overcoat the full electrode with platinum to protect it from chemical attack. There should be no exposed silver at either end of the electrode. Used tools: Beaker 2000ml, Stainless steel pan, Digital pH meter (need to calibrate with pH buffers pH4.01 and pH 7.01 regularly). Used chemicals: HCl 30%, Potassium metabisulfite K2S2O5, Sodium persulphate Na2S2O8, The cell: The cell are running outdoor with a plastic paint bucket and plastic seed bed foil it is covered. With Soft PVC Pipe Tube 6m the resulting gases are led away. Making potassium chlorate: Every 1gramm KCl dissolved 2,9 gram H2O (saturated solution at room temperature) the pH keeped 6-7 2g/l sodium persulphate are used to reduce chlorine gas and help the process. Used cell 0,5l with 400ml solution and 138g KCl pH 6-7 used HCl cc 4ml to the 400ml solution/day and 0,5-1g sodium persulphate additive. Every day added the HCl until the process are end. 6V 4A car battery charger are used as power supply maximum 6A cell temperature 20-45°C runtime 1 week. Maximum of 2 Amps will actually pass through the cell (if a 10mm carbon cathode are used) this power supply with this small anode can handle this comfortably without overheating the cell, or overloading the power supply. The pH controll/day. Used a 1,5l plastic bootle into which the solution is poured added the HCl and shaked. All chlorine gas in the solution must be absorbed in pH 6-7. The pH are tested with digital pH meter what calibrated with pH 7.01 and 4.01 buffers. 1 week later all KClO3 are crystallized in the solutoin washed with ice cold water. Dissolved in hot water filtered with all purpose cloth and recrystallized in double water than crystals when cooled down at room temperature. When the solution are boiled and the crystals started forming this point i stopped the heat and slowly cooled down the solution. Washed again the crystals and recrystallized again, washed again the crystals and dried out the crystals using a hotplate and a saucepan. The result minimum 99,5% pure KClO3. Using MMO RuO2, IrO2, TiO2 or Platinum (thickly coated 0,2mm) are ideal this process. With daily pH control experimentally possible to make the process with graphite anode or welding carbon rood and with NaClO3 too. Making potassium perchlorate from sodium chlorate: Every 1gramm NaCl dissolved 2,8 gram H2O (saturated solution at room temperature) the pH keeped 6-7 2g/l sodium persulfate are used to reduce chlorine gas and help the process. Used cell 0,5l with 400ml solution and 142g NaCl pH 6-7 used HCl cc 4ml to the 400ml solution/day and 0,5-1g sodium persulfate adative. Every day added the HCl until the process are end. 6V 4A are used maximum 6A cell temperature 20-45°C total runtime 3 week. The pH controll/day. Used a 1,5l plastic bootle into which the solution is poured added the HCl and shaked. All chlorine gas in the solution must be absorbed in pH 6-7. The pH are tested with digital pH meter what calibrated with pH 7.01 and 4.01 buffers. At the end the last 1 week when HCl added and no gases are formed this point the pH are keeped 7-8 and no more HCl are added. This point from pH 6 posible to go to pH -1 after a day running only in perchlorate cell. Only with Platinum (thickly coated 0,2mm) from NaCl to NaClO4 this process can make directly. With few micron platinum anode or PbO2 the chlorate must make first with MMO anode than the perchlorate with PbO2 or platinum. After 1,5 week need to test with sugar and methyline blue to calculate when the NaClO3 are complete and perchlorate start forming. At this point must change the MMO anode to perchlorate specific anode or the MMO anode will damaged. As cathode titan and graphite ar all excelent for chlorate and perchlorate production too. We will smell a strong ozone during perchlorate production. When PbO2 are used at the end of the process must keept the pH 7-8 and great care must be taken to wear the anode. Erosion is particularly high at the very end of the process. Lead dioxide is the most sensitive to this. Chlorate test here must be used in a test tube where with HCl and sodium or potassium metabisulfite are destroyed the chlorate. Do not make sensitive chlorate tests directly in the cell solution because some chlorate always left behind! This test is optional. When the perchlorate ready after that only ozone production happened. We cannot harm the process by electrolysis. When graphite cathode and platinum are used and the graphite cathode it starts to wear slightly the NaClO4 are ready. When the solution is absolute NaClO4 the erosion in the anode and cathode are extremely high. When 0,2mm platinum used in a silver rood base in KClO3 and NaClO4 setup no precise pH control is required unnecessary in such a case buy a costly pH meter. Just add the solution every 1000ml solution to 10ml 30% HCl/day this electrode does not hurt if the solution is much more acidic. That it contains in large quantities NaClO3 it can be said with simple tests without costly sensitive tests. Dry from NaClO4 in the solution make it a fine powder and in a aluminum foil wrapped spoon start it to heat in a gas stove. You will can not melt NaClO4 just NaClO3 so not possible to melt together the crystals. Possible to use this test in a hotplate using a stainless steel saucepan is a small aluminum foil. Another test get the cell solution few mililiters heat it and mix it with hot KCl solution (the same concentration or slightly dilute solution than the double displacement reaction used). KClO3 can dissolved the hot solution, KClO4 are not. When the solution are cooled down and lot of colored large crystals forming that are KClO3. If almost nothing crystallize out when the solution cooled down thats KClO4 and thats OK. If in the hot sulution when mixed are not formed white crystals as as that point the solutions meet that not KClO4. If The KClO4 boiled with HCl and K metabisulfide and the solution will turn strongly yellow thats mean the solution strongly contaminated with chlorate. When boiled and you will not see yellowish color change and smell lot of SO2 gas, and when be concentrated, it will be dark brown not yellow thats OK. They are sensitive professional chlorate tests like N-Phenylanthranilic Acid, Aniline Reagent, Aniline Sulphate, Indigo Carmine, they cost a lot. If we keep the cell the same parameters and same runtime we does not need tests like this. We can reproduce the same quality purity from cell regularly. The double displacement reaction: In the cell from every 100g NaCl calculated to get 210g NaClO4. The NaClO4, KCl it is never dried out. Stainless steel saucepan not tolerate to heat in in these wet crystals and get rusted and damaged when heated these wet crystals in it. This solution are boiled close to 1g NaClO4+0,5g H2O (saturated solution at room temperature) When NaClO4 intensive way start to crystalizing out. We need a saturated NaClO4 solution calculated at room temperature. Every 1g KCl dissolved 2,9g H2O (saturated solution at room temperature). And every 1g NaClO4 calculated 0,6g KCl and the KCl+NaClO4 solutions are mixed with hot minimum 80°C. From the 142g NaCl 298g NaClO4 calculated. The 298g NaClO4 dissolved 149g H2O (saturated solution at room temperature). From the 298g NaClO4 179g KCl calculated and the 179g KCl dissolved in 519g H2O (saturated solution at room temperature) and the KCl+NaClO4 solution are mixed with minimum 80°C. After this cooled down at room temperature and the crystals are washed in ice cold water mixed thoroughly with a spoon than filtered in a all purpose cloth. First must make destroy the chlorate in the KClO4 solution calculate the total NaClO4 5-10% sodium or potassium metabisulfide and with HCl make the solution under pH 3. The HCl should be added proportionately tho the K2S2O5 (metabisulfite). For this process must be used a 2000ml beaker, do not use stainless steel! Use a Wire Gauze Heat Shield with Ceramic Center to protect the beaker from thermal shock or will be cracked or use a sand bath this is important. Directtly heating in a hot plate the beaker are easy way cracked if we heated strongly and uneven heat distribution in the hot plate. And boil it important to generate SO2 gas. When boiling add more HCl to form SO2 gas from the metabisulfite. Make first a 130g/l KClO4 solution add to it the 5% K2S2O5 and some HCl, when the salt are hot and dissolved add more KClO4 to get a concentrated solution HCl and metabisulfite. Add this as solution slowly with a pipette, or using a plastic straw and syringe under the solution. Boil it 1 hour and when the crystals start forming make tests with concentrated HCl, when they are stay white that product are ok. When the solution are clean and not yellowish color change and forms lot of SO2 gas that KClO4 are ok. After this cooled down at room temperature the acidic solution must be double than the crystals and filtered. The crystals are washed in ice cold water mixed thoroughly with a spoon washed with potassium or sodium bicarbonate to neutralize the acidic pH washed in ice cold water again than filtered in a all purpose cloth.The next step completely dissolve the crystals in hot water, to form the crystals under double water when the solution cooled down, and recrystallized again 2 time (wash it gently with ice cold water between the two crystallization). The 2X recrystallization are important to get pure KClO4. If you have 200ml crystals, the solution above not be less than 600ml when all the crystals precipitate out of solution when cooled down slowly to room temperature. In a gas stove using a hotplate and a saucepan the crystals are dried out. The fine powdered KClO4 are tested with 30% HCl. First the HCl added to the powder. If stays white no reaction the KClO4 are ok. Yellowish color change are chlorate contamination. Grayish need to re crystal again! The end pure result what measured in a electric balance was 294g KClO4 from this cell. Purity around 99,7%, purer quality than the basic factory technical grade. The NaCl are recovered in a chlorate cell. Ammonium perchlorate: Every 1g NaClO4 calculated 0,5g H2O (saturated solution at room temperature). And every 1g NH4Cl calculated 2,7g H2O (saturated solution at room temperature). Every 1g NaClO4 calculated 0,5g NH4Cl. Here need to dry the NH4ClO4 in a glass or ceramic baking dish at under 100°C because under 200°C starting the NH4ClO4 decomposition. Potassium perchlorate alternative ways: Using sodium or potassium chlorate thermal decomposition. With NaClO3 and KClO3 all of them the minimum are 400°C where possible to start the decomposition process. Using a ceramic crucible and a bunsen burner or propane burner possible to make, High Pressure Propane Stove Outdoor Cooker are the bast way where ceramic crucible can be heated on a large surface. Need a ceramic tool what inert with the melted chlorate and tolerate the high temperature. In a gas stove not possible to get this temperature using a ceramic crucible! See patent US 2733982. Mini grill with a precise thermometer suitable for the process. Recommended to keep the temperature under 450°C. Pans are useless for this process, the chlorates are attack them and they not tolerate this high temperature. Example possible to get 400°C using a ceramic pan in a gas stove, but the pan are not tolerating this extreme heat and after few use will be cracked. When i tested using sodium chlorate are much more ideal to this process than using KClO3. The reaction proceeds faster and the NaClO4 melting point are 468°C so when the reaction complete the melted chlorate turned solid perchlorate. Recommended to using to the process KClO3 and NaClO3 too. The process depends on the temperature minimum one hour. The method is costly and difficult. The NaClO4 from NaCl need to separate with crystallization. The NaCl will precipitates which is less soluble. And the NaClO4 solution must react with KClO4/KCl product to convert all KCl to KClO4. Making perchlorates without platinum or lead dioxide using non reductive acids: 1 way without ozone generator: using 40% Nitric Acid HNO3 (NO2 free), boil it in NaClO3 and you will get NaNO3+NaClO3 at 3:1 ratio with 30% yield. Chlorine will produced in the reaction without explosive ClO2 gas. Nitric acid HNO3 can be prepared from Ca(NO3)2, Mg(NO3)2. H2SO4 can be prepared using oxalic acid C2H2O4 with MgSO4. 2 way more effective way with high yield using ozone generator: Use in this process 60% nitric acid boil it in 15% KClO3 and use a ozone generator minimum 2g/hour (minimum 50% concentrated HNO3 required to this second process!). Remove the KNO3 contamination using recrystallization in 316g/l water the KClO4 crystals and cool it down to room temperature. And make a secondary recystallization in pure water. See more on DTIC AD0016814 research and US 2858188 A patent. By heating a glass wrapped in aluminum foil in sand, we can make a cheap device in which we can heat and distill. By putting ice on top of a container and nitric acid will dropping into a glass inside the glass container, you can make a cheap and simple distillation device. Using the method, perchlorates can also be prepared by those who have simple graphite electrodes and it is a problem for them to reach a high temperature. From barium carbonate with pH control easy to make BaCl2 and Ba(ClO3)2 using even a simple graphite anode, than converting it to Ba(ClO4)2 using HNO3 and ozone. Adding H2SO4 to the Ba(ClO4)2, Ba(NO3)2, HNO3 mixture will convert Ba(ClO4)2, Ba(NO3)2, to HNO3 and HClO4 with insoluble BaSO4. Using filtration, distillation you will get perchloric and nitric acid. Or you can boil in the HNO3+HClO4 mixture KClO3 in presence of ozone more effective way. Heating BaSO4 with charcoal above 600°C we can convert it to BaS, than reacting with HCl we get back the BaCl2, H2S are formed. With sedimentation, filtration, crystallization and washing the BaCl2 with ethanol we can clean it the BaCl2 crystals. Know issues with eletrodes/synthesis: All electrodes all tolerate maximum 6V 400-5000ml setup! In a 400-1500ml setup 4-6A are used. The cell maximal temperature are 45°C. The cell must keep under 40°C in a perchlorate cell or the anode erosion will be high. In the cell with NaClO4 without pH controlling the process will be too slow, and the yield are low too. Hot cells are not important in chlorate production and heating the cell with too much amps are crash perchlorate anodes! Platinum anodes tolerate alkali and acidic solutions too. MMO anodes not tolerate highly acidic sulutions. In long term by users feedback better to protect the MMO from too much acidic cell. PbO2 anodes not tolerate highly alkali solutions slightly acidic solutions more ideal to PbO2. In perchlorate cell only working strong BETA PbO2 coating alfa coatings will crash fast in this setup. Stainless steel limited of them what working in a chlorate and perchlorate cell as cathode, i not recommend it to use. The minimum platinum size for a platinum electrode are 3x70mm pure silver core cylindrical anode with 200micron pure platinum layer. Electrodes below this parameter are unsuitable for chlorate, perchlorate production. Overcoat the full electrode with platinum to protect it from chemical attack. There should be no exposed silver at either end of the electrode. Avoid all platinum electrode where the platinum layer are thinner than 100 micron, 200 micron platinum layer are ideal! However, I do not recommend non-adjustable power supplies because they can easily be overloaded.The best choice are a 10A Laboratory DC Power Supply Variable This avoids overloading the power supply or overheating the cell. Amp calculation for another electrodes a colder 30-45°C clorate/perchlorate setup 0,5-5l cells: As a rule of thumb no more than 2 amperes per 100 ml of electrolyte must be passed through a chlorate cell. I calculated for using 1 amperes per 100 ml for a colder setup. What good for 0,5l to 2l setups 0,5-2l 6V- 4-6A are used, for 1,5l-2l setups 5-6V. 15A are used only if the electrodes are tolerating max 15A like a minimum 50x200mm, 60x150mm and larger PbO2 anode without problems for minimum 5l cells to avoid overheating the cell! 70mm x 3mm x0,2mm pure platinum clad anode in a silver base: Maximum 6V 6A 0,5-2l cell Platinized Titanium Mesh Anode 1" x 4" or 2" x 3"(only in perchlorate setup): 6V 6A (maximum 6A) are not problem for this anode. This should be held between two titanium plates cathode of the same size for the maximum eletrical effectivity important! Too much amps will ruin this anode! I do not recommend to use 2,5 micron platinized titanium anodes they are not durable. Platinum clad anodes 50-100 micron in a thin niobium outer layer and copper core base, or much better 200 micron in a silver base a durable solution for long term. And there is not too high difference in price in the case of size the above-mentioned electrode. For the few micron platinized titanium anodes have too many complaints users that they are not durable at long term. PbO2 and MMO anode: For 50x200mm, 60x150mm and larger anodes 6V max 15A are not problem. For minimum 5l setups 15A are recommended, under 2l max 6A. MMO anode be held between two titanium plates cathode of the same size for the maximum electrical effectivity. PbO2 must keep far from the cathode what pH are alkali and this does not like the PbO2. For minimum 5l setup a computer or used server power supply with 5V 15-17A with connecting together parallel thin wires ideal to cheap way set the required amps for the cell without costly adjustable precision PSU (with adjustable current Amps). Less than 5l with 15A are overheating the cell if the Amps are not precisely controlled! However, I do not recommend non-adjustable power supplies because they can easily be overloaded.The best choice are a 10A Laboratory DC Power Supply Variable This avoids overloading the power supply or overheating the cell. Increasing unstable KClO3 stability: First need to grind the KClO3 to a fine powder. Than this powder need to heat at 150-200°C to get a moisture free powder. When cooled down need to mixed with +5% KHCO3 potassium bicarbonate. If sulfur are used mix the sulfur with 1/4 KHCO3 too important! This process reduce friction sensitivity. I do not recommend the use of potassium chlorate except smoke bombs, mach compositions, shoot plastic disc caps where it cannot be replaced. With Sulfur, Mg, Sb2S3, extremely sensitive for friction. If anyone wants to experiment with it and want make unstable mixtures like KClO3/Mg/S this process reduces minimal to ignite the composition when friction temporarily. The technique could reduce the problem but not eliminate it! In stars, flash powder, whistle mix, highly not recommended to use KClO3! KClO3+NaClO4 setup for cyclic potassium perchlorate production (for advanced users): Platinum anode is recommended for this, because KClO4 can be deposited on lead dioxide. For every 1 cell KClO3 crystals calculated 1 same sized NaClO4 cell solution for the reaction. The KClO3 513g/l added to the not concentrated NaClO4 and both solutions are degree 90°C. The KClO3 must added slowly to the NaClO4 solution, KClO4 crystals must formed, and if this stops, it must be stopped adding the KClO3 because the solution in this case will contaminated with large amount of KClO3! This is therefore very important to monitored. After the reaction the solution with the crystals are cooled down to room temperature and filtered. The NaClO3 converted back to NaClO4 and the KClO4 crystals are boiled in the cell solution, (do not try to dissolve in this solution) to make the crystals less chlorate contamination as possible. After this cooled down to room temperature, filtered and the crystals are putted in ice cold water stir it in the water and filter. This conversion are will be fast! The idea are using the CN102807192A patent. Its reaction formula is following: NaClO4+ KClO3=KClO4+ NaClO3 After this the chlorate are destroyed with the metabisulfite+HCl boiling method. After this cooled down at room temperature and the crystals are washed in ice cold water mixed thoroughly with a spoon washed with potassium or sodium bicarbonate washed in ice cold water again than filtered in a all purpose cloth. And with 2X recrystallization in pure water, and washing the crystals in ice cold water the KClO4 are cleaned. The NaClO4 can be recovered unlimited time in this process. Just need to refill the cell small amount of NaClO3 some times. With this process chlorate anodes does not contact perchlorate ions, and in the perchlorate cell does not have lot of chloride ions what are highly corrosive for the anodes if the sodium are recovered. The method is especially recommended for those who can produce KClO3 quickly, but NaClO3 and NaClO4 production is slow for them. pH control are required in this setup! Sources: http://www.chlorates.exrockets.com/kperchlo.html http://www.chlorates.exrockets.com/destroy.html http://www.chlorates.exrockets.com/tests.html https://patents.google.com/patent/US2733982A/en

Collection of the best pyro tutorials from the internet what helping amateurs to making their fireworks safe and effective way. The collection contains all important basic knowledge for those who make fireworks at home to make all the popular the products at home. Please SEED this torrent the possible longest time you can to keep it alive. Untill if you have the collection add it to your torrent client to keep it alive! The users who seed this file keep it alive! Share the content in the internet. Upload and share freely wherever you like in the internet. Tether USDT and BNB BEP20 or (Matic Polygon) small amount donation to support projects: 0x16829457123552A574441bf38Eeaf93B46105A1d BTC donatin to support projects: 16aiyTMQDagpcD1za5yoVLCMssym52QLnf Content Sites: - Fireworks Painting The Sky Full website (Wichita Buggy Whip) - PyroData and PyroGudie - PyroMaster Hungarian full website - Richard Nakka Experimental Rocketry Web Site - The Chlorates And Perchlorates Full website (with all documents and desription) Video tutorials: - Chemistry making raw materials (ammonium nitrate, Chlorates and Perchlorates, How To Make Dark Aluminum powder In Bulk, Making DEXTRIN for fireworks, Making H2SO4 from Sulfates and HCl, Making Magnalium powder for use in Pyrotechnics, Nitric acid distillation, Synthesis of nitrocellulose) - Colored Compositions - Flash Powders - Fountains - How to Make a Firework Shell - How to make Electric Matches - Firecrackers - Rocketery - Smoke - Stars - Strobe Pots Tutorials and others: - PASSFIRE ARCHIVE - The Best of AFN - black powder and ball shels - Bombette - Cut stars - How to Attach An Ematch to Visco Fuse - How to Make Colored Fireworks Fountains - How to make firework rockets - How to Make Firework Stars Using a Star Pump - How to Make Whistle Mix - Thermalite - Easy PVC Rockets (by Jason Smiley) - Spin_Stabilized_Rockets_Book - ballmill - fireworks_pyro_projects (Skylighter) - How to make extremely reactive KP with ball mill 70KClO4 18C12S - Skylighter How to Make Fireworks - A SYNTHESIS AND SOURCING GUIDE TO OVER THE COUNTER PYROTECHNICS – 2nd EDITION - Firevorks_the_art_stsientse_and_technikue__takeo_shimizu_1996 - Perchlorate Documentations ENG and Hungarian - Periodic Table with mass numbers - Rockettoolsketcher - Solubility table - Testing flash powders for homemade firecrackers - The most possible extreme powerful professional flash powder - The_Complete_Book_of_Flash_Powder - Receptek Sufnipirotechnikusoknak Hungarian Descriptions (Tutorials For Amateur Pyrotechnicans) Links: Direct download link to the 10,4 GB .zip file: The Best Of Pyrotechnics Tutorials 2024 Torrent or magnet links with anonymous I2P setup description: The Torrent seeded through the anonymous I2P network, please follow the instructions! The Best Of Pyrotechnics Tutorials 2024.zip or https://odysee.com/@mx5kevin:a/The-Best-Of-Pyrotechnics-Tutorials-2024:1 https://drive.google.com/file/d/12ggnW0HOHjrBSF04rrpAE20TqLp7GI5G/view?usp=drive_link https://steemit.com/pyrotechnics/@mx5kevin/the-best-of-pyrotechnics-tutorials-2024-anonymous-i2p-torrent

The Fourth of July ignites a fiery passion within us, a longing to come together and revel in the spirit of freedom. What better way to honor this historic occasion than by orchestrating an extraordinary event? Picture a day filled with laughter, shared memories, and a sense of unity that transcends boundaries. In this heartfelt blog post, I'll walk you through the steps of planning a truly remarkable July 4th gathering—one that will leave your guests touched by the magic of the occasion and create cherished moments for years to come. Enchant with a Theme, Unite the Community: As you embark on this journey, let your imagination take flight and embrace the power of a theme. Unleash your creativity with a theme that encapsulates the essence of Independence Day. It could be a passionate display of red, white, and blue, or an unexpected twist like a "Stars and Stripes Fiesta" that sparks intrigue. A theme not only sets the stage for dazzling decorations, delectable treats, and engaging activities—it also fosters a sense of togetherness. Extend an open invitation to your neighbors, friends, and local organizations, encouraging them to join hands and make this celebration a collective triumph. Choose a Venue, Where Dreams Take Flight: The perfect backdrop can breathe life into your July 4th dreams. Let your heart guide you to the ideal location—a sun-kissed backyard sanctuary, a picturesque community park, or a public space that yearns for a touch of celebration. Seek a venue that embraces the spirit of the event and ensures convenience with ample parking, well-maintained restrooms, and facilities that make culinary masterpieces possible. As you secure your chosen sanctuary, weave the tapestry of logistics—seating arrangements that invite conversations, whimsical lighting to set the mood, and a soundscape that will make hearts dance. Nurture Joy with Engaging Activities: A memorable July 4th event blossoms with activities that enchant guests of all ages. Curate a treasure trove of delights, from timeless classics like sack races, water balloon tosses, and spirited three-legged races to an enchanting wonderland for little ones, brimming with face painting, crafts, and inflatable bounce houses. Elevate the atmosphere with live music from local talents or a captivating DJ who will strike chords deep within every soul. Be sure to carve out a space for interactive photo booths or engaging patriotic-themed games like cornhole or horseshoes, igniting laughter and forging connections. Delight in a Feast, A Symphony of Flavors: The path to the heart is paved with culinary delights. Envision a menu that melds traditional favorites with a touch of patriotic flair. Sizzle on the grill with mouthwatering burgers, hot dogs that evoke childhood memories, succulent barbecued ribs, and perfectly seasoned chicken. Infuse your offerings with the vibrant colors of the American flag, using luscious blueberries, ruby-red strawberries, and billows of whipped cream for a dessert that dances on taste buds. Remember to honor dietary restrictions and ensure a diverse range of options, including vegetarian or vegan dishes. Embrace the spirit of community by encouraging guests to contribute their favorite side dishes or desserts, nurturing a shared sense of belonging Illuminate the Night, Paint the Skies: A July 4th event without a mesmerizing fireworks display is like a symphony without its crescendo. Embrace the ethereal beauty of a starlit sky painted with the hues of cascading fireworks. Before embarking on your own pyrotechnic symphony, familiarize yourself with local regulations and safety guidelines. If fireworks are not an option, explore alternatives such Signature Writer for https://fireworkinsider.com/

At friday got really bored at work, called it a day and went to the garage to prepare some fuel 1) Cooked another batch of RNX propellant (oh this is fun one) 2) Cooked finally a decent batch of kno3/sugar/Fe2O3 end burner fuel After trying out different ways of cooking kno3/sugar for more than year, I believe I have finally mastered cooking that propellant type (Im talking about at least +500g batches, small ones are easy). Got most of the moisture out, packed it really well without any bubbles and cracks - whole process took again ca 6 hours. But it is worth it, propellan worked like charmed! But again I had an issue with casing... I do admit that I have not been very careful with that and again, cap failed. I know whats wrong and I will fix this as a first thing tomorrow. As I was able to see my father at weekend, we decided to have some fun and just launch the engine casing :D And that's what happened: :D Oh man, we had so good laugh Sorry about the quality but we were really far away and Iphone does not really have a good zoom. But anyways, took off, quite soon cap failed and started to push the "nose" down and hit the trees and then completely blowed the cap away resulting in CATO. But as I have demonstrated, end burner works really really well, I could even say that it has way too much power. Next steps will be to to fix casing, 3d print the noze, calculate CP and CG and add proper stabilizers and off we go. I'm really getting there, coupe of months and we will have a proper kno3/sugar end burner launch. The fuel and casing mass together was 1.2kg BUT, recentlyI have been doing tests with RNX propellant: Epoxy Kno3 Fe2O3 Aluminium and Sulfur. Small batches worked well and burning speed matched mostly Nakkas experients. But ignition is really difficult! After couple of static "tests" got some idea how the propellant works and decided to give it a try. My father was really sceptical and actually laughed when hearing the propellant made of Epoxy, but he got really serious when we actually set it off The noise! Oh my god, it's like real rocket launch, masssssssive noise. Again, we were quite far away and the video and the noize do not completely reflect live effect but believe me, sugar rockets are nowhere comparable with that one. Whats really impressive about this propellant is that its like 10x times easier to make it than sugar propellant, nor it is hygroscopic. After 24-30 hours it also gets rock solid! I will complete my sugar propellant end burner project, do the proper setup and launch and then completely move to RNX propellant. By the way, I am not using brand Nakka used (really hard to get it in EU). I have other one, cheap as hell but works perfectly as you can see! But in my case, % Nakka used in hes formulas really didnt make any sense nor they worked. Propellant mixture was too liquid and after hardening really did not work. So I improvised a bit, changed formula and bingo- got the good starting point from where I can start fine tuning and testing. What I have to improve: 1) Fine tune nozzle and core 2) Ignition is difficult, this time I used BP from gun ammunition but the amount and "kick" was too low. I need lot of pressure and heat quickly on the whole core to ignite it. This is SO FUN! ------- Electronics: Couple of previous weeks I have spent building wireless ignition system. Transmitter and receiver, wireless signal and 12v system for resistance wire connected to pyro charge. I still need voltage converter and will try to get one in coming days. So, this will again make testing and launching much more safer as I can stay away more than 100 meters if needed. Will add more data after system completely done and tested and working! Cost of it? couple of euros

I am always trying to find a safe inexpensive ways to improve my fireworks. Last 4 th. of July I came up with nice replacement for fire cracker tubes which can also be used as reports in a mortar shell. I had ran out of tubes and forgot to order more in time for the 4th. I decided to run to Menards to get some hdpe pipe to make mortar tubes. As I was walking in the pipe section I noticed a shelf with 5 foot 1/4 inch terra cotta pex tubing for $1.59 a piece. I cut the whole thing in 2 inch pieces about 30 in all. I tried filling them with black power and they just didn't have much pop so I decided to use a 70/30 mix of KCLO4 and dark aluminum. I sealed the bottoms of all of them with hot glue put the mix in the other end followed by twisting a fuse half way into the mix. I sealed the fuse end with epoxy but you could probably use a glue gun if it is unplugged. I was really surprised at the bang when I lit off the first cracker. For something no bigger than a black cat it sure had a loud report. Another thing that amazed me was that the case stay almost always in one piece blowing out one side and can be easily picked up and thrown away. Whereas PVC and other types of pipe shatters to tiny pieces these don't. If anyone wants to try this let me know what you think . And if you have any questions just ask and I will get back as soon as possible. Thanks Have a great day and above all Be Safe!

I've had or made about 4 different versions of ball mills in my day. When things got serious and I moved up to a large ball mill the one thing that never changed was the mill jar that I use. This style has been an "old faithful" for me so I'll share what I have done. The material I use is schedule 40 PVC plumbing pipe and parts. There is a lighter duty PVC pipe known as Drain, Waste, and Vent (DWV). I've lived through a couple of dropped jars in my day and I would like to give the rigid schedule 40 pipe a little bit of credit for at least not making a mess. If I remember correctly I don't believe the two are interchangeable, schedule 40 parts won't fit DWV and visa versa. The joints still hold well and do not leak. I went with a 6" pipe because it is large enough for me to mill powder. Four inch pipe is too small for me to get done the amounts I like to produce and 8 inch would be too heavy and too expensive to make. The next consideration is the cement to glue the parts together. There is a heavy duty PVC cement that I like to use. Every little bit helps as far as I'm concerned and these jars rattling around for hundreds of hours may be a testament to the heavy duty glue. These jars may be a little pricey when done but they have been well worth the cost and have been maintenance free. Now lets go shopping! I checked out a few different big box stores and some or most do not carry 6" PVC supplies. Below is a recent price list of the parts used. 6" X 4" reducing bushing $14.86 6" Coupling $14.33 6" Cap $12.99 6" Pipe X $37.26 (your call) I went with a 10 footer myself. 4" Pipe X 5 feet $8.99 4" Kwik cap $3.49 shown above which is a rubber cap with hose clamp to seal mouth of the jar. 8 oz of heavy duty cement $7.99 4 oz cleaner $3.49 So a trip to the store will cost about $110 unless you want to build more than one. Now that you have all the parts it is time to cut and assemble. I cut my 6" pipe to about 16 to 18" long. You are going to want two pieces of pipe because the second one will be used to cut strips about a 1/2" wide for "lift bars". The second piece of pipe can be a 1/2" shorter than the first so that the lift bars will fit end to end easily enough. These strips are cemented in to keep the contents from staying as one mass of material and help to keep the mill media and your powder constantly mixing and working to mill more efficiently. I cut these strips with a circular saw but you can use other tools. Just watch your fingers please! This is what it looks like when I had clamped my cemented lift bars in place: Once the lift bars are set the rest of the jar can be assembled. If you have never worked with this material before please see the instructions of the cement. Usually you want to clean or prime both PVC mating parts then add cement to both parts and twist them together. Any excess cement that collects at the joint after assembly is spread around the joint to fill the crack. The cement sets up pretty quick so take care when assembling the parts. The next picture below is a shot looking down the inside when the reducing bushing and lift bars are assembled. I like this arrangement because the reducing bushing makes the jar more compact in regard to length. The reducing bushing also keeps the powder more in the jar and not in the mouth of the jar if a reducing coupler was used. And here is the completed jar without the rubber cap. Take a moment to notice that the 4" pipe is just long enough to bottom out in the reducing bushing and then sticks out just far enough to accept the rubber cap. This again helps with trying to keep the milling material in the jar, reduces weight and jar length is kept to a minimum. The jar can be used within an hour or less. I let it sit for a day just to be sure.

What is a bombette in the first place? Simply a tube shot from a small mortar, like we see in commercial cakes linked together to shoot 12, 19, 30 shots one after one. Each shot tube contains a slightly smaller tube containing a clay plug holding the delay fuse, stars and flash burst. When they are fired we see a colored rising tail. Red, green, gold, glitter, silver... followed with whatever is inside the bombette. Making this tail is rather simple, but not obvious. NOTE: this blog only considers the tail compositions and how to apply them, i am not going into details about the bombette itself. The starting materials are the empty bombette casings, with the timefuse (homemade visco, but commercial will do just fine too) and clay plug already in place. Looks like this from the other side, where the stars and burst will be later on: If we flip this bundle we see practically the same, but the clay plug is closer to the end of the tube, just 5 - 7mm space is left. This space is going to be filled with the tail composition. Here's the trick: you'll need NitroCellulose laquer to make your tail composition into a pourable slurry. Water/alcohol based dextrin slurry won't work. It destroys the fuse and forms a weak crumbly mass. Use any star composition you like, just leave the Dextrin out and mix it with the laquer untill you have a pour-able slurry resembling the viscosity of honey. Working with this slurry is rather tricky with a spoon or whatever, so i make batches of 300g and pour it in an empty dish-wash soap can. They have a neat little squirt cap, ideal to portion without spilling! And you can save the rest for a next time. Take your bundle of bombette casings and start pouring some slurry on top and around the fuse. Don't use too much, a teaspoon-like portion is enough. Before they form a dry film (that would be pretty fast) dip them in some fine grained BP to ensure ignition. Set aside and let dry! It should look like this now After drying they are ready to be filled with whatever you where planning to fill them with. Enjoy your colored tails!

Homegrown Oxidizers Part Nine WSM The Experimental Cells The lead dioxide cell with the anode sandwiched between two cathodes. On the left side of the photo above, a close fitting PVC assembly is shown which is used mainly to protect the Pyrex tank we used. It also added an insulating layer, which wasn’t our intention or particularly wanted. In the lid of the cell are four fittings: two for the electrodes, one for a Teflon coated thermal sensor and the last one to vent gasses generated during operation of the cell. In the photos below, showing the running cell, the clear electrolyte appears milky due to the many very fine gas bubbles coming off the electrodes and circulating in a convection-like current within the cell. Many of those bubbles combine and break at the surface of the electrolyte, where the gasses can rise and escape through a vent tube in the lid of the cell. The gasses are primarily hydrogen (H2), oxygen (O2) and ozone (O3). This detail view shows black Viton rubber insulating barriers on the edges of the anode and clear Teflon tubing supports between the electrodes to rigidly maintain spacing. The LD test cell two hours after the initial start up. The LD cell after 48 hours. The voltages in the above two photos are higher than our final reads because they’re from the power supply. For accuracy we later moved the meter connections to the electrode leads. The first cell run is using the lead dioxide (LD) on titanium mesh anode surrounded by two solid titanium sheet cathodes. The electrolyte is sodium chlorate solution with a concentration of 600 grams per liter. Our intention is to run the cell till the chlorate is down to 100 grams per liter. As described in part eight of this series, in order to obtain accurate data from these runs we’ve decided to use a small regulated DC power supply capable of constant voltage (CV) or constant current (CC) operation. We elected to run the cells with constant current (where the current remains the same but the voltage varies as needed to maintain the current delivery), for greater ease in calculating the current efficiency (or CE) of the different systems. In practice the current setting remained “rock solid” with no hint of varying. The voltage in our experiments did vary as the cell chemistry and temperature changed during the runs, but not as much as we thought they might. Running the LD cell In the chlorate process several noxious and toxic materials are generated (primarily a strong bleach smell), but in the perchlorate process this doesn’t appear to be the case. That said, we still recommend running the operation in a controlled and well ventilated area, protected from approach by those unfamiliar with or unprepared to deal with the hazards present. We started with three liters of electrolyte, keeping an additional 400 milliliters in reserve for replenishing the fluid level, should it drop too close to the top of the electrodes during the run. This proved to be a wise decision. After the first 24 hours of operation, the fluid level dropped about an inch (about 25mm), so the rest of the electrolyte was added to the cell. At 48 hours of operation the electrolyte level only dropped half as much, so it appeared that as the chlorate was consumed (and replaced by perchlorate) the water consumption was reduced. This isn’t certain, but follows our observations. For the first 48 hours of operation, we noticed the voltage remained consistent (about 4.19 Vdc at the juncture of the power leads and the electrode leads), but after that began to rise very slowly till about 68 hours to about 4.25 Vdc. Our conservative estimates were for 72 hours of operation at the current density we chose (0.1A/cm2 anode surface area) to the completion of the run. Everything else in our setup was running in textbook fashion. The voltage, current and temperature were all within limits that industry says are normal, and with our LD cell running at about 30% to 40% the current density of commercial cells, the ozone generation we noticed was much less than anticipated. The temperature at the start of the run was at ambient (20°C or 68°F) but slowly rose to between 45° and 50°C (113° and 122°F) and stabilized. We believe we ran our system a bit too long. After running the cell 69 hours (of our planned 72 hour run), the electrolyte began to have a brown color develop in it. As a result, it’s possible our anode may have some minor damage, as evidenced by the brown tint in the electrolyte. Fortunately, after the shutdown and sitting for two days, the brown color faded and any residue dropped out to the bottom of the cell. Filtering the electrolyte solution should remove the residue, which we’ll test later for lead (Pb) content. The brown coloration of the electrolyte appeared after about hour 69. The photo on the left is of the LD cell at shutdown, after roughly 71 hours of operation. The photo on the right is the same cell after sitting two days. The brown material has faded and dropped to the bottom of the cell. There is some good news though; within a short time of starting the run, we got positive tests for perchlorate. As the run progressed, the positives were immediate and strong. We use methylene blue solution to test for the presence of perchlorate in the electrolyte and a change of color from blue to purple is indicative of perchlorate (even in the presence of chlorate or nitrate). Methylene blue use is a qualitative test (meaning it tells us whether or not perchlorate is there). What we need is a quantitative test which will tell us how much perchlorate is there. Methylene blue leaves a blue spot as on the left side, which is the original chlorate solution. The purple spot (showing perchlorate is present) is from the cell electrolyte after running for ten hours in the cell. The best news is that the qualitative test means we have nearly three liters of raw sodium perchlorate solution (with an unknown amount of sodium chlorate residue) to process from the LD cell. Running the platinum (Pt) cell A photo of the Pt cell soon after start up. A photo of the Pt cell at 72 hours of operation. Operation of the second cell was with a platinized titanium mesh anode and a pair of titanium cathodes. We ran it with a current density of 0.2A/cm2 anode surface area. The anode surface area was roughly one third the area of the LD anode. Things ran similarly to the LD anode. Due to the higher current density, the side reaction electrolysis of water and the ozone generation was more pronounced than with the LD anode. The voltage values were also higher by half a volt or more, depending on which part of the run was monitored. With a little off hand calculation we determined to run the Pt test 82 hours, and everything seemed to operate just fine, with no visible damage to the anode. The end point liquor has a light yellow tint to it (as seen in the photo below), but we can’t tell if it’s due to the differences in the two cells because we used sodium chlorate from different sources in each of the two tests. The Pt cell fluid has a faint yellow tint to it, after running 82 hours. The test for perchlorate with methylene blue solution in the Pt cell is immediate and positive. We estimate the final fluid level to be about 2.75 liters (roughly 73% of a US Gallon). Results of the tests As expected, both setups produced sodium perchlorate. Between the two, it seems the lead dioxide anode shows more promise for longevity in an amateur perchlorate cell, and at a reasonable cost. We were impressed with how close to industrial numbers it ran, but the actual efficiencies of the two cells are still unknown. Now that we’ve proven we can make sodium perchlorate in a small working model cell, we need to research the purification and conversion of it to more useful perchlorates, such as (sodium-free) pyrotechnics grade potassium perchlorate. A few steps need to be undertaken to get us to that point. As for the actual efficiency, we don’t know it at this point. The vast majority of the gas generated at the anode was oxygen, and at the cathode was hydrogen, due to the electrolysis of water (the main side reaction). We’re not certain we can accurately, or even roughly, determine the efficiency yet, but we’ll try. More tests are called for...

Hi, As a beginner first batch of chemicals has arrived. I will keep updating the blog as and when things arrive and i make something. 1. Salt peter 2. Barium Nitrate 3. Strontium nitrate 4. Bentonite powder. Now, waiting for Sulphur, Charcoal (airfloat and 80 mesh), Titanium powder, Acetone, Ethanol, Shellac. Still, struggling to get Aluminium. Any other chemicals i require? I want to stay away from chlorates and perchlorates at the moment. Enquiring about a H type hydraulic press. Downloaded the turbo pyro projects too. Getting a rawhide hammer and 80 mesh charcoal 40 mesh and 200 mesh Magnalium with me now. Regards

I'm writing this blog entry because I'd like to share my techniques and findings. I think it will be a nice introductory tutorial to those who are considering making paper ball shells. Starting my second big shell building project got me thinking about efficiency. I wanted to get these shells built in the minimum time possible, while still being as safe as possible. Of course, it is safer to build one shell at a time- the total amount of pyrotechnic compositions on the bench at one time is a lot less with 1 shell than 10, 20, or 30. As such, I did some processes all at once, and others (like loading the shells) in batches, building one type of shell at a time. I felt this struck a balance between safety and efficiency. First, I looked at the stuff I had on hand and what I needed to make. Supplies on hand: 2 kg BP mill dustTub of mill dust used only for spolettesSome BP coated rice hulls, looked to be enough to finish 30 shellsPaper products and fuseStars (Chrys 6 + Ti, Tiger Tail, Zn Pearl)Plenty of pyro chemicalsNeeded to make: SpolettesColor & White starsWhistle Mix for burst boosterLift cupsGranulated liftFencepost and BP PrimeMortar rack Didn't sound like too much work, aside from assembling the shells. PRE-ASSEMBLY I figured the first thing I should do is prepare everything. Night 1 - Mixed Fencepost Prime, BP Prime, Ruby Red, Veline Blue, and Skylighter Rubber White star compsNight 2 - Granulated BP with red gum/alcoholNight 3 - Cut red, white, and blue starsNight 4 - Mixed ~150g Whistle MixNight 5 - Sat down with roommate who would design mortar rack and templates for kraft paper lift cup piecesSPOLETTES Next, I needed something to stick in those shell hemis. First, I made oak dowel rammers that fit snugly into 1/4" ID spolette tubes. Design is critical- especially the tip and taper- it's hard to keep from binding the dowel in the tube. Measured and drew lines to help guide the ramming process. A light wax coating seemed to help. After that, it was a simple matter to ram the correct amounts of powder into the tube with a rubber-faced mallet. The tricky part is filling the tube- a funnel that small just doesn't work well. The first increment is loaded with the dowel inserted. This one is "super-duper-pounded" to make sure the end of the spolette is as tough is it can be. I got the process to where a couple partial scoops would make a nice increment to ram. It's important to ram spolettes in increments to make sure the powder is consolidated well. Next, the hemispheres needed to be fused. I taped over the existing fuse holes, preferring to drill my own in the center of the hemi. ...all ready for blackmatch pieces!!! SHELL ASSEMBLY To balance efficiency and safety, I laid out hemisphere sets for all of each type of shell I was going to make. That is, I made 6 Tiger Tail shells, so I put out 6 hemi sets. Then: Put black match in each spolette tube for passfireLoad each hemi with a scoop of starsGo down the line arranging stars in the hemisGrab the rice hull bucket, go down the line filling hemis, then stash the rice hullsGrab the Whistle tub, go down the line dolling out the booster charge, stash the whistle tubAssemble each shell and have assistant help tape them togetherTag the spolette end with tape to protect it and label the shellPut completed shells in airtight ammo box for storage until pastingRepeat with the next batch. Stash leftover stars, bring out new ones. I found this to be a very efficient method. I didn't record time, but 30-some odd shells (35? Not sure) took at most 4 hours to assemble. Probably more like 2 1/2. (Keep in mind they were already fused- that process took an hour or so) PASTING This was the part that worried me. 5 turns of 3-strip method on each shell!??!?! I used gummed tape, 3/4". I stacked 7 rolls of tape on the table. By pulling and rotating the stack of rolls, one can bring the tape together in one neat stack, and cut strips with shears. A huge amount of strips can be cut this way in 10 minutes! Each shell took about 75 minutes, including strip cutting and a short break between each shell. Shells were burnished for no more than 1 minute on layers 1, 2, and 4. Shells were burnished for no more than 2 minutes on layers 3 and 5. PRIMING, FUSING, FINISHING A buddy got bored and grabbed the sharpies to "help me with color-coding." It sure wasn't much help, using red light while firing shells, and...uh...he didn't do all of 'em. A couple pictured below were lumpy shells done when we were experimenting with time-saving pasting methods- no burnishing, no smoothing out strips. Didn't save much time and made sloppy shells. Also, we don't smoke in the house. Uhoh, one day before shooting!!! I had my trusty assistants doing lift cups and cutting leader fuses the previous day, while I was finishing up pasting and cutting visco. I stripped lengths of fast firecracker fuse to harvest black match. I cut short lengths to prime the ends of my spolettes. These were hot glued on (gun unplugged and plugged back in by assistant). After that dried, a twine clove hitch was tied around the spolette tube and match ends, and secured with a dab of hot glue. Then, I weighed out all the lift charges 10 at a time, once again compromising between safety and efficiency. We grabbed the pre-cut leader fuses to which visco had already been attached. We skipped match pipe, because we just didn't have time to make it. Fuse was taped to the shell, leaving the exposed match ends dangling right by the primed spolette. An additional piece of tape stuck the fuse to the top of the shell. The lift cup was then taped onto the shell with masking tape. Shells were then loaded into .50 cal cans in the order they were to be shot. The finale shells were timed with different lengths of visco and numbered. The others were just grouped so there was a nice variety for hand-firing. Ammo cans kept moisture and pesky little sparks off the shells.

Hi all, Here is a 3 lb rocket with Ti tail, the 4 " cylinder has 3/4 " glitter comets and timed reports( the timing was not great) I also put a bottom shot on that must have had a seal problem, because it burst during the shell burst( you can see it in slow motion view, and hear it in the video as almost a double burst.) overall , home made tooling with a short spindle, 6 ", nice lift, nice tail, good break , good umbrella effect with the glitter. The glitter was a bit course so the flashes are hard to separate from the reports. Next might be larger 1.5 inch comets with smaller mesh metals. Better timing for reports, and Seal the bottom shot so the fuse lights it. Work to do for sure.

Very cool - a "Post to Blog" function. I thought I'd give it a try, since this post has some hopefully good information in it. pH Probes and Meters for the (per)chlorate process I spent far too much time on pH probes today. Again, the idea behind the simple bucket cell is so one doesn't have to mess with pH probes and meters, but I still need to use them to verify it works without them. That makes no sense at all, does it? I've always been a fan of Milwaukee pH stuff. They occupy a niche between school and aquarium junk, and expensive lab stuff. I have a MW-101 equivalent. Look for a meter with a manual temperature adjustment on front. Those with automatic temp compensation inside either require a special probe, or a separate temperature probe, and all of that is a pain. It's easier just to set it manually, because we generally know the temperature of the sample. Look for one with simple calibration procedures, because you'll have to recalibrate often, or it's all junk, because even the best probes drift. For the (per)chlorate process, don't even bother with a pH pen or some junk from eBay. You've got to pay to play, and a decent setup will run at least $200 for meter and probe. You'll need two buffers for calibration - get the 7.0 and the 10.0, and get the big bottles. They are cheap, and you'll go through it fairly rapidly. The good news is, a nice pH meter can be used for a number of other lab processes. And if a pH meter is out of your price range, pH papers can be used with a bit of care and sneaky manipulation. But the best you'll probably be able to do is pH +/- 1.0 or so. And one last warning, NEVER buy a pH probe from eBay, even one new in box, because they have a shelf life. It might be like buying an alkaline battery with a use-by date of 2002. These things get thrown out all the time from labs, and guys going dumpster-diving get them free and then re-sell them. A decent meter lasts forever, but probes never do. I have four probes. http://www.5bears.com/perc/probe.jpg Two MA911 epoxy gel-filled probes, a higher end MA917, and a cheap aquarium probe off eBay. All had been stored correctly, with the tips immersed in 3M KCl. The two MA911 probes had served me very well, but they are at the end of their lives. You can tell when a probe is about dead when two things happen... the response is really slow, like 30 to 60 seconds, or it cannot be calibrated. My MA911 probes can still be calibrated, but they are a bit slow, so I opened up the NIB MA917. This probe has a glass body, and is refillable with electrolyte! This makes me happy, because when it begins to sicken, I can replace the internal electrolyte, which is nothing more than 3.5M KCl. A good read on pH probes in general can be found here. I recommend a glass probe because I am hopeful that the toxic and harsh environment it will see, can be repaired with fresh electrolyte. We'll see. Anyway, the $20 aquarium probe fell apart in my hands. Literally. It was a total waste of money, and even when new, it managed only a dozen pH readings. The gel-filled yellow MA911 probes have hung in there. Both of them calibrated OK, but were just very slow. The glass probe was like a Ferrari... very fast readings. But again, I haven't used it yet with chlorate. To check cell sample pH readings, get a stack of plastic bathroom cups. Set up 4 in a row, Fill one with your sample, and three with distilled water. Remove your probe from its container, rinse in distilled cup one, then into the liquor. Count to 5, and if it's not settled yet, make your best guess, because if you leave it in there longer, it'll die sooner. Remember, at best, all we need is pH within 0.2 or so, so 6.6 or 6.8, they are all the same. Immediately rinse the probe in water cup one, then two, then three, then back into it's special storage container. That was my exciting afternoon! I was glad to see the glass probe perform so well, because it had been sitting on a shelf since 2009 or so. I had prepared some ultra-pure 3.5M KCl just in case to refill it, but it turned out to not be necessary. Tomorrow, I'll do a final set up and hopefully power-on. Source: The Bucket Cell - Start to Finish

It has been a long road, but I now have two anodes plated... one of them looking fairly sad, while the other looks excellent. The weather has NOT cooperated, and in addition to the physical discomfort (cold!), there are process issues as well. Jugs of distilled water are ice cold, and the hot bath (60 to 70 degrees C) must really struggle to maintain heat. Evaporation from the bath is at a ferocious rate. Anyway, I am getting ahead of myself. I've spent probably a month preparing for this moment, making equipment, gathering chemicals, and above all, educating myself. This process has been somewhat of a holy grail for home chemists. The electroplating itself of lead dioxide is well known, but the problems that are associated with it are many, and ultimately cause the lead dioxide anode to fail in use. The primary failure mode is poor adhesion, meaning the electroplating simply does not stick well, to itself, or to the substrate. Pieces of lead dioxide simply flake away or fall off the anode. The second failure mode is chemical attack of the substrate rather than the lead dioxide, which by itself is quite inert in use. Assume for a moment that you have a nice titanium anode which you successfully plate with lead dioxide. It looks good. But in use, the potent liquor attacks the titanium beneath the lead dioxide; it oxidizes, and you lose continuity between the Ti and the lead dioxide. Eventually there is little or no conductivity between the two, and the anode fails. Several patents address the adhesion problem with the use of surfactants, especially those of the polyoxyethylene variety. I found a good one in Triton X-100. Think of the surfactant as a very powerful detergent. The second failure mode (attack of the substrate) I hope to overcome by plating the very tough MMO mesh which has proven itself in extreme environments. By the way, I have plenty of this mesh available... (shameless plug) - check the Agora. It is GOOD stuff! The setup is human and mechanical. The human, of course, is me. In my entire life, I have never worked with such noxious and toxic materials. I prepared accordingly: http://www.5bears.com/ld/ld00a.jpg Respirator, gloves, face shield, and a disposable painter's Tyvek suit that costed 7 bucks - worth it. Looks cool, too, or dorky, depending upon your love of science! I suppose the neighbors wondered a bit, though, when I crossed between the house and the shop! The separate portions of the setup were gathered together on a portable table. I layed down a plastic drop cloth, and taped it to shelves behind the table. Several layers of newsprint paper (from "Staples") were placed on the plastic to soak up spills and droplets. http://www.5bears.com/ld/ld01.jpg From left to right: a mag stirrer plus 4l beaker, a heater, a vacuum jar plus gauge (the vac pump is below the table), and a dual power supply. On top of the supply is a cheap powered HEPA filter that I was hoping would gather local airborne contaminants, and contain them. Finally, to the right, is the plating rig, seen before. It both vibrates AND rotates the anode. There was some doubt about the viability of rotation as a methodology, but I will flatly state that it works, and works well. The grey box at the edge of the table is the heater controller, also seen in a previous blog. The next batch of pictures will include pics of both anode 1 and anode 2 plating sessions. The difference between the two is primarily the bath size... for anode two, I went with the 6.5 liter bath. Anode 1 used a 2.5 liter, cheap plastic container that I was not happy with, but it had a good shape. There were important chemical differences as well, which I will describe as we proceed along. The first step was to prep the MMO anode. I began by simply immersing it in a beaker full of acetone, and allowing it to soak for perhaps an hour, with occasional agitation. While soaking, I also prepared another beaker full of distilled water, and added to the beaker approximately 2 ml of Triton X-100, a powerful surfactant. The Triton has a viscosity about like that of heavy molasses, but disperses well and easily. This beaker went on the heater to heat up to 70 degrees. http://www.5bears.com/ld/ld03.jpg Once heated, the Triton plus water mix became milky and a bit opaque. http://www.5bears.com/ld/ld04.jpg While the anode was soaking, I filled the 4 liter beaker with 2.5 liters of distilled water, and on the magnetic stirrer, began to add the chemicals. The "recipe" I used was a carefully thought-out mixture from a number of patents. The MS Word doc I have created which contains this recipe and much other info can be found here: Lead Dioxide Plating for Dummies http://www.5bears.com/ld/ld09.jpg Note the fancy custom labels. The two jars on the left were purchased in bulk from Duda Diesel, and the majority of my chemicals I bagged and stored in these HDPE jars. While not especially high quality, they are nice, and best of all, they stack. Very handy for tight storage locations. In the background is a 2.5 liter FEP bottle of concentrated nitric acid, the last chemical to add to the bath. The plating bath (2.5 liter, anode #1) consisted of the following: Compound gm/l Lead Nitrate – Pb(NO3)2-- 375 Nitric Acid – HNO3-- 10 Bismuth Nitrate - Bi(NO3)3.5H2O-- 20 Copper Nitrate - Cu(NO3)2.3H2O-- 14 Nickel Nitrate Ni(NO3)2.6H2O-- 10 Sodium Fluoride (NaF)-- 0.5 Surfactant – Triton X-100-- 0.5 I started with the less toxic and more easily dissolved salts: The copper nitrate and nickel nitrate. There is some controversy on the use of nickel nitrate. Older patents make use of it as a grain-refiner, and anything that refines grain (finer, denser lead dioxide) is desirable to me. I decided to try it. Use caution: Nickel Nitrate is both toxic AND a suspected carcinogen. After the lead nitrate, it is probably the most noxious of the chemicals. http://www.5bears.com/ld/ld11.jpg The Copper Nitrate is not required if using copper cathode(s), but in my case, I decided to use a CP (Commercially Pure) Titanium tube, so into the bath went 35 grams of Copper Nitrate: http://www.5bears.com/ld/ld10.jpg The water in the 4 liter beaker had already been heated to about 80 degrees C on the hot plate to ease in the mixing of the chems. For the 6.5 liter bath, this process had to be done twice... the first 3 liters were loaded with all of the chems except the lead nitrate, and added to the polypropylene bath. The beaker was refilled with an additional 3.5 liters of distilled water, heated, and used to dissolve the huge amounts of lead nitrate the "big bath" required. Back to the original bath, the 2.5 liter job... I decided to use Bismuth salts. From my research, in the patents, Bismuth was added to improve the efficiency of the anode in colder environments; not a player for perchlorate production, but there were some obscure references to it also being a grain-refiner. Into the bath it went. Being completely insoluble in a neutral solution, all it did was cloud the stirred electrolyte. One of the last chemicals to be added was the surfactant, 2.5 grams of Triton X-100. This too is controversial, because ultimately the acidic environment breaks down the polyoxyethylene chains; the bath life becomes limited as a result, unless the ruined surfactant is extracted with 1-propanol or similar. I decided to give this first run the very best chance for success, so it too went into the bath along with the Bi salts. With the cloudy mixture being magnetically stirred, I began to weigh out the lead nitrate on a kilogram scale. The various patents have a range of 200 to 400 grams per liter of lead nitrate. Despite the 375 g/l in the "Dummy" doc, I used instead 300 g/l, so 750 grams of lead nitrate was used. The lead nitrate was from Chemsavers, one of my (and Tentacles) favorite resources. Chemsavers has since nearly DOUBLED the cost of lead nitrate, yielding not a few epiphets on my end. Fortunately, I had purchased 10 kg from them back when it was a bit cheaper. There are now less expensive sources of lead nitrate that Chemsavers. A bit of search will reveal them! Lead nitrate should cost approximately $12 to $15 per kilogram... much more than that, and you are getting ripped off. http://www.5bears.com/ld/ld14.jpg Lead Nitrate is a useful chem beyond plating... it can be used to make nearly any other nitrate needed (such as Barium or Strontium) by simply adding the salt of interest to the lead nitrate solution. Since nearly every other lead salt is completely insoluble, the newly-formed lead salt precipitates and you can then harvest the aqueous nitrate of interest. Tentacles is the expert at this... I tend to be a lazy bastard and basically buy what I need. Anyway, I am rapidly drifting off topic. The lead nitrate dissolves with ease if the water is hot enough. This is one case where a combined mag stirrer + heater is a good thing to have. Not being blessed with one of these, I simply heated the solution first, then moved it to the stirrer to dissolve the lead nitrate. The final addition was the nitric acid. In both cases, I added 5ml of stock 70% nitric per liter to the bath. This is definitely on the low end of various recommended acid concentration ranges. Since the process itself generates nitric acid, and excess nitric is fatal to a good plating job, I erred on the side of caution. http://www.5bears.com/ld/ld12.jpg With the bath prepared, it was transferred from the large beaker to the 2.5 liter plastic container, and the immersion heater (encased in copper) was fixed into the bath and the controller turned on. Most resources state 60 to 80 degrees C. For both plating attempts, I set the controller for about 65 degrees, and the controller did a fantastic job throughout, maintaining +/- 2 degrees C. http://www.5bears.com/ld/ld16.jpg While the bath warmed up and stabilized, and the anode continued to soak, I prepared the cathode. Resources state the cathode should be between 1/3 and 1/2 the are of the anode. These anodes measured aproximately 8 cm X 4cm, for a surface area (as cut) of 32 square cm. The mesh actually has 2.2X this area, so the surface are of the anode was determined to be 75 square cm, counting the shank portion immersed in the bath. In my lathe, I took the titanium tubing (1/2" OD) and scored it every cm, so by counting the rings as they immerse, I was able to determine how much cathodic surface area is presented to the anode. Converting the 1/2" to metric, and doing a bit of math, I calculated roughly 4 cm squared for each cm of immersion. The cathode carrier was machined from a strip of PVC plastic, and I set it up for three cathode diameters, 0.312", 0.500" and 0.750" http://www.5bears.com/ld/ld07.jpg http://www.5bears.com/ld/ld15.jpg The grooves machined in the plastic carrier allows repositioning of the cathode on the plastic bath container, with stability. Once the bath had stabilized at 70 degrees, I continued with the preparation of the anode. It had been soaking in hot water plus surfactant. I decided to apply vacuum to the beaker to pull any bubbles or voids on and in the MMO away from the surface of the anode. http://www.5bears.com/ld/ld05.jpg The beaker + anode was set up in the bell jar, and the vacuum applied. The gauge slowly crept downward: http://www.5bears.com/ld/ld06.jpg At this pressure, the water began to boil, so I allowed a bit of air to creep into the bell jar to cease the boiling, yet still continue to draw off any trapped air. It was left at this pressure for 1/2 hour. To this point, both runs were identical with three major differences: The 2.5 liter bath had added Bismuth salts Additionally, it had added surfactant to the bath itself Finally, the volumes were greatly different, 2.5 liters vs. 6.5 liters. The anode was attached to the rotating arm with 316SS hardware. http://www.5bears.com/ld/ld21.jpg With everything completely ready to go, it was time, finally, to apply current. Like so much else associated with this process, suggested currents vary wildly. I took a number of them and essentially averaged the current. From "Plating for Dummies"... the list is phase of plating, Current in amps per square cm, and duration... Initial: 0.125 -- 15% Median: 0.050 -- 50% Final: 0.030 -- 35% Note that NO TIME is specified, mainly because I was unable to truly determine how long a plating job should last! I figured I'd keep an eye on the anode in the initial phase, and when it exhibited 100% lead dioxide coverage, I'd move on to the next phase. At this moment, minor catastrophe #1 occurred. I didn't even bother to check the required current... for some stupid reason, I figured it would be below 3 amps, which is the maximum my smaller lab supply can do. At 75 square centimeters, 0.125 A per, I needed 9.37 amps! I had two supplies to choose from, a lightweight inverter supply, which is 240V, and an 80 pound beast, my old Sorensen. Since I had no 240V at the plating station, I dragged the Sorensen over, and ten minutes later I had my 9.37 amps on the anode. I am not sure if soaking (with no current) of the anode, during this period, was harmful. Normally, you do not want electrodes to soak unpowered in an electrochemical cell. The rotation was turned on, setting the stage (again, I am referring to anode #1) for a more major catastrophe. I am not a completely stupid engineer... but for some reason, I decided a 0.375" copper round rod would rotate for days in a simple drilled hole in the aluminum anode support arm. Metal on metal at low RPM... normally not a problem. Immediately, I heard a bit of squalling from the system. That alone should have warned me! I added a couple of drops of oil, and soldiered on. The anode support arm has both rotational and vibrational capabilities. The vibrator was nothing more than a Pittmann motor mounted to the boom arm, and a variable brass weight was attached to the output shaft. By varying the voltage to the vibrator, I could go from only a barely perceptible shaking, to a vibration so severe that the bath contents were being ejected from the container! THAT would not be good with this toxic bath. Here is a test with water from a previous day: http://www.5bears.com/chem1/rig02.jpg The purpose behind rotation was primarily to create an even coating; secondarily, it was hoped that the rotation would eject pinhead bubbles. The sole purpose behind the vibration was to eject nasty bubbles from the surface of the anode. Much thanks to Xenoid (from SMDB) for this ingenious idea. I dialed the vibration down, set the rotation very slow, and waited... and watched. The anode darkened almost instantly, with the lead dioxide being flashed on. I ran anode #1 at the initial stage for approximately 1 hour. Then, I began to dial the current down to the median stage. In all stages of the project, the power supply was run in CC (Constant Current) mode. Interestingly, I was able to easily control the nitric acid evolution (a very important function) using a pH meter and PbO, litharge. The pH of the initial bath in both cases was 0.5. Within an hour, due to evolved nitric acid, it had dropped to below 0.0, into the negative range. Most meters and probes have a difficult time dealing with such a low pH, but my pH system seemed to work fine. Patent (and other) sources suggested 10 grams of litharge per liter, per hour of operation, to control pH and replenish Pb++ ions. A bit of experimentation on the fly showed this number to be fairly accurate. http://www.5bears.com/ld/ld19.jpg Approx 1/2 teaspoon of litharge every hour or so would bring the pH back up to 0.5, and that is where I tried to keep it. Lead Carbonate worked in much the same manner, with the bonus feature of a sizzle of CO2 gas as the carbonate hits the acidic bath, but litharge is cheaper and more convenient. Some sort of stirring or agitation is necessary during litharge additions. I used a PTFE rod as a stirrer. Future setups will definitely use some sort of motorized stirrer. I strongly believe that powerful agitation is helpful in this process. About three hours into plating #1, the copper rotation shaft siezed with the aluminum boom arm. The gearmotor that powers the rotation pulled the belt right off the toothed timing pulley used on the Cu shaft. The only way to free it was to manipulate it with quite a bit of oil, some of which definitely drained down the shaft, polluting the bath. With the entire rotational rig suspect, I pulled the plug at the 7 hour point; otherwise, I would have let it run overnight. Anode #1 is one ugly POS, and I doubt that it will be functional. The plating is rough and ugly. The lead dioxide that plated onto the pure CP Ti shank rubbed right off, probaby due to the oil dribbling down the shaft. LD on other parts of anode #1 seem flaky and fragile. To say I was unhappy was not an exaggeration. I had one more free day... Waking up early, I tore down the boom arm and machined some PET plastic bushings for the rotating shaft. The 6.5 liter bath was prepared with the exceptions I mentioned... no Bismuth, and no surfactant in the bath. Two other major differences - I boiled anode #2 in a fairly heavy solution of surfactant, and from there, it went into the plating bath directly, no rinsing. The initial plating was onto a surfactant-slick MMO surface. The second difference was in the spacing of the anode to the cathode. I probably tripled it... being farther away, and as a simple tubular form, the cathode becomes more of a point source. With good bearings in the boom arm, I was able to plate overnight. My goal was to close off the mesh. I didn't quite make it, but I am ecstatic with the quality of the plating. It is heavy, and so far, quite strong, shrugging off normal handling, whereas anode 1 is flakey, Since I have no basis for comparison, I am going to claim that yes indeed, it has that oft-mentioned "ceramic-like" surface. Anode #1: http://www.5bears.com/ld/ld24.jpg Anode #2: http://www.5bears.com/ld/ld28.jpg http://www.5bears.com/ld/ld30.jpg The odd blobules on the edge are even and strong. I don't think there is any way to make a mesh lead dioxide anode that doesn't have a slew of warts, and is generally ugly, but a strong, even grain is what is needed. I think that I may have nailed it with this one. Only testing will determine the truth of this. Remembering that these are actually small test anodes, their specs: MMO Mesh: 8.0 X 3.5 cm, 14.33 grams Anode #1: Little change dimensionally; 27.17 grams PbO2 deposited Anode #2: 9.0 X 4.7 cm, 182.78 grams PbO2 deposited Assuming anode 2 works, I believe the following attributes were important to the success: Thorough prep, to include boiling in a polyoxyethylene surfactant A bath including lead, copper, and nickel nitrates, plus NaF Lead Nitrate concentration high, >350 g/l Introduction of anode strongly wetted with surfactant to the bath Lengthy hi-amperage session to deposit strong alpha PbO2 Small Ti cathode, spacing 5" or greater Large, chemically stable bath Next on the list is an analysis of the bath remnants, check of Pb++ ion concentration, filtration, and an attempt to continue plating with the "used" bath, assuming ion concentration is acceptable. This anode took on 182 grams of PbO2, or 0.76 moles of lead. The 6.5 liter bath started with 6.95 moles of Pb in solution, so the anode "took up" 10.9% of the lead. I did not track litharge addition. A guess would be 200 grams, or an addition of 0.90 moles of Pb, so the lead concentration of the bath should be fairly close to start. Concentration is easy to check... take a sample of the bath, precipitate the lead ions with NaCl or MgSO4, and weigh the dried precipitate. Calculate the molar amount in the sample, and extrapolate. Historically, "used" baths don't plate as well as freshly-prepared baths, and I'm not sure why. It would be well worth investigating, given the cost of the chemicals, and the need to keep lead sequestered, safe, and not part of our local environment. You simply don't pour lead salts down the drain! If you experiment with lead, do so responsibly; be adult. One of the goals was to plate enough lead dioxide to actually "close" the MMO mesh. In retrospect, I'm not sure this is necessary. It will require 275+ grams of PbO2, and a plating duration of at least 24 to 36 hours, on a small 8 X 4 cm anode. An odd part of me prefers an aesthetically pleasing appearance for my anodes. I'd love to find a Ti rod, MMO coated, to plate with PbO2... this will definitely make a more attractive anode, and importantly, it will be strong. This has been a lengthy and massive blog. Thank you for following along. I realize that this plating process as I have presented it is overly complicated, and certainly not for everyone. One of the future goals is a simple and relatively small "one-pot, one shot" plating process using a very basic bath with a SS wire "cage" cathode. I believe (again, always assuming that these anodes perform) that the anode prep was perhaps the most important aspect to the plating, along with, in the case of #2, a large, chemically stable bath.

Houston, we have perchlorate. I've been finding this blog, for me, has become a source for easily accessible notes. For example, a while back I made an entry where I did a bit of math to determine expected yields, and investigated costs and efficiencies... THAT particular entry, I have referred to a few times for data and information. This is probably going to be another one like that. Online note-taking. The situation in the War Room - the perchlorate cell has amazed me with its cleanliness and ease of operation. After an initial shock over the generation of what I am convinced is ozone, the cell settled down (albeit with continued ozone production) and the perc begain to fall like rain. The crystals are much finer than the chlorate variety. The cell chemistry seems exceptionally straightforward. There is no chloride, chlorite, or hypochlorite. Just a simple mechanism at the anode whereby the chlorate ions are getting one more oxygen molecule jammed down their throats, and as they oxidize, they wave goodbye to their more soluble brothers, and sink to the bottom. The ozone is unmistakeable... I have worked with ozone outside any lab for years, first with reef aquaria, then with pool ozonators, so I do know what it smells like. It's pretty unique. But certainly I may be wrong. Somewhere in that cell, just a guess: ClO3- + 2O2 ----> ClO4- + O3 This seems extraordinarily inefficient. There are a number of references to ozone generation on the WWW using platinum anodes; for example: http://www.5bears.com/perc/tpc10.jpg Regardless of the mechanism, ozone is an extremely potent oxidizer, and may be involved heavily in the production of perchlorate ions, much more so than being a simple byproduct. My chemistry theoretical knowledge is nowhere near what it used to be. It is probably at a college freshman level, rather than at a graduate level. My college senior paper in p-chem (yuk) is titled An Investigation into microwave-excited gaseous emissions spectra, with considerations of Doppler and Lifetime-broadenings, and dealt with the hash of atomic species produced when low-pressure gasses are chopped with microwaves. It used an Oriel 7240 grating monochrometer and a chart recorder, Ar, Xe, and CO2 gasses, and a military-grade uWave generator; a pretty cool setup. The handwriting is mine, but the language is foreign! Anyway, with beaucoup perch in my cell, I am at a loss as to how to identify the endpoint. Wouter suggests some titrations that would work, but are more complex that your average titration, and in a practical sense, day to day, would be too much work. Some options: 1) Cell resistance: Everyone's setup is different, but with good notes, one might be able to determine endpoint with a good ohm meter. 2) Specific Gravity: Since the chlorate in a perc cell is dissolved, the SG will be well above 1.0, and as it converts to perchlorate, the SG will steadily drop due to the ultra-low solubility of the perch. This would be VERY temperature-dependant, and perc solubility varies greatly with heat, so a sample would have to be chilled in a refrigerator to a specific temp. It's possible, and one way to do it would be to create a series of standards, known samples with X chlorate and Y perchlorate, saturated at a higher temp and allowed to cool to a temperature of Z. This would drive a proportion of both salts out of solution, leaving you with a sample at a certain SG. In use, pull a sample with a turkey baster, cool to temperature Z, measure SG, and compare. With good hydrometers, it just might work. 3) Voltage, current, and time plots. Wouter states that 50 ampere-hours is required (at 100% efficiency) to convert 100 grams of sodium chlorate to sodium perchlorate. The MW of sodium chlorate is 106.44, thus 53.25 AH is needed to convert one mole of chlorate ion to perchlorate ion. My cell contained 600 grams of potassium chlorate, or 4.894 moles. 4.894 X 53.25 = 260 AH for this particular cell, at 100% efficiency, to convert ALL of the chlorate. Assumptions... the cell is 70% efficient (assumption), so 371.4 AH is needed. But converting ALL of the chlorate is a bad idea - stresses the anode. Let's assume the goal is to convert 80% of the chlorate present to perchlorate. 0.80 X 371.4 = 297 AH. Another way to look at it, in reference to the stop-point... no one's homemade cell is 100% efficient, so if you halt production at the theoretical 100% conversion point, you will leave behind a percentage of chlorate roughly equal to the inefficiency of your cell. As of this moment, I have pumped 307 AH into this system, somewhat higher than the theoretical 100% level of 260 AH. I will go to my lab and pull the plug, dry and weigh the product. The comes purification. Postscript: The yield, while it didn't quite suck, was less than I thought. Even worse, these crystals are super-fine, of the sort sometimes referred to as "mashed potatoes" crystals. You spoon a gelatinous blob into your filter, and wait... and wait... for the liquid to drain. Then you have to wash the stupid things, which makes it worse. Right now they're drying, I'm guessing the yield at maybe 150 grams. No big deal, all the chlorate is still there in the electrolyte, which I saved. I simply need to learn how long (and how hard) I can run a perc cell. This is the first step. Double Secret Postscript: The yield was better than I thought, at 320 grams. Still, it is not acceptable given 600 grams of chlorate in the cell. Better this than a fried Pt anode. At 20 degrees C and 4 liters, 100 grams of perchlorate remains in solution. Total perchlorate yield: 420 grams or 3.03 moles. Summary... Start: 600g / 4.89 moles KClO3 End: 420g / 3.03 moles KClO4 Dry Yield: 320g / 2.31 moles KClO4 In solution: 228g / 1.86 moles KClO3, and 100g / 0.72 moles KClO4 307 AH ---> 3.03 moles ClO4-, efficiency 52.6%