4. DESCRIPTION
4.1. Field of the invention:
The present invention relates to improved chemical composition for the production of safety matches suitable burning. More particularly relates to a chemical composition used for friction matches not containing sulfur in the conventional chemical composition of sulphurated tip for friction matches and to a method for manufacturing same.
4.2. Background of the invention:
The modern safety matches are usually a mixture of potassium chlorate (oxidizer), sulphur (igniter) and phosphorus (fuel) designed to burn when ignited. The basis of burning is a reaction between the oxidizer and the fuel. The use of potassium chlorate and phosphorus mixture is eliminated in the manufacturing of fireworks due to its ease of ignition and burning speed. Properties such as ease of ignition and burning speed are essential for the application of commercial matches. These very properties render match head chemical mixtures to be sensitive to impact energy, frictional load and temperature. Knowledge of the impact sensitivity of the match head mixture is required to assess its hazard potential as well as to make suitable plans for safety measures during manufacturing. The match head manufacturing process involves manual and mechanical operations.
Safety match has a head that ignites at a much higher temperature and must be struck on a specially prepared surface containing ingredients that pass ignition across to the head. The substance commonly used for obtaining combustion at the temperature of frictional heat is a compound of phosphorus. This substance is found in the head of strike-anywhere matches and the striking surface of safety matches. Red phosphorus, which is nontoxic and is not subject to spontaneous combustion, led to the safety match, with its separation of the combustion ingredients between the match head and the special striking surface.
In addition to the phosphoric igniting agent, three other main groups of chemicals are found in the match: (1) oxidizing agents, such as potassium chlorate, which supply oxygen to the igniting agent and the other combustible materials; (2) binders, such as animal glue, starches and gums, and synthetics, which bind the

ingredients and are oxidized during combustion; post-combustion binders, such as ground glass, which fuse and hold the ash together, must also be used; and (3) inert materials, such as diatomaceous earth, which provide bulk and regulate the speed of reaction. Commercial available match sticks consist of 48% of Potassium chlorate. 5.7% of Sulphur, 12.42% of Manganese dioxide, 0.95% of potassium dichromate, 21% of powdered glass, 0.95% of rosin, 2.6% of Zinc oxide and 8.4% of glue.
When sulphur burns in the atmosphere it forms sulphur dioxide gas. Sulphur dioxide is irritating to the eyes, nose, throat and lungs in concentrations greater than 6-20 parts per million (ppm). At 150 ppm, irritation is extreme. Concentrations in excess of 400-500 ppm may result in suffocation. The workplace exposure standard, eight-hour time-weighted average (WES-TWA-[1992]) is 2 ppm. Exposure to sulphur dioxide has no permanent systemic effect.
4.3. Objective of invention:
• To conduct thorough experiments by varying chemical composition, particle size, porosity of explosives.
• To assess the event of ignition timing and critical load of ignition under impact load by employing a modified version of impact test equipment.
• To assess the effect and interaction of the various heterogeneity of the energetic materials on impact sensitivity using the statistical tool, Design of Experiments.
• To study the thermal hazards and identify the role of each components and the physical characteristics of energetic materials in inducing ignition under Differential Scanning Calorimetry (DSC) and Thermo Gravimetry Analyser (TGA).
4.4. Description of Method:
To avoid the liberation of sulphur dioxide during combustion, match heads must be free from sulphur content. By conducting scientific and systematic survey

potential alternative fuel for sulphur have to be identified. By varying chemical composition, particle size, porosity of alternate match works chemical mixture; ignition timing and acritical load of ignition under impact load are assessed.
4.4.1. PREPARATION OF MATCHSTICKS
Woods used to make matchsticks must be porous enough to absorb various chemicals, and rigid enough to withstand the bending forces encountered when the match is struck. They should also be straight-grained and easy to work so that they may be readily cut into sticks. White pine and aspen are two common kinds of wood used for this purpose.
Once the matchsticks were formed, they were soaked in ammonium phosphate, which is a fire retardant. This prevents the stick from smouldering after the match has gone out. During manufacture, the striking ends of the matchsticks were dipped in hot paraffin wax. This provides a small amount of fuel to transfer the flame from the burning chemicals from the tip to the matchstick itself. Once the paraffin burns off, the ammonium phosphate in the matchstick prevents any further combustion. The matchsticks are displayed in the frameis shown in figure 4.4.1.

conventional match sticks are used along with identified sulphur alternatives.
4.4.2.1. SAMPLE 1
650 gof 10.8 percent caseinwas mixed with 50 ml of fevicol, and 500 ml of ammonia and sufficient amount of water was added for the preparation of binder. Then. 3000 g of potassium chlorate was added thereto and the mixture was further stirred very actively for about 10 minutes so that the solution was placed in a spongy condition through development and mixing of very fine air voids.Further two litersof hot water was added to this spongy solution and the temperature of same was maintained at 50°C. A blend wascomposed of 421 g of 7 percent silicon dioxide, 4 g of 0.1 percent calcium oxide was added to 700 g of 11.7 percent powdered glass. Then 1000 g of 16.7 percent manganese dioxide was added to the spongy solution along with 75 g Of 1.25 percent potassium dichromate, 50 g of 0.8 percent rosin and 35 g of 0.6 percent zinc oxide.Then the mixture was taken to aconical grinding machine for effective mixing of chemicals and also to reduce the particle size of chemicals used. Also, sufficient amount of water must be added to make the chemical adhere to the matchstick when thedipping process was done. The conical grinding machine should not run continuously for more than 15 minutes, and the entire grinding process should not take more than 30 minutes. The preparation of match head chemical composition in ball mi!! is shown in figure 4.4.2.1.
The dipped match sticks should be allowed to dry in shadows and it should not be disturbed for atleast 4 hours. The performance test and another quality test must be performed on the fourth day from the date of manufacturing. The match

4.4.2.2. SAMPLE 2
700 g of 11.6 percent caseinwas mixed with 50 ml of fevicol. and 150 ml of ammonia and sufficient amount of water was added for the preparation of binder. Then, 3000 g of potassium chlorate was added thereto and the mixture was further stirred-very actively for about 10 minutes so that the solution was placed in a spongy condition through development and mixing of very fine air voids.Further two liters of hot water was added to this spongy solution and the temperature of same was maintained at 50°C. A blend that is composed of 421 g of 7 percent cellulosic substance, 4 g of 0.1 percent calcium oxide was added to 600 g of 10 percent powdered glass. Then 1000 g of 16.7 percent manganese dioxide is added

to the spongy solution along with 75 g Of 1.25 percent potassium dichromate, 50 g of 0.8 percent rosin and 35 g of 0.6 percent zinc oxide.Then the mixture was taken to aconical grinding machine for effective mixing of chemicals and also to reduce the particle size of chemicals used. Also, sufficient amount of water must be added to make the chemical adhere to the matchstick when thedipping process is done. The conical grinding machine should not run continuously for more than 15 minutes, and the entire grinding process should not take more than 30 minutes. The dipped match sticks should be allowed to dry in shadows, and it should not be disturbed for atleast 4 hours. The performance test and another quality test must be performed on the fourth day from the date of manufacturing.The match composition for sample 2 is shown in table 4.4.2.2.

ammonia and sufficient amount of water was added for the preparation of binder. Then, 3000 g of potassium chlorate was added thereto and the mixture was further stirred very actively for about 10 minutes so that the solution was placed in a spongy condition through development and mixing of very fine air voids.Further two liters of hot water was added to this spongy solution and the temperature of same was maintained at 50°C. A blend was composed of 125 g of 2.08 percent silicon dioxide, 125 g of 2.08 percent cellulose, 125 g of 2.08 starch and 50 g Of 0.83 percent aluminium hydroxide was added to 550 g of 9.17 percent powdered glass. Then 1000 g of 16.7 percent manganese dioxide was added to the spongy solution along with 75 g Of 1.25 percent potassium dichromate, 50 g of 0.8 percent rosin and 35 g of 0.6 percent zinc oxide. Then the mixture is taken to a conical grinding machine for effective mixing of chemicals and also to reduce the particle size of chemicals used. Also, sufficient amount of water must be added to make the chemical adhere to the matchstick when the dipping process is done. The conical grinding machine should not run continuously for more than 15 minutes, and the entire grinding process should not take more than 30 minutes.The dipped match sticks should be allowed to dry in shadows, and it should not be disturbed for atleast 4 hours. The performance test and another quality test must be performed on the fourth day from the date of manufacturing.The match composition for sample 3 is shown in table 4.4.2.3.

650 g of 10.8 percent caseinwas mixed with 50 ml of fevicol, and 150 mi of ammonia and sufficient amount of water was added for the preparation of binder. Then, 3000 g of potassium chlorate was added thereto and the mixture was further stirred very actively for about 10 minutes so that the solution was placed in a spongy condition through development and mixing of very fine air voids.Further two litersof hot water was added to this spongy solution and the temperature of same was maintained at 50°C. A blend was composed of 375 g of 6.25 percent starchwas added to 700 g of 11.7 percent powdered glass. Then 1000 g of 16.7 percent manganese dioxide was added to the spongy solution along with 75 g Of 1.25 percent potassium dichromate. 50 g of 0.8 percent rosin and 35 g of 0.6 percent zinc oxide. Then the mixture was taken to a conical grinding machine for effective mixing of chemicals and also to reduce the particle size of chemicals used. Also, sufficient amount of water must be added to make the chemical adhere to the matchstick when the dipping process is done. The conical grinding machine should not run continuously for more than 15 minutes, and the entire grinding process should not take more than 30 minutes. The dipped match sticks should be allowed to dry in shadows and it should not be disturbed for atleast 4 hours. The performance test and another quality test must be performed on the fourth day from the dale of manufacturing.The match composition for sample 4 is shown in table 4.4.2.4.

4.4.2.5. SAMPLE 5
650 g of 10.8 percent caseinwas mixed with 50 ml of fevicol, and 150 ml of ammonia and sufficient amount of water was added for the preparation of binder. Then, 3250 g of potassium chlorate was added thereto and the mixture was further stirred very actively for about 10 minutes so that the solution was placed in a spongy condition through development and mixing of very fine air voids.Further two litersof hot water was added to this spongy solution and the temperature of same was maintained at 50°C. A blend was composed of 400 g of 6.67 percent starchwais added to 700 g of 11.7 percent powdered glass. Then 1000 g of 16.7 percent manganese dioxide was added to the spongy solution along with 90 g Of 1.5 percent potassium dichromate, 50 g of 0.8 percent rosin and 35 g of 0.6 percent zinc oxide. Then the mixture was taken to a conical grinding machine for effective mixing of chemicals and also to reduce the particle size of chemicals used. Also,

sufficient amount of water must be added to make the chemical adhere to the matchstick when the dipping process is done. The conical grinding machine should not run continuously for more than 15 minutes, and the entire grinding process should not take more than 30 minutes. The dipped match sticks should be allowed to dry in shadows and it should not be disturbed for atleast 4 hours. The performance test and another quality test must be performed on the fourth day from the date of manufacturing.The match composition for sample 5 is shown in table 4.4.2.5.
4.4.2.6. SAMPLE 6
650 g of 10.8 percent caseinwas mixed with 50 ml of fevicol, and 150 ml of ammonia and sufficient amount of water was added for the preparation of binder. Then, 3000 g of potassium chlorate was added thereto and the mixture was further

stirred very actively for about 10 minutes so that the solution was placed in a spongy condition through development and mixing of very fine air voids.Further two Iitersof hot water was added to this spongy solution and the temperature of same was maintained at 50°C. A blend was composed of 450 g of 7.5 percent corn flourwas added to 700 g of 11.7 percent powdered glass. Then 1000 g of 16.7 percent manganese dioxide was added to the spongy solution along with 90 g Of 1.5 percent potassium dichromate, 50 g of 0.8 percent rosin and 35 g of 0.6 percent zinc oxide. Then the mixture was taken to a conical grinding machine for effective mixing of chemicals and also to reduce the particle size of chemicals used. Also, sufficient amount of water must be added to make the chemical adhere to the matchstick when the dipping process was done. The conical grinding machine should not run continuously for more than 15 minutes, and the entire grinding process should not take more than 30 minutes. The dipped match sticks should be allowed to dry in shadows and it should not be disturbed for atleast 4 hours. The performance test and another quality test must be performed on the fourth day from the date of manufacturing.The match composition for sample 6 is shown in table 4.4.2.6.

4.5.1 STRIKING PERFORMANCE TEST
Striking performance test was carried out in a draught-free environmentand that matches were not moved once ignition has been initiated.With the match box hold over an A4 sheet of white paper of grammage 80 + 5 g/m, holding the match firmly between the first finger and thumb and striking it against the striking surface of the box with the minimum pressure necessary to cause ignition. The mode of striking is shown in firure 4.3.1. The match should be held approximately 100 mm above the sheet of paper during testing.
Record any breakage or fracture of the stem prior toignition and whether ignition occurs or is delayed. At ignition, record any explosion or fragmentationof the match head or any breakage of the stem thatresults in separation of the broken pieces. During ignition, record any dropping of hot ashsufficient to permanently mark the paper with bum marks.

The match was allowed to continue to burn with the stemhorizontal until the flame has spread halfway along thestem. Record whether liquid drips from the stem duringburning.When the flame reaches half-way along the stem, or after burning for at least 10s, it was extinguished with a puff of air and whether the charred stem continues to glow for more than 4 s or cardboard and wax matches, for more than 6s was recorded. If the match extinguishes before the flame reacheshalf way along the stem, record events at and after the momentof extinguishing. Strike the matches on a supported flint sheet ofIS Grit 120(3/0) and record whether ignition can be initiated.
4.5.2. IGNITION BELOW 170°C
The test was carried out by placing the matchsticks in anoven maintained at 170°C examined for ignition.Oven to be used shall be air circulated thermostaticallycontrolied electric oven of which electrical elements shall be totally enclosed.To read up to 200°C with a divisional accuracy of 1°C, thethermometer has to be used. The Wooden block shall be 30 mm thick and 50 mm square, having a holeof 10 mm diameter to a depth of 25 mm at the centre toserve as a receptacle to hold the sticks.
Take ten normal match sticks ready for use from the selectedmatch boxes of the test sample and placed them with theheads up in the receptacle of the wooden block. The block was placed in the centre of the oven. Suspend thethermometer in such a way that its bulb was on the levelwith the match heads and is at a distance of about 50 mmfrom the match heads. Thermometer bulb shall be coveredwith wire mesh. Close the door of the oven and raise its temperature to 140°C. After this, raise the temperatureuniformly at a rate of approximately 3°C per minute until 170°C temperature was reached.The sample shall be taken to have passed the test if noneof the matchsticks catches fire.
4.5.3. IGNITION UNDER IMPACT TEST
The test was carried out by striking the matchsticks with a hammer of 170 g and examined for ignition.

Tenmatchstickswere laken from the selected match boxes of the test sample and tested each matchstick separately. Stick was placed on the anvil of polished steel, in such a way that the stick was horizontal and the head was its centre. Drop thestriking hammer by releasing the spring catch. It wasObserved that whether the head catches fire under this impact. Even, if the smoke is produced during this test is considered that the impact energy of 833.85mJis enough to start the ignition. The sample shall be taken to have passed the test if none ofthe matchsticks catches fire or produces smoke. The apparatus for impact test is shown in figure 4.3.3.
4.5.4. TEST FOR DAMP PROOFNESS
The test was carried out by keeping the match boxes in adesiccator containing water for 24 h and examined fortheir burning quality.Inside diameter of

about 250 mm and overall height 303 mm, with a plate inside.The desiccator shall contain porcelain plate having5 mm thickness or aluminium plate having 2 mm thicknessconsisting of 162 holes each of 5 mm diameter and acentral hole of 2.3 mm diameter.Five boxes each containing 50 serviceable sticks ware made. The match sticks ware conditioned at 27 - 2°C temperature and 65-5 percent relative humidityfor six hours. Sufficient amount of water wastaken in the desiccator so that the distance between thewater surface and the bottom surface of porcelain plate waisabout 25 mm. Five match boxes was placed in the desiccator in a way that the head side of each matchboxis half open and each box was resting on its edge with thefriction surface vertical as well as heads up. This fillingof desiccator with match boxes shall take not more thantworain when it is again placed in the ambient conditionsmentioned above. The match boxes wereput onthe desiccator plate so that each matchbox is not closerthan 15 mm to the walls of the desiccator. The desiccatorwas closed for 24 h in the same ambient conditions. Figure 4.3.4 shows arrangement of match boxes in desiccator.
4.5.5. Differential Scanning Calorimeter(DSC) Test
DSC measures the heat into or out of a sample and measures the heat of a sample relative to a reference. There by it helps to determine the onset exothermic and endothermic temperatures and maximum temperature reached during

'exothermic and endothermic reaction. In matchsticks, endothermic reaction is always followed by exothermic reaction and study of maximum temperature reached during endothermic reaction helps to determine amount of heat required to start exothermic reaction which in turn states the sensitivity of matchstick.
4.6. References:
1. Jaime Wisniak, "Matches-The manufacture of fire", Indian Journal of Chemical Technology, volume 12, may 2005, pp.369-380.
2. Klimont, S J Smith and J Cofala, "The last decade of global anthropogenic sulfur dioxide: 2000-2011 emissions", Environ. Res. Lett. 8 (2013) 014003
(6PP).
3. Nigel J. Ricketts and Simon P. Cashion," Hydrofluorocarbons as a
replacement for sulphur hexafluoride in magnesium processing", Cooperative Research Centre for Cast Metals Manufacturing (CAST).
4. Zandaryaa S and Buekens A, "Control of sulfur oxides", Pollution Control Technologies.
5. Azhagurajan A , Selvakumar N, Suresh Aa "Environment-Friendly Fireworks Manufacturing using Nanoscale flash powder", Journal of Scientific and Industrial Research, volume 73,pp.479-484.
6. HighBeam™ Research, Inc.,"Match manufacturing".
7. Hiroshi Hijikata, Shizuoka, "Chemical composition for combustible tip used for friction matches and method for manufacturing same" US Patents 3775198.
8. Bryant and May, "Match-Head composition" US Patents 4060434.

5. CLAIMS
I CLAIM
1. The composition provided above is without sulphur for match head preparation.
2. Starch is potential alternative for sulphur.
3. The match head composition and the method of preparation.
DATE AND SIGNATURE (To be given at the end oflast page of specification)