U.S. patent number 3,622,408 [Application Number 04/683,127] was granted by the patent office on 1971-11-23 for water-bearing explosives thickened with a partially hydrolyzed acrylamide polymer.
This patent grant is currently assigned to E. I. du Pont de Nemours and Company. Invention is credited to William M. Lyerly.
United States Patent |
3,622,408 |
Lyerly |
* November 23, 1971 |
WATER-BEARING EXPLOSIVES THICKENED WITH A PARTIALLY HYDROLYZED
ACRYLAMIDE POLYMER
Abstract
Water-bearing explosives thickened with polyacrylamide
containing at least 10 percent by weight of carboxylate (-COO-)
moieties and having a molecular weight of about from 3 to 15
million.
Inventors: |
Lyerly; William M. (Hagerstown,
MD) |
Assignee: |
E. I. du Pont de Nemours and
Company (Wilmington, DE)
|
[*] Notice: |
The portion of the term of this patent
subsequent to November 28, 1984 has been disclaimed. |
Family
ID: |
24742681 |
Appl.
No.: |
04/683,127 |
Filed: |
November 15, 1967 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
573206 |
Aug 18, 1966 |
3355336 |
|
|
|
Current U.S.
Class: |
149/108.8;
149/39; 149/44; 149/38; 149/43; 149/60 |
Current CPC
Class: |
C06B
47/14 (20130101) |
Current International
Class: |
C06B
47/00 (20060101); C06B 47/14 (20060101); C06b
001/00 () |
Field of
Search: |
;149/38,39,43,44,60,109 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Quarforth; Carl D.
Assistant Examiner: Lechert, Jr.; Stephen J.
Parent Case Text
CROSS REFERENCE TO PRIOR APPLICATION
This is a divisional application of applicant's copending
application Ser. No. 573,206, filed Aug. 18, 1966, Pat. No.
3,355,336.
Claims
I claim:
1. In thickened water-bearing explosives comprising inorganic
oxidizing salt, fuel and water, the improvement which comprises
said explosives thickened with polyacrylamide containing at least
about 10 percent by weight of carboxylate moieties and having a
molecular weight of about from 3 to 15 million determined from the
relation
V = 3.73 .times. 10.sup..sup.-4 (m.w.) .sup. 0.66, wherein V is
intrinsic viscosity in dl/grams and m.w. is molecular weight, said
explosive additionally containing guar gum cross-linked with the
combination of a soluble antimony compound and alkali metal
dichromate, said carboxylate moieties are alkali metal base salts.
Description
This invention relates to improvements in water-bearing explosive
compositions and more particularly, to improvements in
water-bearing explosive compositions thickened with
galactomannan.
Considerable commercial interest has developed in the use of
water-bearing explosives in recent years. Generally, water-bearing
explosive compositions comprise an aqueous solution or slurry of
inorganic oxidizing salts mixed with organic or metallic fuels and
sensitizing agents which can also act as fuels.
While these water-bearing explosive compositions have many inherent
advantages such as a wide range of explosive properties, and better
safety characteristics and economy, both in manufacture and use,
there are likewise many difficulties encountered in their use.
Among the major problems encountered in the use of
water-bearing-explosive compositions are dilution of the explosive
composition by water which may be present in the borehole and the
leaching out of the dissolved and undissolved, but water-soluble,
oxidizing salts thus leading to changes in composition which result
in losses in explosive power or even in failures to detonate. In
addition, even in dry boreholes segregation of components can take
place under certain conditions so that solid components separate
into layers above or below the aqueous salt solutions to the extent
that gross inhomogeneity occurs, again leading to loss of strength
and failure to propagate. Many attempts have been made in the art
to overcome the aforementioned difficulties.
Galactomannans, particularly guar gum, have found wide utility as
thickening or gelling agents in improving the water-resistance of
water-bearing explosives. However, if the galactomannans are not
highly cross-linked, such products gradually segregate and do not
meet the stringent water-resistance requirements of current
commercial explosives. On the other hand, guar compositions
sufficiently cross-linked for good water-resistance yield
relatively immobile gelled masses which, in some cases, are
disadvantageous and difficult to handle and load into boreholes.
For example, stiff, nonpourable gels tend to spread and plug
boreholes partially filled with water when they strike the surface
of the water. Also, such compositions are somewhat more
inconvenient to remove from contains than more pourable products
and do not spread to fill the available space in the borehole
leaving voids which could present propagation of detonation. The
foregoing problems become progressively greater as the diameter of
the borehole is reduced.
Substantially linear, water-soluble or water-dispersible vinyl
polymers also have been proposed to gel or thicken water-bearing
explosives. However, unless these polymers are cross-linked, as in
U.S. Pat. No. 3,097,120, or are present in high concentration, they
give very little body to the explosives. Furthermore, such polymers
are relatively expensive.
This invention provides thickened water-bearing explosives which do
not segregate and are water resistant over a wide range of
viscosities. Preferred compositions of this invention have a unique
combination of pourability and fluidity coupled with resistance to
water and segregation which makes them particularly suitable in
small diameter holes and in holes partially filled with water.
Accordingly, this invention provides water-bearing explosive
compositions comprising inorganic oxidizing salt, fuel and water,
which improvement comprises thickening said compositions with the
combination of polyacrylamide and cross-linked galactomannan, the
weight ratio of said polyacrylamide to galactomannan being from
about 0.1:1 to 10:1, and preferably 1:1 to 5:1. "Thickened" as used
herein refers to compositions in which the viscosity of the aqueous
phase has been increased, e.g., to 10,000 centipoises or more, as
well as to gelled products, including those gels which are
cross-linked.
The polyacrylamide used is a preformed polymer which has a
molecular weight of 1 to 25, and especially 3 to 15 million.
Molecular weight can be determined from the relation:
V=3.73.times.10.sup..sup.-4 (m.w.).sup.0.66
wherein V is the intrinsic viscosity of the polymer in dl/grams and
m.w. is its molecular weight. Intrinsic viscosity can be determined
in the conventional manner from inherent viscosity measured in
dilute solutions in water at 30.degree. C. with an Ostwald Fenske
Viscometer. Preferred polymers have a pH as a 1 percent by weight
solution in water at 30.degree. C. of about from 6 to 8, and
preferably 6.5 to 7.5. Preferably, the polymer contains at least 10
percent by weight of carboxylate (-COO-) moieties neutralized with
alkali, alkaline earth metal or ammonium bases.
Galactomannans which can be used in this invention include, e.g.,
guar gum and locust bean gum, and also other galactomannan gums
which include those from endosperm seeds of leguminous plants such
as the sennas, brazilwood, tara, honey locust, paloverde,
rattlebox, alfalfa gum, clover gum and fenugreek gum. Of these,
guar gum is particularly preferred because of its ready
availability, stability and general compatibility with aqueous
solutions of inorganic oxidizing agents.
The galactomannans are cross-linked in the aqueous solution of the
inorganic oxidizing salt to form stable gelled products at
relatively low concentrations of preformed polyacrylamide and
galactomannan and to impart greater strength, cohesiveness and
water-resistance to the resulting compositions. Any of the known
cross-linking agents conventionally employed for galactomannans can
be used including potassium and sodium dichromate; sodium
tetraborate as described in U.S. Pat. No. 3,072,509; soluble
antimony and bismuth compounds at a pH of from about 6 to 13 as in
U.S. Pat. No. 3,202,551; and transition metal compounds as in Ser.
No. 343,140, filed Feb. 6, 1964, the teachings of each of which is
included herein by reference. Systems, especially those comprising
soluble antimony and bismuth compounds plus oxidizing agents are
preferred for forming water-resistant, pourable compositions. The
terms "soluble antimony and bismuth compounts" as used herein refer
to antimony or bismuth in ionic form, preferably as Sb.sup..sup.+3,
Bi.sup..sup.+3, SbO.sup..sup.+1 or BiO.sup..sup.+1 or a combination
thereof, in the gelation system, for example, in aqueous or aqueous
nitrate containing solutions of galactomannan gum during the
gelatin reaction. In general, the foregoing is fulfilled by
antimony or bismuth compounds soluble to the extent of at least
about 1 part per million in the gelatin system. Examples of
antimony or bismuth compounds which can be used in the process of
this invention include oxides and organic and inorganic salts of
bismuth and antimony such as antimony oxide, antimony chloride and
antimony oxychloride, antimony sulfate, antimonyl sulfate, antimony
tartrate, potassium antimonyl tartrate, sodium pyroantimonate,
antimony fluoride, antimony citrate, bismuth oxide, bismuth
chloride, bismuth citrate, sodium bismuthate, bismuth nitrate and
mixtures thereof. Alkali metal antimony salts of hydroxylate
polybasic acids, particularly potassium antimony tartrate, are
preferred. Oxidizing agents used in combination with the above
include hydrogen peroxide, alkali and alkaline earth peroxides, and
alkali, alkaline earth and ammonium permanganates, chromates and
dichromates. However, alkali metal dichromates, e.g., sodium and
potassium dichromates are especially preferred.
In the process of this invention the particularly preferred
cross-linking agent is potassium antimony tartrate and the
particularly preferred oxidizing agent is alkali metal, especially
sodium or potassium dichromate. The concentration of antimony or
bismuth cross-linking agent based on the amount of galactomannan is
about from 1 to 15 percent, preferably 2 to 10 percent by weight of
potassium antimony tartrate or an equivalent and about from 0.2 to
5 percent, preferably 0.5 to 3 percent by weight of potassium
dichromate.
The rate of gelation and final viscosity of the gelled compositions
of this invention is related to the kind and concentration of the
galactomannan, the molecular weight and concentration of the
preformed polyacrylamide, and the kind and concentration of the
cross-linking agent. Thus, it will be apparent that the variables
are interrelated and conveniently are adjustable to provide a gel
having the desired properties during manufacture, storage, shipping
and use. As indicated earlier, a particularly preferred composition
of this invention is a pourable, water-resistant, water-bearing
explosive composition containing a ratio of polyacrylamide to guar
gum of about from 1/1 to 5/1, most preferably 2/1 to 3/1, the total
amount of guar gum and polyacrylamide employed being less than
about 2 percent, and preferably less than 1 percent, by weight of
the total explosive composition. The cross-linking agent, used in
the quantities set forth above, will react with the guar gum to
form a gel in the aqueous phase of the blasting composition, the
polyacrylamide functioning primarily as a thickening agent.
Thicker, i.e., more viscous, less pourable compositions can be
obtained by employing a larger weight percentage of galactomannan
(guar) and/or polyacrylamide, by employing a higher ratio of
cross-linking agent to galactomannan, by using polyacrylamide of
higher molecular weight, and/or by providing a cross-linking system
which will provide a more highly cross-linked, stable structure
with the galactomannan.
In its broad aspects the improvement of this invention can be
applied to any of the known general types of water-bearing
explosives fluid at room temperature having a continuous phase
comprising water. The compositions of this invention usually
contain at least about 20 percent by weight of an inorganic
oxidizing salt. Such salts include ammonium, alkali metal and
alkaline earth metal nitrates and perchlorates as well as mixtures
of two or more of such salts. Examples of such salts are ammonium
nitrate, ammonium perchlorate, sodium nitrate, sodium perchlorate,
potassium nitrate, potassium perchlorate, magnesium nitrate,
magnesium perchlorate and calcium nitrate. Preferably, the
inorganic oxidizing salt component contains at least 45 percent of
at least one salt which is highly soluble in water at room
temperature, that is, at least as soluble as ammonium nitrate, and
preferably, the aqueous phase in the composition contains a
substantial portion of ozidizing salt, for example, 40 to 70
percent by weight thereof. Inorganic oxidizing salt mixtures
containing at least about 50 percent by weight of ammonium nitrate
and at least about 50 percent by weight of sodium nitrate are
particularly preferred.
The fuels employed in the compositions of this invention can be,
for example, self explosive fuels, nonexplosive carbonaceous and
metallic fuels, or mixtures of the aforementioned types of fuels.
The fuel or fuels used in the compositions of this invention can be
varied widely, provided that in the composition in which any
particular fuel is used, the fuel is stable, that is, prior to
detonation, during preparation and storage, the fuel is chemically
inert with the system. "Self-explosive" fuel as used herein refers
to a substance which by itself is generally recognized in the art
as an explosive. Examples of selfexplosive fuels include organic
nitrates, nitro compounds, and nitramines such as TNT,
pentaerythritol tetranitrate (PETN), cyclotrimethylenetrinitramine
(RDX), cyclotetramethylenetetranitramine (HMX), tetryl,
nitrostarch, explosive-grade nitrocellulose and smokeless powder,
as well as mixtures of the aforementioned self-explosive fuels such
as, for example, pentolite (PETN/TNT), Composition B (RDX/TNT) and
tetratol (tetryl/TNT). The self-explosive fuel can be, for example,
in any of the conventional flake, pelleted or crystalline forms.
The amount of fuel varies with the particular fuel employed. In
general, up to 40 and, preferably, 10 to 40 percent by weight based
on the weight of composition of self-explosive fuel is used.
Examples of carbonaceous nonexplosive fuels include finely divided
coal and other forms of finely divided carbon; solid carbonaceous
vegetable product such as cornstarch, woodpulp, sugar, ivory nut
meal and bagasse; organic liquids such as hydrocarbon oils, fatty
oils and vegetable oils; urea; and mixtures of two or more of the
aforementioned carbonaceous fuels are employed.
Metallic fuels include, for example, alumina and iron, and alloys
of such metals such as aluminum-magnesium alloys, ferrosilicon,
ferrophosphorous, as well as mixtures of the aforementioned metals
and alloys. Although, as disclosed in U.S. Pat. No. 2,836,484, up
to about 50 percent by weight of metallic fuel can be employed in
water-bearing compositions, usually on the order of 1 to 20, and
preferably 1 to 8 percent by weight of metals such as aluminum, and
on the order of about 10 to 30 percent by weight of heavier
metallic fuels such as ferrophosphorus and ferrosilicon are
employed.
Preferably, the total amount of fuel is adjusted so that the total
composition has an oxygen balance of from about -30 to +10 percent
and, excepting for those compositions containing the aforementioned
heavier metallic fuels such as ferrophosphorus and ferrosilicon,
preferably the oxygen balance is between about -15 to 0
percent.
To further enhance fluidity of the compositions of this invention,
particularly at low temperatures, they can contain 0.25 to 10
percent, and preferably 1 to 5 percent, based on the total weight
of composition of fluidizing agent as described in U.S. Pat. No.
3,190,777, which is incorporated herein by reference. Preferred
fluidizing agents include dimethyl sulfoxide, methanol, formamide
and methyl cellosolve.
As previously indicated, the composition of this invention contain
at least about 5 percent by weight of water. The water-bearing
compositions to which this invention is directed generally contain
less than about 45 percent by weight of water and, preferably on
the order of about 10 to 30 percent by weight of water based on the
total composition.
In general, the explosive compositions of this invention can be
prepared by the conventional formulating techniques used for
preparing galactomannan or cross-linked galactomannan aqueous
explosives. Preferably, however, the galactomannan, mixed with
soda, preformed polyacrylamide and fuels is added to a hot
(100.degree.-200.degree. F.) concentrated solution containing the
major proportion of oxidizing salt, then the cross-linking agents
are added, the solution is mixed and the product packed. It has
been found particularly advantageous for improved uniform
dispersion to add approximately one-third of the ammonium nitrate
liquor first, then to add the remaining ingredients, and finally,
after about 30 seconds, add the balance of the ammonium nitrate
liquor.
This invention provides a means for making water-bearing explosive
compositions having excellent water-resistance in products varying
in characteristics from pourable fluids to moldable, tough plastic
masses. The compositions of this invention have excellent
cohesiveness over a wide range of viscosities. Furthermore, the
improvement of this invention alters the crystal growth of
inorganic salts, reduces crystal size, and improves sensitivity.
When measured at 25.degree. C. in the aqueous phase without solids,
the preferred fluid compositions have a viscosity of about from
100,000 to about 400,000 centipoises, preferably 150,000 to 300,000
centipoises, as measured on a Brookfield Synchrolectric viscometer,
Model RVT with a helipath attachment using a TC spindle at 1 r.p.m.
These fluid compositions are particularly outstanding in their ease
of packing and loading and the facility with which they fill
boreholes yet resist segregation, leaching and dilution in the
presence of water. Such fluid products are also eminently suited
for rapid loading in small diameter holes giving ease in borehole
loading which has heretofore only been obtainable with products
blended in situ at the blasting site, e.g., in slurry trucks, but
economically infeasible for use in smaller blasting operations.
As previously indicated, the explosive compositions of this
invention can vary from pourable fluids to moldable, tough plastic
masses, all having excellent water-resistance and excellent
cohesiveness. Particularly preferred compositions of this invention
are pourable explosive compositions having a viscosity of 150,000
to 300,000 centipoises, and containing, by weight, 20 to 60 percent
ammonium nitrate alone or in combination with 10 to 40 percent
sodium nitrate; 15 to 40 percent fuel, preferably TNT; 10 to 30
percent water; 0.1 to 0.5 percent guar gum; 0.2 to 1.0 percent
preformed polyacrylamide; and, based on the weight of
galactomannan, about from 0.5 to 3 percent of oxidizing agent,
preferably an alkali metal dichromate such as sodium or potassium
dichromate and 2 to 10 percent of an antimony compound soluble in
the system, preferably potassium antimony tartrate.
The compositions of this invention possess greater fluidity,
homogeneity, resistance to disintegration or leaching by water and
stability, i.e., resistance to degradation and settling out of
components, than compositions which contain only substantially
linear, water-soluble or water-dispersible vinyl polymers or those
which contain only cross-linked galactomannans. This greater
fluidity, homogeneity, stability and water-resistance is
particularly advantageous when the compositions are to be used in
wet locations, since disintegration and leaching of a composition
by water, if such occurs, can lead to failures to detonate or to
propagate a detonation throughout the length of an explosive
column. If the explosive structure degrades, i.e., by virtue of
disintegration of the gel structure, subsequent segregation of
components, particularly undissolved (solid) fuels and sensitizers,
can occur under the force of gravity, and the components in a
borehole, whether in a container or cartridge, shucked therefrom,
or simply poured into a borehole will become so heterogeneous that
complete failure of detonation or propagation of detonation through
the entire length of the column of the explosive charge will occur.
Further, the compositions can be packaged in contains compatible
with the ammonium nitrate liquor employed, e.g., of polymeric
materials, and stored until time of use without deterioration or
separation of components. Even when freed from the container these
compositions retain an optimum degree of resistance to
disintegration and leaching by water which may be already present
in the borehole or which may enter the borehole after the
compositions are loaded. With the compositions of this invention,
bottom of the hole loading is not required. Likewise, the material
will not block a borehole as a conventional water gel very often
does. The higher loading per foot of borehole and speed of loading
compared to either cartridged products or normal water gels are
significant advantages which are manifest in the compositions of
this invention.
In the following examples which illustrate this invention parts,
percentages and ratios are by weight unless otherwise
indicated.
EXAMPLES 1 TO 5
Water-bearing explosive compositions of this invention are prepared
from the materials noted in table I. The formulations are prepared
in a rotary mixer in the following sequence of steps:
1. One-third of 65 percent ammonium nitrate solution at
150.degree.-170.degree. F., is placed in the mixer, and to the
ammonium nitrate solution, with continuous agitation, is added 6 to
8 mesh pelleted TNT or smokeless powder, hydrocarbon oil ("Corvus"
oil), metal fuels and/or sulfur as indicated in the Table.
2. A premixed composition of sodium nitrate, polyacrylamide and
galactomannan is added and the contents of the resulting mixture
are agitated for 15 seconds.
3. The balance of the ammonium nitrate liquor and formamide, where
used, are added and the contents of the mixture are agitated for
3-1/2 minutes.
4. The oxidizing agent is added and incorporated in the blend by
agitating for 15 seconds.
5. Cross-linking agent is added and the blend is mixed 30 seconds
more.
6. Contents of mixer are discharged into polyethylene bags.
##SPC1##
In examples 1 to 4, the finished compositions are pourable,
water-resistant gels having a density of from about 1.45 to about
1.65 g/cc. and a pH of about 7 to 9. The viscosity of the
compositions is from about 100,000 to 400,000 cps. The composition
in example 5 is a stiff water-gel suitable for use in mudcapping
operations. All the compositions in table I are uniform in
appearance and composition, and undissolved components remain
uniformly dispersed. Even when the compositions are dropped
approximately 40 or more feet into water, no evidence of breakdown
of the gel structure is noted. No evidence of incompatability with
water-filled boreholes is found. Deliberate attempts to plug a
borehole with compositions of examples 1 to 4 are not successful.
The formulations in examples 1 to 4 will flow through a
1-inch-diameter funnel at 70.degree. F., and have sufficient
water-resistance whereby bottom of the hole loading is not
required. The compositions are not capsensitive but can be
detonated by a conventional 25 g RDX primer and detonate with a
velocity of about 4100 meters/second in a 2-inch-diameter
column.
In the foregoing examples, similar results are obtained when a
bismuth compound or a transition metal compound, especially TYZOR
LA*, is employed in place of the potassium antimony tartrate as the
cross-linking agent for the galactomannan.
*Titanium-antimonium lactate E. I. ##SPC2##
available from E. I. du Pont de Nemours & Company
EXAMPLES 6-10
In order to evaluate the stability of the gelled water-bearing
explosive compositions of this invention and to compare them with
compositions containing only polyacrylamide or only guar gum, a
sample of each composition, described in table II, and prepared by
the general procedure of examples 1 to 5 is placed in a tightly
closed glass container in a chamber maintained at 20.degree. F. The
composition in example 7 which contains only guar gum becomes hard
at this temperature, is not pourable, and separation of the
ingredients occurs in a matter of hours. All the other compositions
are pourable, water-resistant compositions at this temperature.
About four weeks later, the compositions in examples 6, 8, 9, and
10, which are still pourable, coherent, water-resistant gels, are
transferred to a chamber maintained at 100.degree. F. This is
representative of a moderately high temperature which might be
experienced in a field storage magazine or a service truck. The
compositions stored at 100.degree. F. are inspected at intervals
for evidence of deterioration such as obvious softening and
clumping of gel structure, visible segregation of liquid
(syneresis) or insoluble high density material such as TNT, foaming
and development of tackiness and stickiness in compositions which
were originally pourable, water-resistant gels. As illustrated in
table II, the composition in example 6 which contains only
polyacrylamide has started to deteriorate whereas compositions of
the instant invention containing a combination of polyacrylamide
and guar gum do not break down of noticeably deteriorate in 12
weeks or more of storage at 20.degree. F. or 100.degree. C.
##SPC3##
* * * * *