|Publication number||US3927993 A|
|Publication date||Dec 23, 1975|
|Filing date||Nov 21, 1973|
|Priority date||Nov 21, 1973|
|Publication number||US 3927993 A, US 3927993A, US-A-3927993, US3927993 A, US3927993A|
|Inventors||Griffin Ronald W|
|Original Assignee||Griffin Ronald W|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (2), Referenced by (20), Classifications (13)|
|External Links: USPTO, USPTO Assignment, Espacenet|
nited States Patent 1 Griffin Dec. 23, 1975 FIRE STARTER AND METHOD  Inventor: Ronald W. Griffin, 2047 E. Fifth,
Albany, Oreg. 97321  Filed: Nov. 21, 1973  Appl. No.: 418,044
Primary ExaminerCarl F. Dees Attorney, Agent, or Firm-Klarquist, Sparkman, Campbell, Leigh, Hall & Whinston  ABSTRACT A fire starter is composed of particles of zirconium, hafnium or titanium sponge bonded together under high pressure or with a binder, or both, into a dense cake or pellet. The binder, if used, is preferably a combustible wax or resinous substance having a lower spontaneous ignition temperature than the particle mass to aid in igniting the sponge. In one form the pellet is contained in waxed paper or other combustible wrapper which serves as a means for igniting the pellet. The pellet can be formed by compacting the loose metallic sponge particles together into a desired shape under high pressures of at least about 6,000 psi and then dipping the resulting pellet into a liquid wax or resin bath to impregnate the pellet. Alternatively the pellet can be formed by mixing the loose metallic sponge particles with a liquid resin, wax or other binder to form a wet mixture and then pressing, molding or extruding the wet mixture into the desired shape.
25 Claims, No Drawings FIRE STARTER AND METHOD BACKGROUND OF THE INVENTION 7 1. Field of the Invention The present invention relates to fire starters and other incendiary devices.
2. Description of the Prior Art Large numbers and types of fire starters have been marketed for years for use by woodsmen, householders and others in igniting wood, charcoal and other materials. These have embodied 'such diverse materials as flammable chemicals in liquid or tablet form, mixtures of wood particles or dust and various resins, wax candles and various semi-solid compounds sold in tubes. Despite the wide variety of fire starters available, a need still exists for one that is truly effective in kindling combustible materials which are difficult to ignite, such as wet wood, charcoal, and other materials having a high spontaneous ignition temperature.
Most known fire starters have one or more of the disadvantages: (a) difficult ignition; (b) dangerous and unstable because of high flammability or low spontaneous ignition temperature; (c) low burning temperature; (d) short burning time; or (e) large volume making transport and storage difficult.
Some of the rare earth metals, principally zirconium and titanium, in their pure or highly refined powder form, have been recognized as having pyrophoric properties and therefore have been suggested for use as fulminators in flash bulbs and as an ingredient in incendiary compositions for munitions to produce short bursts of intense heat or flame. However, such metal powders are generally recognized as being unsuitable for use in fire starter applications requiring long buming periods of several minutes because of their tendency to flash-bum in short bursts measured in milliseconds and because of their low self-ignition temperatures making them unstable and dangerous to handle. Also, such rare earth metals are extremely expensive because of the high cost of processing them to their refined state.
Accordingly, there is still a need for an effective fire starter having all of thedesirable characteristics of small size, light weight, easy ignition yet high enough spontaneous ignition temperature to avoid accidental self-ignition, long burning time, high burning temperature and low cost.
SUMMARY OF THE INVENTION Applicant has discovered that grain-sized particles of zirconium, hafnium and titanium sponge, which is a porous material formed at an intermediate step in the refining of these metals, when compacted into a small dense mass either under high pressure or under' low pressure in combination with a binder, is an effective fire starter. Such a mass has surprising pyrophoric properties in that it can be easily ignited from a flame or other heat source and Yet has 'a high enough spontaneous ignition temperature to avoid the danger off accidental self-ignition, has a slow burning rate and therefore a long burn time, and burns at a high temperature. A small 30-gram pellet of zirconium sponge particles and one inch in diameter compacted under 20,000 psi pressure has been found to have a spontaneous ignition temperature of about 650F, a maximum burning temperature of about 2600F upon ignition, a burn time of over forty-five minutes, and a relatively 2 constant post-ignition burning temperature over most of the burn time of about l500F.
A preferred composition of such a pellet includes zirconium sponge recovered from the zirconium refining process and crushed into particles of about sandgrain size and then coated with a combustible wax or resin binder either before or after the particles are compacted together into a dense mass of the desired size and shape. The resulting pellet or cake is advantageously packaged in a wrapper or other envelope of waxed paper, cardboard or other readily combustible material which then serves as the initial ignition means for the pellet. However, the invention is of sufficient scope to include any other suitable ignition means including fuseor detonator-type ignition agents.
Although the present invention has obvious applications for woodsmen, householders and others in kindling wood, charcoal and other materials commonly burned for warmth or cooking, such invention also has application to incendiary components of bombs, projectiles and other munitions where a stable, long-burning, high temperature incendiary device is needed.
A principal object of the invention'is to provide a fire-starting composition or device having all of the desirable characteristics of a fire starter including high 'i stability, easy ignition, sufficiently high spontaneous ignition temperature to avoid accidental self-ignition, high burning temperature, long burning time, small size, light weight, low cost and easy manufacture.
Another primary object is to provide a simple lowcost mehtod of making a fire starter of the described composition.
The foregoing objects, features and advantages of the invention will become more apparent from the following detailed description.
DETAILED DESCRIPTION The basic and essential raw material for the fire-kindling or incendiary composition of the present invention is zirconium, hafnium or titanium sponge. These metallic sponge materials are produced at an intermediate step in the processes of refining the pure metals from their ores. For example, zirconium metal is produced from zircon (zirconium silicate, ZrSiO and baddeleyite (zirconium oxide, ZrO The zircon is commonly recovered from certain kinds of beach sands. The well-known Kroll process is used to refine zirconium. In this process zircon is converted to zirconium oxide by liquid extraction. Then zirconium oxide is converted to zirconium chloride (ZrC1 which is then reduced by molten magnesium to produce zirconium sponge. The sponge is then melted in consumable vacuumarc furnace to recover the zirconium metal.
Although the device of the present invention can utilize either zirconium, titanium or hafnium sponge as its basic raw material, zirconium is preferred and therefore will be emphasized over titanium and hafnium sponge throughout this description.
The fire-starting composition of the present invention is preferably made from low-grade zirconium sponge. This type of sponge burns hotter and ignites more easily than the purer form of such sponge from which zirconium metal is recovered in the production process. The low-grade sponge is recovered in chunks from such vessel. The sponge chunks are then crushed into particles of a suitable size.
A typical sample of scrap zirconium sponge yielded the following chemical analysis:
TABLE 1 CHEMICAL ANALYSIS OF LOW-GRADE ZIRCONIUM SPONGE RECOVERED FROM PRODUCTION VESSEL C 500 ppm Mg 650 ppm N 0.20% Pb less than 50 ppm Hf 28 ppm Si 97 ppm Cb less than 100 ppm Ti 29 ppm Ta less than 200 ppm U 0.60 ppm Fe 4240 ppm Cl 1350 ppm Cr 235 ppm P 42 ppm Ni less than 35 ppm 0.33% Al 206 ppm 4 ignition, but the metal pellet burned at a much faster rate than the comparable zirconium sponge pellet. The cost factor is also significant. Refined zirconium metal powder costs from four to five times as much per pound as zirconium sponge.
When zirconium sponge particles are bonded together into a dense mass, they are much more diffieult to ignite than when loose, because as particle size increases, particle volume increases with respect to surface area causing increased surface heat loss through conduction into the sample. Thus, in general, small metal or metallic sponge samples can self-heat to ignition from a lower initial surface temperature than can larger samples. In other words, smaller samples of either metal or metal sponge particles tend to be more pyrophoric than larger samples.
In one series of tests, one-inch diameter pellets weighing 30 grams each, compacted under a pressure of 20,000 psi and composed of sponge particles of zirconium, titanium or hafnium, alone and in various combinations, and in various particle sizes, were tested for ignition characteristics and burning time. The results of this series of tests is shown in Table 2.
TABLE 2 COMPARISON OF IGNITION AND BURNING PROPERTIES OF VARIOUS SPONGE PELLET COMPOSITIONS Size of Particle Particle Example Pellet Size Material Comment I l diam. A in. Zirc. sponge Ignition good, but short burn 30 grams time. I 2 l" diam. A; in. Zirc. sponge Ignition good, burn time good.
30 grams 3 1" diam. 0.131 in. Zirc. sponge Ignition good, long burn time.
30 grams 4 l" diam. 20 mesh Zirc. sponge Ignition good, but not quite as 30 grams (0.0331 in.) long time as 0.131 in. zirc. sponge 5 l" diam 0.131 in. 50% zirc. sponge Ignition not as good as 100% zirc.
30 grams 50% Ti sponge sponge; burn time shorter than 100% zirc. sponge. 6 1 diarn. 0.131 in. zirc. sponge Difficult to ignite; burn tempergrams 75% Ti sponge ature not as high as with 100% zirc. sponge; burn time not as long as with 100% zirc. sponge. 7 1" diam. 0.131 in. zirc. sponge Ignition as good as 100% zirc.
30 grams 50% hf. sponge sponge; approx. same burn time and burn temperature as 100% zirc. sponge. 8 1" diam. 0.131 in. Titanium Difficult to ignite; burn temper- 30 grams sponge ature not as high as zirc. sponge;
burn time half that of zirc. sponge; performance still satisfactory. 9 I" diarn. 0.131 in. Hafnium Ignition good; burn temperature 30 grams sponge good; burn time good; comparable to 0.131 in. zirc. sponge.
This compares to a Brinell hardness of approximately 140 for the purer form of zirconium sponge used in the production of the metal. The purer sponge has a lower iron, nitrogen, oxygen, magnesium and chlorine content than the low-grade sponge.
Zirconium sponge exhibits surprisingly different burning properties than refined zirconium metal powder. In this regard refined zirconium metal powder of approximately 0.0331 inch size (20 mesh, Tyler Screen Scale Equivalent Designation of U.S. Sieve Series) when compacted into a dense pellet had a self-ignition temperature of approximately 270F. However, a comparable dense pellet of zirconium sponge particles of the same size had a self-ignition temperature of approximately 500F. Therefore the compacted sponge is far more stable and thus more safe to handle than the compacted zirconium metal powder. The pellet of zirconium metal attained approximately the same maximum tmeperature as the zirconium sponge pellet upon PELLET AND PARTICLE SIZES In testing pellets or compacts of various sizes composed of sponge particles of different sizes, it was found that the smaller the pellet, the smaller should be the size of particles used in the pellet. The size of the pellet did not affect either the maximum burning temperature of the pellet or its average burning temperature. Not surprisingly, the larger the pellet, the longer was the resulting burn time. Thirty-gram pellets of zirconium sponge, one inch in diameter, burned for more than forty-five minutes up to two hours or more depending on particle size. However, a ten-gram pellet, one-half inch in diameter, composed of zirconium sponge particles of comparable size, burned for twenty minutes or less, depending on particle size.
Table 3 gives a recommended range of sponge particle sizes for various-sized compacts.
TABLE 3 RECOMMENDED RANGE OF SPONGE PARTICLE SIZES AND COMPACTION PRESSURES FOR COMPACTS OF VARYING SIZES It was also found that the maximum size of zirconium sponge that would burn so as to oxidize completely the sponge was approximately 3/16 inch. Larger sponge particles, such as inch particles, did burn, but they did not burn as long as particles in the Vs inch size range or smaller and they were more difficult to ignite.
IGNITION AND BURNING PROPERTIES One 30-gram sample of zirconium sponge particles ranging in size from 0.131 inch to mesh (0.0331 inch) and compacted under a pressure of 20,000 psi into a 1-inch diameter pellet approximately /a inch thick exhibited a spontaneous ignition temperature of 787F and a maximum temperature of 2801F, 22 seconds after spontaneous ignition. Thereafter it settled down to a reasonably steady temperature of around 1500 to 1600F from about three minutes following spontaneous ignition on (referred to herein as the post-ignition" burn). The complete results of this test The results of testing -gram zirconium sponge compacts made up of sponge particles of different sizes are tabulated in Table 5.
TABLE 5 LENGTH OF BURN FOR 30-GRAM ZIRCONIUM SPONGE COMPACTS OF DIFFERENT PARTICLE SIZES Sponge Size Length of Burn Example (Mesh Opening, Inches) (Minutes) From the foregoing it was concluded that the smaller the size of particles making up the compact, the longer was the burning time of the compact, other conditions being equal.
The following Table 6 reveals other pyrophoric propare shown in Table 4. erties of the 30-gram zirconium sponge compacts sted in Table 5: TABLE 4 te TABLE 6 PYROPI-IORIC PROPERTIES OF ZIRC. SPONGE PELLETS Sponge Size Spontaneous Igni Temperature Temperature 10 (Mesh Opening tion Temperatures Upon Igni- Minutes After Example in Inches) (F) tion (F) Ignition (F) TIME AND TEMPERATURE TEST ZIRC. SPONGE COMPACTED UNDER 20,000 PSI TO ONE-INCH DIAMETER PARTICLE SIZE 0.131 INCH TO 20 MESH Time in Seconds from Spontaneous Ignition Point Temperature in Degrees F.
In general it was found that neither the size of the compact nor the size of the sponge particles used in the compact varied the maximum or continuous burning temperature of the compact significantly. However, particle size did vary considerably the spontaneous ignition temperature. The smaller the particle sizes used, the lower was the spontaneous ignition temperature.
In most of the foregoing tests a zirconium sponge cake or pellet was used weighing 30 grams, having a diameter of about one inch, and a thickness of about /2 inch. The compaction pressure was about 20,000 psi. Such a pellet has been found to be ideal for use in starting wet or dry wood and charcoal tires. The pellet burns for 45 minutes or longer when grain sizes of 0.131 inches or less are used, exhibits a high, yet not excessive, spontaneous ignition temperature of about 600 to 650F, reaches a maximum temperature of about 2600F, and burns for most of its postignition burn time at l000 to 1500F.
Of course, pellets of smaller or larger sizes and of any desired shape can be used depending on the intended application.
IGNITION MEANS The pellets, whatever the size, must be provided with an ignition means for heating it to its spontaneous ignition temperature. This ignition means can either by a wax-type coating or any other material that will heat the compact to its spontaneous ignition point. Other ignition means can include an open flame, or other heat source. A fuse wrapped around or through the pellet can be used to provide self-ignition. Also an explosive charge can be used to ignite the compact by heat and pressure.
METHODS OF MANUFACTURE For experimental purposes, commercial-type pellets for use as fire starters were made using a mold with a cavity one inch in diameter and a plunger conn cted to a hydraulic press to press sponge particles into pellet or cake form using pressures ranging from about 6,000 psi to 60,000 psi, but preferably in the range 20,000 to 35,000 psi. Pressures in the latter range are sufficient to physically bond the sponge particles together without the use of a binder. However, to ensure that each pellet remains in one piece until ready for use and to hasten ignition, each pellet following formation is preferably dipped in hot liquid wax. The pellet retains sufficient porosity so that it readily absorbs the liquid wax into its pores. When the pellet is removed from the wax bath and cured at room temperature, the wax solidifies and thus the pellet becomes permanently wax-impregnated. Of course, any other binder material could be used rather than wax, but preferably it should be a combustible binder having a lower spontaneous ignition temperature than the compacted sponge so as to serve as to aid in ignition of the pellet. For example, many resinous materials could be used for this purpose as well as various waxes as already mentioned.
After each pellet is impregnated with wax or other binder and cured, it is preferably wrapped in a waxed paper or other material that is readily combustible and that can be ignited easily with the flame from a conven tional match. The combustible wrapper preferably should be waterproof, especially if the fire starter is for outdoor use.
With a pellet of zirconium, titanium or hafnium sponge material compacted, impregnated and wrapped as described, the pellet can be heated to its spontaneous ignition temperature by first igniting its wrapper with the flame from a match so that the wrapper itself burns and elevates the temperature of the sponge material and at the same time ignites the combustible binder of the pellet. Within a very short time the sponge material itself will begin buming. When this occurs the pellet gives off a bright glow, but does not flame.
Another method used successfully to make metallic sponge compacts suitable for use as fire starters is to pour loose sponge particles directly into a hot liquid wax to form a wet mixture of the wax and sponge parti cles having the consistency of wet sand. The wet mixture is then packed into small wax-coated semi-rigid paper or paperboard cups or other containers under low pressures. The complete coating of the particles with liquid wax enables the wax to act as a good binder to hold the resulting cake together despite the low packing pressures used. These compacts, however, are
of a larger size for a given weight of material than the first-mentioned compacts because of the lower compaction pressures under which they are formed.
In the wet-mixture method just described, the waxcoated container together with the wax binder material serves as the ignition means for igniting the sponge material itself, the container being readily ignitable from a match, candle or other open flame.
Another suitable method adaptable to high production technique for forming commercial pellets of small size is a variation of the wet-mixture method just described. According to this method the loose sponge particles are mixed with liquid wax as before to form a wet mixture. Then the mixture is packed into an extrusion die cavity and extruded through an orifice at the bottom of the die cavity using a die plunger or auger to extrude a long strip of the compacted mixture of circular or any other desired cross-sectional shape depending on the shape of the extrusion orifice. The continuous extruded length of material is then sliced into shorter-length pellets or tablets by moving the compacted extruded mixture past a slicing station having a reciprocating knife that moves at intervals across the path of the moving extrusion. The resulting pellets can then be wrapped in waxed paper or other easily ignitable combustible wrapping material, suitably packaged and then marketed. In this method the extrusion die preferably would be heated to maintain the wax and sponge mixture in a flowable state.
As previously indicated, hafnium sponge has been found to have pyrophoric properties very closely ap proximately those of zirconium sponge. However, titanium sponge exhibits a shorter average burning time than zirconium sponge, a lower post-ignition burning temperature, in the 500 to 600F range, and a higher ignition temperature. Therefore titanium sponge is less desirable for most fire starter applications than either zirconium sponge or hafnium sponge on the basis of pyrophoric properties alone. However, the titanium sponge still is an effective fire starter where a suitable ignition source is available and where the higher temperatures and longer burn time obtainable from hafnium or zirconium sponge is not a requirement. Zirconium sponge is preferred to hafnium sponge, not necessarily on the basis of pyrophoric properties, but merely because the zirconium sponge is much less expensive to obtain at this time.
Although in the preferred embodiment of the invention the sponge particles are mixed with a binding agent, in fact a binding agent is not necessary if suffi ciently high compaction pressures are used. These preferably should be in the range of 6,000 to 60,000 psi, 01' any pressure sufficient to cause a mechanical bond between the sponge particles. The smaller the particle size, the higher will be the minimum compaction pressure required to obtain a mechanical bond. Preferred particle sizes range from less than inch down to about mesh. Also, the higher the bonding pressures used, the higher will be the spontaneous ignition temperature of the pellet. A spontaneous ignition temperature of at least 300F is preferred for safety, and a maximum spontaneous ignition temperature not exceeding about 850F is preferred for most applications for ease of ignition, depending on the ignition means used. In fact, in the test results tabulated above, the compacts or pellets used as the test samples did not include any binder material.
Having described a preferred embodiment of my invention and several operable alternative embodiments and methods of manufacture, it should be apparent to those skilled in the art that the composition, pellet size, particle size, pressures, and methods of manufacture are capable of modification. I claim as my invention all such modifications as come within the true spirit and scope of the following claims.
1. A fire starter comprising particles of metallic sponge material from the group consisting of zirconium, titanium and hafnium bonded together into a compact mass in combination with ignition means associated with said mass for igniting said sponge material.
2. A device according to claim 1 wherein said mass is impregnated with a substance comprising said ignition means.
3. A device according to claim 1 wherein said ignition means comprises combustible envelope means surrounding said mass.
4. A device according to claim 1 wherein said ignition means comprises a combustible substance impregnated in said mass and a combustible envelope means surrounding said mass.
5. A device according toclaim 2 wherein said substance comprises a combustible wax.
6. A device according to claim 2 wherein said substance comprises a combustible resin.
7. A device according to claim 3 wherein said envelope means comprises a waxed paper wrapper.
8. A device according to claim 1 wherein said ignition means includes a binder interspersed with said particles'and at least aiding the bonding of said particles into said mass.
9. A device according to claim 8 wherein said binder means has a lower spontaneous ignition temperature than said massed particles and comprises at least a portion of said ignition means.
10. A device according to claim 8 wherein said binder comprises a wax.
11. A device according to claim 8 wherein said binder comprises a resin.
12. A device according to claim 1 wherein said igni tion means comprises a fuse means in contact with said mass.
13. A device according to claim 1 wherein said ignition means comprises a detonator means in close proximity to said mass.
14. A device according to claim 1 wherein said particles are compacted together into said mass under pressure.
15. A device according to claim 14 wherein said pressure of compaction is at least about 6000 pounds per square inch.
16. A device according to claim 1 wherein said particles are in the size range of 0.0070 to 0.750 inches.
17. A device according to claim 1 wherein said mass has a spontaneous ignition temperature of at least 300F.
18. A device according to claim 1 wherein said parti cles comprise zirconium sponge.
19. A device according to claim 1 wherein said particles comprise hafnium sponge.
20. A device according to claim 1 wherein said parti cles comprise titanium sponge.
21. A device according to claim 1 wherein said particles are coated with a wax and bonded together under pressure into cake or pellet form and enveloped in a readily combustible wax-coated wrapping.
22. A device according to claim 1 wherein said particles are coated with a combustible binder material and compressed into a compacted mass so as to have a spontaneous ignition temperature of at least 300F, and a post-ignition burning temperature in the range of 1,000F to 1,700F.
23. A device according to claim 1 wherein said particles are coated with a combustible binder material and compressed into a compacted mass so as to have a spontaneous ignition temperature in the range of 300F to 850F, a post-ignition temperature in the range of 1,000F to l,700F and a burning time in the range of 20 minutes to minutes.
24. A fire starter comprising grain-sized particles of metallic sponge material from the group consisting of Zirconium, titanium and hafnium bonded together into a dense mass under sufficient pressure to effect a mechanical bond between said particles, said particles being in the size range of 0.0070 to 0.750 inches.
25. The method of starting a fire comprising compacting particles of metallic sponge selected from the group zirconium, titanium and hafnium under sufficient pressure to bond mechanically said particles into a dense mass, igniting the particles of said mass to cause them to burn for an extended period of time by applying sufficient external detonating pressure to said compacted mass to raise the temperature thereof to its spontaneous combustion temperature, and applying said ignited particles of said metallic sponge to a material to be burned.
UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3, 927, 993 DATED December 23, 1975 INVENTOR(S) Ronald W. Griffin It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column 1, line 59, change "Yet" to --yet-; column 1, line 60, change "off" to -of; column 2, line 31, change "mehtod" to -method-; Column 2, line 52, after "in" and before "consumable", insert a-; Column 3, line 68, change "tmeperature" to -temperature-; Column 5, Table 3, Example 2, change "178 in." to l/2 in.-; Column 7, line 8, change "by" to be-; Column 8, lines 31-32, change "approximately" to approximating.
Signed and Sealed this twentieth D y f April 1976 [SEAL] Arrest.
RUTH C. M A SON C. MARSHALL DANN Arresting Ojjwer (mnmissimwr nflarenls and Trademark:
UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 1 3,927,993
DATED 2 December 23, 1975 |NV ENTOR(S) Ronald W. Griffin It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown beiow:
Column 1, line 59, change "Yet" to -yet; column 1, line 60, change "off" to -of--; column 2, line 31, change "mehtod" to method-; Column 2,. line 52, after "in" and before "consumable", insert -a-; Column 3, line 68, change "tmeperature" to temperature; Column 5, Table 3, Example 2, change "178 in." to -l/2 in.--; Column 7, line 8, change "by" to -be-; Column 8, lines 3l-32, change "approximately" to -approximating.
Signed and Sealed this twentieth I 3) Of April 1976 [SEAL] Arrest:
RUTH. C. M X SON C. MARSHALL DANN Atlestmg ()jjwer Commissioner nj'latc'nts and Trademarks
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|U.S. Classification||431/6, 419/2, 423/288, 428/547, 44/628, 431/267, 264/3.3, 44/641, 264/3.1, 428/566|