US2759807A - Gelatinous explosive compositions - Google Patents

Gelatinous explosive compositions Download PDF

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US2759807A
US2759807A US388215A US38821553A US2759807A US 2759807 A US2759807 A US 2759807A US 388215 A US388215 A US 388215A US 38821553 A US38821553 A US 38821553A US 2759807 A US2759807 A US 2759807A
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explosive
liquid
gel
nitrocellulose
gelatinous
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Delore L Kouba
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Hercules Powder Co
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    • CCHEMISTRY; METALLURGY
    • C06EXPLOSIVES; MATCHES
    • C06BEXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00Compositions containing a nitrated organic compound
    • C06B25/28Compositions containing a nitrated organic compound the compound being nitrocellulose present as less than 10% by weight of the total composition
    • C06B25/30Compositions containing a nitrated organic compound the compound being nitrocellulose present as less than 10% by weight of the total composition with nitroglycerine
    • CCHEMISTRY; METALLURGY
    • C06EXPLOSIVES; MATCHES
    • C06BEXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/001Fillers, gelling and thickening agents (e.g. fibres), absorbents for nitroglycerine
    • CCHEMISTRY; METALLURGY
    • C06EXPLOSIVES; MATCHES
    • C06BEXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B31/00Compositions containing an inorganic nitrogen-oxygen salt
    • C06B31/28Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate
    • C06B31/32Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate with a nitrated organic compound
    • C06B31/44Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate with a nitrated organic compound the compound being nitroglycerine
    • C06B31/48Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate with a nitrated organic compound the compound being nitroglycerine with other explosive or thermic component
    • C06B31/50Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate with a nitrated organic compound the compound being nitroglycerine with other explosive or thermic component the other component being a nitrated organic compound

Definitions

  • This invention relates to explosive compositions and more particularly to gelatinous explosive compositions for various blasting purposes.
  • gelatinous explosives are prepared for almost every purpose and vary in strength from blasting gelatin to semigelatinous dynamites, some types of which are relatively insensitive. Most of the gelatinous explosive compositions owe their gelatinous properties to the presence of a nitrocelluloseexplosive oil gel in the composition. Explosive oil is the term employed by the explosives art to characterize the liquid components of an explosive, that is, liquid explosive nitric ester or esters with or without desensitizers and/or plasticizers.
  • Blasting gelatin is almost a homogeneous gel containing an explosive oil comprising explosive liquid nitric ester, usually nitroglycerin or low freezing mixture of nitric esters, and up to about nitrocellulose.
  • an explosive oil comprising explosive liquid nitric ester, usually nitroglycerin or low freezing mixture of nitric esters, and up to about nitrocellulose.
  • the entire explosives industry has shifted almost entirely from employing straight nitroglycerin in gelatin and semigelatinous dynamites to the use of mixtures of nitroglycerin with ethylene glycol dinitrate, with or without desensitizer, as the explosive oil.
  • a gelatinous dynamite is essentially a straight dynamite in which an initially prepared gel of explosive oil and nitrocellulose is employed in place of liquid nitroglycerin.
  • Probably the most popular gelatinous dynamite at this time is the semigelatinous type where part of the nitroglycerin is replaced by ammonium nitrate.
  • These compositions may be relatively insensitive as compared to other commercially available explosive compositions,. especially when desensitizing ingredients are added.
  • the more insensitive compositions are generally diflicultly detonatable or incapable of detonation with conventional commercial blasting caps, such as the #6 cap.
  • the semigelatinous dynamites are popular since they can replace the extra gelatin dynamites, yet are materially lower in price.
  • Whiskers an indication of the degree of cohesiveness of the composition, are short, fine strings stretching between the particles of the composition when it is extended.
  • the water resistance of this type of explosive varies with the consistency of the composition.
  • the uni- I ice formity and consistency of the composition are important factors from the standpoint of packaging, particularly where either squeezing or vibration packing is employed.
  • gelatinous explosive compositions containing liquid explosive nitric ester-nitrocellulose gels which are characterized by greatly improved consistency.
  • the improvement is particularly outstanding in the popular semigelatinous dynamites and it has been found that semigelatinous dynamites can be prepared which have greatly improved water resistance, whiskers, and plasticity and which contain very few of the highly undesirable gel lumps of the prior art compositions.
  • the gelatinous compositions of the invention are characterized by enhanced packagability, especially in the case of the semigelatinous dynamites.
  • the present invention is a gelatinous explosive composition
  • a gelatinous explosive composition comprising explosive oil containing liquid explosive nitric ester, an amount of a hydrogenated terphenyl not substantially in excess of the amount miscible with the explosive oil and an amount of nitrocellulose sufiicient to form a gel with the solution of explosive oil and hydrogenated terphenyl. Since the outstanding function of the hydrogenated terphenyl in the explosive compositions of the invention is to improve. the consistency and uniformity of the explosive o'il1- nitrocellulose gel, the hydrogenated terphenyl may be employed in any type of gelatinous explosive composition inwhich such gels are present.
  • the hydrogenated terphenyl may be employed in blasting gelatins to facilitate the formation of the gel and improve its consistency and may be employed in straight and extra gelatin dynamites for the same purpose.
  • the hydrogenated terphenyl finds its greatest utility in semigelatinous dynamites where the presence of uniform gels of the desired consistency is the most critical.
  • the conventional dope ingredients of straight and semigelatinous dynamites may be employed in the conventional manner known to the prior art.
  • Such in gredients may include, without limitation, oxidizing salts such as ammonium nitrate, sodium nitrate, potassium nitrate, sodium chlorate, and sodium perchlorate; various carbonaceous ingredients such as meals, pulps, and starch; and antacids such as chalk. Additional fuels such as sulfur may also be included.
  • the explosive compositions in accordance with the invention are preferably prepared by initially forming a pregel of the liquid ingredients with nitrocellulose and then mixing in the dope ingredients to produce the final. composition.
  • the liquid explosive nitric ester may be nitroglycerin, tetranitrodiglycerin, ethylene 4 1 Y 1 general y: d cr b d the intention, the :lg'olgIoW: a e am l a is, e vfor h PQTQQSQ of more sneefiie illustration fcompjositiens in ordaneeiwiththeinvjen from the standpoint of desired properties and economy i oi-med from stores of nitroglycerin, with ethylene n; a'c'rdain; wt oar/enam l prao;
  • the i u pperv urvei represents an explosive ;oil containing 570%; g nitroglycerinand ethylene glycol dinitrate; While the lower curve represents mixtures containing 20% nitroglycerin and 80% ethylene glycol dinit'rate. All com- P3361 (schradel /2 min. positions above the curve are miscible. AS indicated, Fmal Mix 1min. best results are obtained with compositions either directly Oxygen balance 7 on the curve or slightly above. Hydrogenated terphenyl Type P Hand actually has only a limited solubility in pure explosive 1361191133, 1% X 8 n.
  • EXAMPLE 3 a out .2 0 of hy rogenated te been is soluble in straight nitroglycerin and about 1 56% in straight Nlgg/gggcenn/ethylene glycol dmltratb" ethylene glycol dinitrate.
  • the solubility of hydrogenated terphenyl is in- Dlggigioluene/orthomtrotoluene 7 5 J creased by addition to the explosive liquid nitric ester of ggzgg g; ;figg;f m nitrated aromatic compounds such as dinitrotoluene, Nitr llulo (Dynamite grade) H 0 375 mononitrotoluene and the like.
  • compositions in accordance with the inven- S i nitrate 11375 tion may contain from about 5% to 85% dope ingre- Pulp n 2 dicnts, depending on the particular type of explosive Starch m desired.
  • a semigelatin'ous dynamite in accordance with Chalk the invention will probably have the following general l formula: Pregel (Schrader bowl) /2 min.
  • HE-40 is prepared by hydrogenating to 40% by weight the normally solid hydrocarbon boiling above 350 C. at 760 mm. pressure which is formed in the synthesis of hiphenyl by pyrolysis of benzene at elevated temperatures.
  • the process for preparing this product is disclosed in U. S. 2,364,719 to Jenkins.
  • the semigelatinous dynamites employed to illustrate the invention have several outstanding advantages over currently employed semigelatins. Better consistencies and water resistance have been obtained with smaller amounts of nitrocellulose, thus allowing the production of a superior product at a lower cost.
  • the undesirable lumps of currently produced semigelatinous dynamites have been greatly reduced or eliminated by the presence of hydrogenated to.- phenyl in the gel. While it is not desired to be bound by any particular theory of operation, it is believed that this result is due to a controlled deceleration of attack of the explosive oil on the nitrocellulose, thus allowing thorough dispersion of the nitrocellulose through the explosive oil mixture before substantial gelation occurs.
  • gelatinous explosive compositions in accordance with the invention without departure from its scope.
  • the invention has been principally illustrated with the highly popular semigelatinous dynamite compositions, it is to be understood that these illustrative compositions are not limiting and that the invention is equally operable in any other gelatinous dynamite containing liquid explosive nitric ester-nitrocellulose gels. It is therefore intended that the scope of the invention shall be limited only by the scope of the appended claims.
  • a gelatinous explosive composition comprising a liquid explosive component containing in major proportion at least one liquid explosive nitric ester, an amount of a hydrogenated terphenyl not substantially in excess of the amount miscible with the said liquid explosive component, and an amount of nitrocellulose suificient to form a gel with the resulting solution of liquid explosive and hydrogenated terphenyl.
  • a gelatinous dynamite composition comprising a liquid explosive component containing at least one liquid explosive nitric ester in major proportion and an aromatic nitrocompound as a desensitizer for the said liquid explosive nitric ester, dope ingredients, a hydrogenated terphenyl not substantially in excess of that amount miscible with said liquid explosive component, and an amount of nitrocellulose suflicient to form a gel with the resulting solution of the said liquid explosive component and hydrogenated terphenyl.
  • a gelatinous dynamite composition comprising from about 5 to about 85% dope ingredients, a liquid explosive component containing liquid explosive nitric ester in major proportion and an aromatic nitrocompound as a desensitizer for the liquid explosive nitric ester, an amount of a hydrogenated terphenyl not substantially in excess of the amount miscible with the said liquid explosive component, and an amount of nitrocellulose sufficient to form a gel with the resulting solution of liquid explosive and hydrogenated terphenyl.
  • a gelatinous explosive composition comprising a liquid explosive component containing, based on said composition, from about 10 to about 40% liquid explosive nitric ester and from about 5 to about 30% of aromatic nitrocompound, an amount of hydrogenated terphenyl not substantially in excess of the amount miscible with the said liquid explosive component, an amount of nitrocellulose sufiicient to form a gel with the said explosive component and hydrogenated terphenyl, from about 50 to about of inorganic oxidizing salt, from about 1 to about 12% carbonaceous material, and about 1% chalk.
  • a gelatinous explosive composition comprising from about 10 to about 40% liquid explosive nitric ester, from about 0 to about 30% of aromatic nitrocompound, from about 0.1 to about 5% of hydrogenated terphenyl, from about 0.20 to 2% nitrocellulose, from about 50 to about 80% of inorganic oxidizing salt, from about 1 to about 12% carbonaceous material, and about 1% chalk.
  • composition of claim 1 wherein said liquid explosive component is a mixture of nitroglycerin with ethylene glycol dinitrate.
  • composition of claim 2 wherein said aromatic nitro compound is at least one nitrotoluene.
  • a composition of claim 8 wherein said aromatic nitro compound is a dinitrotoluene, in major proportion, and orthonitrotoluene.
  • a gelatinous explosive composition comprising a liquid explosive component containing a liquid nitric ester in major proportion, and wherein nitrocellulose is added to the said ester-containing liquid component to form a gel
  • the improvement comprising admixing at least a portion of the amount of a hydrogenated terphenyl described hereinafter with said nitric ester and then adding said nitrocellulose to the resulting admixture to form said gel, the total amount of said hydrogenated terphenyl being not substantially in excess of that miscible with said liquid explosive component, whereby a gel of substantially lump-free consistency is formed.
  • nitric ester is a mixture of nitroglycerin and ethylene glycol dinitrate.
  • nitrotoluene is dinitrotoluene, in major proportion, and orthonitrotoluene.

Description

Aug. 21, 1956 D. L. KOUBA GELATINOUS EXPLOSIVE COMPOSITIONS- Filed Oct. 25, 1955 ai z ig c 8 v/ $QXN3 V x o vf DELORE L. KQUBA INVENTOR.
AGENT.
United States Patent GELATINOUS EXPLOSIVE COMPOSITIONS Delore L. Kouba, Newport, Del., assignor to Hercules Powder Company, Wilmington, Del., a corporation of Delaware Application October 26, 1953, Serial No. 388,215
15 Claims. (Cl. 52-11) This invention relates to explosive compositions and more particularly to gelatinous explosive compositions for various blasting purposes.
Since the invention of the gelatin dynamite by Nobel, the popularity of this type of explosive composition has continually increased. At the present time, gelatinous explosives are prepared for almost every purpose and vary in strength from blasting gelatin to semigelatinous dynamites, some types of which are relatively insensitive. Most of the gelatinous explosive compositions owe their gelatinous properties to the presence of a nitrocelluloseexplosive oil gel in the composition. Explosive oil is the term employed by the explosives art to characterize the liquid components of an explosive, that is, liquid explosive nitric ester or esters with or without desensitizers and/or plasticizers. Blasting gelatin is almost a homogeneous gel containing an explosive oil comprising explosive liquid nitric ester, usually nitroglycerin or low freezing mixture of nitric esters, and up to about nitrocellulose. In recent years, however, the entire explosives industry has shifted almost entirely from employing straight nitroglycerin in gelatin and semigelatinous dynamites to the use of mixtures of nitroglycerin with ethylene glycol dinitrate, with or without desensitizer, as the explosive oil.
A gelatinous dynamite is essentially a straight dynamite in which an initially prepared gel of explosive oil and nitrocellulose is employed in place of liquid nitroglycerin. Probably the most popular gelatinous dynamite at this time is the semigelatinous type where part of the nitroglycerin is replaced by ammonium nitrate. These compositions may be relatively insensitive as compared to other commercially available explosive compositions,. especially when desensitizing ingredients are added. The more insensitive compositions are generally diflicultly detonatable or incapable of detonation with conventional commercial blasting caps, such as the #6 cap. The semigelatinous dynamites are popular since they can replace the extra gelatin dynamites, yet are materially lower in price. They find extensive use in mining, quarrying and construction industries and contain from about 10 to about 40% of liquid nitric ester; desensitizing agents such as nitrated aromatic compounds and plasticizers; inorganic oxidizing salts, such as ammonium nitrate or sodium nitrate; a small amount of carbonaceous ingredients such as wood pulp; and a small amount of an antacid such as chalk. All of the solid ingredients of such compositions are known to the art as dope ingredients. In View of the relatively large amount of dope ingredients present in semigelatinous dynamites, it is quite difiicult to obtain the desirable composition consistency in terms of plasticity, body (firmness), whiskers, and substantial absence of gel lumps. Whiskers, an indication of the degree of cohesiveness of the composition, are short, fine strings stretching between the particles of the composition when it is extended. The water resistance of this type of explosive varies with the consistency of the composition. Furthermore, the uni- I ice formity and consistency of the composition are important factors from the standpoint of packaging, particularly where either squeezing or vibration packing is employed.
In view of the demand for this relatively inexpensive semigelatinous type of explosive composition, there is a constant effort by the art to improve the performance of semigelatinous dynamites and at the same time keep its cost at the lowest possible level. One of the most expensive single items in the composition is the nitro-. cellulose, the presence of which is essential to form the gel. The consistency and general properties of some presently marketed semigelatins, while satisfactory, leave considerable to be desired. The compositions are generally quite lumpy as a result of improper dispersion of the nitrocellulose in the explosive oil prior to gelatinization. This is usually the result of too rapid an attack by the explosive oil on the nitrocellulose. The rapidity of this attack is increased still further when an increased amount of nitroaromatic modifying compounds are employed in the explosive oil. The art has attempted to overcome this difliculty by improved mixing techniques and by addition of various additive materials, but without any very substantial success.
Now, in accordance with this invention, it has been found possible to prepare gelatinous explosive compositions containing liquid explosive nitric ester-nitrocellulose gels which are characterized by greatly improved consistency. The improvement is particularly outstanding in the popular semigelatinous dynamites and it has been found that semigelatinous dynamites can be prepared which have greatly improved water resistance, whiskers, and plasticity and which contain very few of the highly undesirable gel lumps of the prior art compositions. Moreover, the gelatinous compositions of the invention are characterized by enhanced packagability, especially in the case of the semigelatinous dynamites.
Generally described, the present invention is a gelatinous explosive composition comprising explosive oil containing liquid explosive nitric ester, an amount of a hydrogenated terphenyl not substantially in excess of the amount miscible with the explosive oil and an amount of nitrocellulose sufiicient to form a gel with the solution of explosive oil and hydrogenated terphenyl. Since the outstanding function of the hydrogenated terphenyl in the explosive compositions of the invention is to improve. the consistency and uniformity of the explosive o'il1- nitrocellulose gel, the hydrogenated terphenyl may be employed in any type of gelatinous explosive composition inwhich such gels are present. Thus, if desired, the hydrogenated terphenyl may be employed in blasting gelatins to facilitate the formation of the gel and improve its consistency and may be employed in straight and extra gelatin dynamites for the same purpose. However, the hydrogenated terphenyl finds its greatest utility in semigelatinous dynamites where the presence of uniform gels of the desired consistency is the most critical.
Therefore, the conventional dope ingredients of straight and semigelatinous dynamites may be employed in the conventional manner known to the prior art. Such in gredients may include, without limitation, oxidizing salts such as ammonium nitrate, sodium nitrate, potassium nitrate, sodium chlorate, and sodium perchlorate; various carbonaceous ingredients such as meals, pulps, and starch; and antacids such as chalk. Additional fuels such as sulfur may also be included.
The explosive compositions in accordance with the invention are preferably prepared by initially forming a pregel of the liquid ingredients with nitrocellulose and then mixing in the dope ingredients to produce the final. composition. As indicated, the liquid explosive nitric ester may be nitroglycerin, tetranitrodiglycerin, ethylene 4 1 Y 1 general y: d cr b d the intention, the :lg'olgIoW: a e am l a is, e vfor h PQTQQSQ of more sneefiie illustration fcompjositiens in ordaneeiwiththeinvjen from the standpoint of desired properties and economy i oi-med from stores of nitroglycerin, with ethylene n; a'c'rdain; wt oar/enam l prao;
the preferned s'et'rli'g'elatlnons, dynamiies nitrobenzen an n1v ofly amounts to desen" m v, hafth liquid Xplosive n f {5; ya I i sv i ,r r should be chosen :to' give; 'pourable; s
en reater amounts than those miseilil system are employed; small; eajcesses ar arbonaceoirs ingredients of the: mixture.
r 7 ed explosive ii urclniti" ster mixtures. The i u pperv urvei represents an explosive ;oil containing 570%; g nitroglycerinand ethylene glycol dinitrate; While the lower curve represents mixtures containing 20% nitroglycerin and 80% ethylene glycol dinit'rate. All com- P3361 (schradel /2 min. positions above the curve are miscible. AS indicated, Fmal Mix 1min. best results are obtained with compositions either directly Oxygen balance 7 on the curve or slightly above. Hydrogenated terphenyl Type P Hand actually has only a limited solubility in pure explosive 1361191133, 1% X 8 n. r ridge 1.48 liquid nitric esters. The degree of solubility varies with Count, 1% X 8 ll 99 the particular ester or mixture of esters. As shown in Consistency Very good the drawing, hydrogenated terphenyl is soluble in nitro- Water resistance, CaPtridge, 5 at glycerin/ethylene glycol dinitrate70/ 30 to the extent P- 95% of about 0.8% and in nitroglycerin/ethylene glycol dir7lgralt:e-0/8% tg ythe exent of about 2%.l Also at Formula. EXAMPLE 3 a out .2 0 of hy rogenated te been is soluble in straight nitroglycerin and about 1 56% in straight Nlgg/gggcenn/ethylene glycol dmltratb" ethylene glycol dinitrate. As indicated by the drawing, however, the solubility of hydrogenated terphenyl is in- Dlggigioluene/orthomtrotoluene 7 5 J creased by addition to the explosive liquid nitric ester of ggzgg g; ;figg;f m nitrated aromatic compounds such as dinitrotoluene, Nitr llulo (Dynamite grade) H 0 375 mononitrotoluene and the like. 60 A i i t d 1 1 115 5g 75 Gelatinous compositions in accordance with the inven- S i nitrate 11375 tion may contain from about 5% to 85% dope ingre- Pulp n 2 dicnts, depending on the particular type of explosive Starch m desired. A semigelatin'ous dynamite in accordance with Chalk the invention will probably have the following general l formula: Pregel (Schrader bowl) /2 min.
I Percent Final MiXQ. 1min. Liquid explosive nitric ester 10-40 Oxygen balance -9=1 Aromatic nitrocompound 5-30 Type packing Vibrator Hydrogenated terphenyl 0.1-5 Density, :2 x 8 in. cartridge 1.45 Nitrocellulose 50-80 Count, 1% x8 in. cartridge 98 Inorganlc oxidizing salt 50-8O Consistency .i Very good Carbonaceous 1-l2 Water Resistance, 2 ,x 8 in. cartridge 5 hrs. at I Antacld 0.3-1 45 p. s. i
EXAMPLE 4 Pulp 1.0 Starch 3.0 l Chalk 0.5
Nltroglycerm/ ethylene glycol d1n1trate- 70/30 139% 5 Pregel (Schrader bowl) mm. Dinitrotoluene/orthonitrotoluene Fmal MIX 1 66/34 95 Oxygen balance -5.24 Hydrogenated terphenyl 2.5 Typc paCkmg-T Hand Denslty, 2 X 8 1n. cartridge 1.54 Nitrocellulose (Dynamite grade) 0.375 Consistency y g 1 T m l f filtrate 1 26 10 Water Resistance, 2 x 8 in. cartridge 5 hrs. at
3 filtrate 2 45 p. s.i 95% u p Starch l 5 In Table I are recorded data comparing the properties Chalk 05 of semigelatinous dynamites prepared in accordance with m the invention with similar dynamites' in which dibutyl p l (Schrader bowl) 1 m phthalate has been employed in placeof the hydrogenated Final Mix l min terphenyl. It Wlll be noted that 1n all cases similar oxyuen balance 8 amounts of hydrogenated terphenyl gave improved water T Z ackin Vibrator resistance and consistency as compared to dibutyl phthalyp 2 "Y u 1 40 20 ate which has previously been considered as one of the f X ge best desensitizing plasticizers for such use. 111 all cases Conslstencl Very good the formulas were prepared by 2 /2 min. pregelling of the Water Reslstance, 2 X 8 cal'trldge 5 at liquid ingredients with nitrocellulose and a final mixing p. s. i 85% period of 2 /2 min.
Table 1 Water Resistance, 2 x8 in. Cartridge, 45 p. s. i. for 2 57 Percent Powder 5 hrs. 35-60 F. Consistency (average) Example Formula Desen sl- N Density tizer (av.) Loss or Apparent Gainin Percent Wt., g Good (av.) Powder Plasticity Body Whiskers Gel (av.) Lumps 6 1. 51 Excellent ISqome Mlzgny.
, flTIP (L (See 1) {1HT 0.75 1. 51 15 E ellent Verymany None. at 3-23 its 22 5 DBP 0143 53 -7 81 .do 'Eid do .1: Many HT 1.00 1.50 -17 90 Satisfactory--. Excellent Very many. None. 11 at 8%.? iii 1; 22
"a; a HT 0:43 1150 +15 99 556d :IIdn dn Do: HT 0. 376 1. 47 --4 89 Satisfactory--. Satisfactory- Some Do.
1 DBP-dibutyl phthalate. I HT-hydrogenated terphenyl.
Formulas (Note 1) (Note 2) I II Nitroglycerin/ethylene glycol dinitrate-20 80.. 13.0 N itroglycerin/ethylene glycol dinitrate-70 30 15. 0 Dinitrotoluene/orthonitroto1uene66/34. 9. 5 8. 5 Do on itiver 2.5 1.5 Ammonium nitr 59. 0-58. 75 59.12558.50 Sodium nitr 11. 0 11. 0 Star h 2.0 1.5 Pulp 2.0 2.5 Chalk 0.5 0.5 N itrnnellnlmn 0. -0. 75 0. 375-1- 00 EXAMPLE 5 In Table II compositions containing dibutyl phthalate Formula: l are again compared with similar compositions containing Nltl'oglycerln/ethylene glycol infiltrate hydrogenated terphenyl to illustrate the superiority of 9 1 150% the powders of the invention in terms of adaptability to D mmoto uene/orthomtmtoluene 70 packing by vibration. Higher packing densities and bet- 66/34 8.5 Hydrogenated terphenyl 1 5 ter water resistance were obtamed in each case with the Nitrocellulose (Dynamite grade) Q4 composition of the invention. Pregel times of one-half A i nitrate 1 d 1 1 59 1 minute and final mixing times of one minute were em- Sodium nitrate 11.0 ployed.
Table 11 Further examples of gelatinous dynamite compositions in accordance with the invention are given in Table IV.
Water Resistance, Table IV 2 x 8 in. Cartridge, 45p.s.i.for5l1rs., Powder 35-e0 F. 5 Example 35 Example 55 Example Powder Desensi- Percent en- Formula tizer NC sity Loss or Apparent Formula: Gain in Prcelt Ng/tggQlycerin/eths lehe glycol dmitrate- 11.0 11.0. wt., g.
Powder Dinitrotoluene/orthonitrotoluene-60/34- 7.5 s- 7.5. ]0 gadrogfinzlited Terphenyl iroce uose 17 DBP 0.50 1.23 84 5 Ammonium nitrate" 6 1s I 1 DB? 0. 375 1.38 -95 75 Sodium nitrate 19 (See Note HT 0. 50 1. 35 -4 s5 Starch 20 HT 0. 375 1. 42 5o 75 Chalk 21 DBP 0.50 1. 28 144 25 Pregel (Schrader bowl) 22 H DBP 0.375 1.37 120 50 r Mix 23 s N 3 DB]? 0125 1.46 20 8O Oxygen Balance- 24 g HT 0. 50 1.38 14 80 Type Packing 25 HT 0. 375 1.44 s3 85 Dens1ty,4x in. Cartridge- 26 HT 0.125 1.50 -22 E0 Consistency Very good-.. Very good.
Water Resistance, 4 x 10 in. Cartridge-24 95% 95%.
hrs. at 45 p. s. i. I DBP-d1butyl phthalate. I FIT-hydrogenated terphenyl.
In the foregoing examples the water reslstance of the 2 various compositions as recorded was tested by loading Formulas (Nolte 1) i the compositions in similar paper cartridges of the sizes indicated. These cartridges were placed in an autoclave Nitroglycerm 30% A 150 130 for the indicated periods under a water pressure of 45 Dlnltrqtqluen'e/orth nitrot0 8.5 9- p. s. i. After removal from the autoclave, the cartridges gffi gt fgfg s DBP FK were cut lengthwise and the powder examined for the per Ammonium nitrate 5025-590 59 590 cent remaining which was not leached or wet. Each Smhum };f; f; cartridge, after opening, was drained for a few seconds,
2.5 2.5 then weighed in order to determine loss in weight. Oxygen Balance. In order to test for consistency in Examples 1-26, the DB -40 -7. 7 powders were allowed to stand several days under outdoor HT storage conditions. The powders were then allowed to come to room temperature and examined for plasticity, body whiskers, and gel lumps. 35 h d Since the undesirable gel lumps are formed in the pregel T1213 Y P Y 111 9 31166 h the period when the explosive oil and nitrocellulose are ad- Yentlon y f p i f q from Y d6 $11ed sq CEPt mixed, the improvement wrought by addition of hydroin small quantltles it IS dlfficult, lf not lrnposslble, to obtaln genated terphenyl can readily be demonstrated prior to a Smgle p hydrogenated 1somer. v y addition of the dope ingredients. In Table III, the proper- 40 genflted mlxtufes 9 the Vflrlous terphenyl ISOmeIS are ties of such gels, with and without addition of hydroflvallabl? (fmllmeffllally i $1161} a mlXtlll'e b56111 t genated terphenyl, are compared. In preparing the gels, ployed 1n illustrating the lnventlon. The 1921111613131 mix; wet nitrocellulose (2% dry basis) was added to 30 grams tlfre mp y 1S marketed under th trt {18 16 HB 40 of pure explosive liquid nitric ester, or mixtures of esters Whlch IS a Practlcally 601011655, y llquld f g a ester to hi h th i di d amount f h d d falnt and pleasant odor, and the following characterlstlcs: terphenyl had been added) in a 30-ml. beaker with stlr- Distillation rangg 340.3%?, o ring being continued for 5 minutes after addition of the Freezmg Pomt (511119180015)- nitrocellulose. After mixing, the gel was allowed to stand specific gravity um at :5 o G. at -75 F. for one hour. A flow test was then made by tipping the beaker to a horizontal position and measur- 50 Refractive index .5fii0.0075 at 25 0. H at icomb t 10,200 1. 2. mg the tlme taken by the gel to reach the 11p of the beaker. i i f ifi fl 5 Table III Percent Mixing (5 min.) Hydro- Appearance of Gel After Two Days of Example Explosive Ester genated Time, Spreading Out Terphenyl Initial Medium Stiff minutes Gel Gel Gel 27 NG No initial gelin 5min. 1 Smfoot? thilllulgel medium hard lumps 0 111 T000 050. 28 NG 0.28 No initial gelinfimin. 1 Smooth thin gel-nitrocellulose lumps finch srallg; and better consistency 8.11111 X. 29 NG/EGDN70/30.-.- 3 min- N0 medium gel in Stifi gel-quite a few large lumps.
5min. 30 NG/EGDN70/30 0.93 3min... Ng medium gel in 40 Stifitgelftegv srEl;1all2lJumpsbetter mm min. sl's ency an x. 31 NG/EGDN20/80 1 min... 2min 4min--- 90 Smooth gel-several large softlumps. 32 N G/EGDN20/80.-.. 1.47 111101... 2min... 4min--- 90 Smooth gel-several medium lumps better consistency than Ex. 31. 33 EGDN V; min 1% min- 3 min 90 Smooth ge1numerous large soft lumps. 34 EGDN 3.36 %min 1% min. 3min..- 90 Smooth gel-m0 lumps-excellent consistency.
NG-nitr0g1ycerin.
EGDN-ethylene glycol d nitrate.
Vapor pressure- Temperature, 0. mm. Hg
H ents:
Evaporation Loss at 100 C. for 6 hours... 0.0337.
HE-40 is prepared by hydrogenating to 40% by weight the normally solid hydrocarbon boiling above 350 C. at 760 mm. pressure which is formed in the synthesis of hiphenyl by pyrolysis of benzene at elevated temperatures. The process for preparing this product is disclosed in U. S. 2,364,719 to Jenkins.
As will be seen from the foregoing examples, the semigelatinous dynamites employed to illustrate the invention have several outstanding advantages over currently employed semigelatins. Better consistencies and water resistance have been obtained with smaller amounts of nitrocellulose, thus allowing the production of a superior product at a lower cost. The undesirable lumps of currently produced semigelatinous dynamites have been greatly reduced or eliminated by the presence of hydrogenated to.- phenyl in the gel. While it is not desired to be bound by any particular theory of operation, it is believed that this result is due to a controlled deceleration of attack of the explosive oil on the nitrocellulose, thus allowing thorough dispersion of the nitrocellulose through the explosive oil mixture before substantial gelation occurs. However, it will be seen that this advantage is obtained without any way slowing down the process of production since conventional pregel and final mix times have been employed. Additionally, the semigelatinous compositions containing hydrogenated terphenyl, despite their being gelatins, will readily pack on a vibrator, thus greatly facilitating the packaging of such compositions. This packing is achieved without undesirable sacrifice in density, water resistance, or sensitivity. Furthermore, straight gelatin and extra gelatin dynamites containing hydrogenated terphenyl may be prepared which are readily extrudable in a gelatin squeezer.
It is apparent that many variations may be made in gelatinous explosive compositions in accordance with the invention without departure from its scope. Although the invention has been principally illustrated with the highly popular semigelatinous dynamite compositions, it is to be understood that these illustrative compositions are not limiting and that the invention is equally operable in any other gelatinous dynamite containing liquid explosive nitric ester-nitrocellulose gels. It is therefore intended that the scope of the invention shall be limited only by the scope of the appended claims.
What I claim and desire to protect by Letters Patent 1s:
1. A gelatinous explosive composition comprising a liquid explosive component containing in major proportion at least one liquid explosive nitric ester, an amount of a hydrogenated terphenyl not substantially in excess of the amount miscible with the said liquid explosive component, and an amount of nitrocellulose suificient to form a gel with the resulting solution of liquid explosive and hydrogenated terphenyl.
2. A gelatinous dynamite composition comprising a liquid explosive component containing at least one liquid explosive nitric ester in major proportion and an aromatic nitrocompound as a desensitizer for the said liquid explosive nitric ester, dope ingredients, a hydrogenated terphenyl not substantially in excess of that amount miscible with said liquid explosive component, and an amount of nitrocellulose suflicient to form a gel with the resulting solution of the said liquid explosive component and hydrogenated terphenyl.
3. A gelatinous dynamite composition comprising from about 5 to about 85% dope ingredients, a liquid explosive component containing liquid explosive nitric ester in major proportion and an aromatic nitrocompound as a desensitizer for the liquid explosive nitric ester, an amount of a hydrogenated terphenyl not substantially in excess of the amount miscible with the said liquid explosive component, and an amount of nitrocellulose sufficient to form a gel with the resulting solution of liquid explosive and hydrogenated terphenyl.
4. A gelatinous dynamite composition in accordance with claim 3 in which the dope ingredients comprise inorganic oxidizing salt, carbonaceous ingredients, and an antacid.
5. A gelatinous explosive composition comprising a liquid explosive component containing, based on said composition, from about 10 to about 40% liquid explosive nitric ester and from about 5 to about 30% of aromatic nitrocompound, an amount of hydrogenated terphenyl not substantially in excess of the amount miscible with the said liquid explosive component, an amount of nitrocellulose sufiicient to form a gel with the said explosive component and hydrogenated terphenyl, from about 50 to about of inorganic oxidizing salt, from about 1 to about 12% carbonaceous material, and about 1% chalk.
6. A gelatinous explosive composition comprising from about 10 to about 40% liquid explosive nitric ester, from about 0 to about 30% of aromatic nitrocompound, from about 0.1 to about 5% of hydrogenated terphenyl, from about 0.20 to 2% nitrocellulose, from about 50 to about 80% of inorganic oxidizing salt, from about 1 to about 12% carbonaceous material, and about 1% chalk.
7. A composition of claim 1 wherein said liquid explosive component is a mixture of nitroglycerin with ethylene glycol dinitrate.
8. A composition of claim 2 wherein said aromatic nitro compound is at least one nitrotoluene.
9. A composition of claim 8 wherein said aromatic nitro compound is a dinitrotoluene, in major proportion, and orthonitrotoluene.
10. In the preparation of a gelatinous explosive composition comprising a liquid explosive component containing a liquid nitric ester in major proportion, and wherein nitrocellulose is added to the said ester-containing liquid component to form a gel, the improvement comprising admixing at least a portion of the amount of a hydrogenated terphenyl described hereinafter with said nitric ester and then adding said nitrocellulose to the resulting admixture to form said gel, the total amount of said hydrogenated terphenyl being not substantially in excess of that miscible with said liquid explosive component, whereby a gel of substantially lump-free consistency is formed.
11. The improvement of claim 10 wherein dope ingredients are mixed with the gel thus formed.
12. The improvement of claim 10 wherein said nitric ester is a mixture of nitroglycerin and ethylene glycol dinitrate.
13. The improvement of claim 10 wherein a liquid aromatic nitro compound is employed in said liquid explosive component as a desensitizer for the said ester.
14. The improvement of claim 13 wherein said aromatic nitro compound is at least one nitrotoluene.
15. The improvement of claim 14 wherein said nitrotoluene is dinitrotoluene, in major proportion, and orthonitrotoluene.
No references cited.

Claims (2)

1. A GELATINOUS EXPLOSIVE COMPOSITION COMPRISING A LIQUID EXPLOSIVE COMPONENT CONTAINING IN MAJOR PROPORTION AT LEAST ONE LIQUID EXPLOSIVE NITRIC ESTER, AN AMOUNT OF A HYDROGENATED TERPHENYL NOT SUBSTANTIALLY IN EXCES OF THE AMOUNT MISCIBLE WITH THE SAID LIQUID EXPLOSIVE COMPONENT, AND AN AMOUNT OF NITROCELLULOSE SUFFICIENT TO FORM A GEL WITH THE RESULTING SOLUTION OF LIQUID EXPLOSIVE AND HYDROGENATED TERPHENYL.
10. IN THE PREPARATION OF A GELATINOUS EXPLOSIVE COMPOSITION COMPRISING A LIQUID EXPLOSIVE COMPONENT CONTAINING A LIQUID NITRIC ESTER IN MAJOR PROPORTION, AND WHEREIN NITROCELLULOSE IS ADDED TO THE SAID ESTER-CONTAINING LIQUID COMPONENT TO FORM A GEL, THE IMPROVEMENT COMPRISING ADMIXING AT LEAST A PORTION OF THE AMOUNT OF A HYDROGENATED TERPHENYL DESCRIBED HEREINAFTER WITH SAID NITRIC ESTER AND THEN ADDING SAID NITROCELLULOSE TO THE RESULTING ADMIXTURE TO FORM SAID GEL, THE TOTAL AMOUNT OF SAID HYDROGENATED TERPHENYL BEING NOT SUBSTANTIALLY IN EXCESS OF THAT MISCIBLE WITH SAID LIQUID EXPLOSIVE COMPONENT, WHEREBY A GEL OF SUBSTANTIALLY LUMP-FREE CONSISTENCY IS FORMED.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3236180A (en) * 1966-02-22 Blasting charge and method
US3951706A (en) * 1962-07-03 1976-04-20 Eldridge Judson B Solid propellant mixtures and process of preparation
US6508177B1 (en) * 1999-09-13 2003-01-21 The Ensign-Bickford Company Explosives with embedded bodies

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3236180A (en) * 1966-02-22 Blasting charge and method
US3951706A (en) * 1962-07-03 1976-04-20 Eldridge Judson B Solid propellant mixtures and process of preparation
US6508177B1 (en) * 1999-09-13 2003-01-21 The Ensign-Bickford Company Explosives with embedded bodies

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