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(12) United States Patent (io) Patent No.: US 7,371,784 B2

Guillot et al. (45) Date of Patent: *May 13,2008

EPDM ROCKET MOTOR INSULATION 5,007,343 A 4/1991 Marks

5,024,818 A 6/1991 Tibbetts et al.
Inventors: David G. Guillot, Tremonton, UT 5,024,860 A 6/1991 Chang
(US); Albert R. Harvey, Brigham City, 5,209,872 A * 5/1993 Takahashi et al. .......... 252/511
UT (US) 5,209,972 A * 5/1993 Super et al. ................ 428/349
5,212,944 A 5/1993 Martin et al.
5,225,457 A 7/1993 Borowczak et al.
Assignee: Alliant Techsystems Inc., Edina, MN 5,352,312 A 10/1994 Guillot
(US) 5,352,507 A 10/1994 Bresson et al.
5,364,905 A 11/1994 Bauer et al.
Notice: Subject to any disclaimer, the term of this 5,374,415 A 12/1994 Alig et al.
patent is extended or adjusted under 35 5,409,775 A 4/1995 Harada et al.
U.S.C. 154(b) by 510 days. 5,498,649 A 3/1996 Guillot
5,547,525 A 8/1996 Bennett et al.
This patent is subject to a terminal dis- 5,569,716 A 10/1996 Okamoto et al.
claimer. 5,594,060 A 1/1997 Alig et al.
5,621,045 A 4/1997 Pate1 et al.
Appl. No.: 10/931,778 5,767,221 A 6/1998 Poulter et al.
5,821,284 A 10/1998 Graham et al.
Filed: Aug. 31, 2004 5,830,384 A 11/1998 Stephens et al.
5,989,459 A 11/1999 Nguyen et al.
6,627,702 B1 * 9/2003 Uesaka ....................... 525/139
Prior Publication Data 6,691,505 B2 2/2004 Harvey et al.
US 200610009567 A1 Jan. 12. 2006 7,070,705 B2 * 7/2006 Harvey et al. ................ 252/62

FOREIGN PATENT DOCUMENTS

Related U.S. Application Data
EP 0 446 573 A2 9/1991
Continuation of application No. 101310,005, filed on EP 0 543 663 A1 * 5/1993
Dec. 3, 2002, now Pat. No. 6,787,586, which is a JP 08127674 A 5/1996
division of application No. 091481,709, filed on Jan. wo 01/04198 A1 1/2001
12, 2000, now Pat. No. 6,566,420. wo 01/20966 A2 3/2001
Provisional application No. 601115,859, filed on Jan.
wo 01-46279 A1 6/2001
13, 1999, provisional application No. 601115,857, OTHER PUBLICATIONS
filed on Jan. 13, 1999, provisional application No.
Chang, Karl K., Aramid Fibers, ASM International Handbook, vol.
601115,856, filed on Jan. 13, 1999, provisional appli-
21, p. 41, 2003.
cation No. 601115,855, filed on Jan. 13, 1999. DuPont Dow Elastomers, Introducing Nordel IP, Setting a New
Standard in Predictability, “Delivering a New Standard of Perfor-
Int. C1. mance,” (1997), pp. 1-6.
FOZK 9/34 (2006.01) Product Description, Grades of Nordel IP Based on Insite Catalysts
COSK 3/04 (2006.01) and Process Technology (1997), p. 3.
COSK 3/36 (2006.01) DuPont Dow Elastomers, Nordel IP NDR 4640, “Nordel IP Grade
U.S. C1. ....................... 523/138; 5241492; 5241495 Comparison, ” (1997), pp. 1-7.
DuPont Dow Elastomers, Nordel IP NDR-4520, “Nordel IP Grade
Field of Classification Search ................ 5231138;
Comparison,” (1997), pp. 1-5.
5241492, 495 DuPont Dow Elastomers, “Nordel IP Product Specification Infor-
See application file for complete search history. mation,” pp. 2-3, 1997.
Sutton, G.P., “Rocket Propulsion Element,” 1992, Wiley & Sons,
References Cited
New York, US, pp. 106-109.
U.S. PATENT DOCUMENTS * cited by examiner
3,347,047 A 10/1967 Hartz et al.
3,421,970 A 1/1969 Daly et al.
Primary Examiner-Tae H Yoon
3,562,304 A 2/1971 Tucker (74) Attorney, Agent, or Firm-TraskBritt
3,637,576 A 1/1972 Sutherland
3,686,868 A 8/1972 Chase et al. (57) ABS TRAC’I
3,973,397 A 8/1976 Chase et al.
4,066,590 A 1/1978 Eldred et al. A novel and improved EPDM formulation for a solid
4,373,048 A 2/1983 Schubert et al. propellant rocket motor is described wherein hexadiene
4,492,779 A 1/1985 Junior et al. EPDM monomer components are replaced by alkylidene
4,504,532 A 3/1985 Herring norbornene components, and, with appropriate adjustment
4,514,541 A 4/1985 Frances of curing and other additives, functionally required rheo-
4,550,130 A 10/1985 Kishida et al. logical and physical characteristics are achieved with the
4,649,701 A 3/1987 Wendel desired compatibility with any one of a plurality of solid
4,663,065 A 5/1987 Herring filler materials, e.g., powder silica, carbon fibers or aramid
4,711,086 A 12/1987 Offe et al. fibers, and with appropriate adhesion and extended storage
4,878,431 A 11/1989 Herring or shelf-life characteristics.
4,953,476 A 9/1990 Sayles
4,956,397 A 9/1990 Rogowski et al. 11 Claims, 3 Drawing Sheets
U.S. Patent Sheet 1 of 3 US 7,371,784 B2

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U.S. Patent May 13,2008 Sheet 2 of 3 US 7,371,784 B2
 48
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 US 7,371,784 B2
1 2
EPDM ROCKET MOTOR INSULATION
TABLE 1-continued
CROSS-REFERENCE TO RELATED
APPLICATIONS
STW4-2868 THERMAL INSULATION FORMULATION
5
This application is a continuation of application Ser. No. (carbon fiber; parts by weight)
101310,005,filedDec. 3,2002,nowU.S. Pat.No. 6,787,586,
issued Sep. 7, 2004, which is a divisional of application Ser. Parts by
No. 091481,709 filed Jan. 12, 2000, now U.S. Pat. No. Ingredient Function Weight
6,566,420, issued May 20, 2003. 10
This application claims the benefit of priority of Provi-
Tellurac Accelerator 0.50
sional Application Nos. 601115,855, 601115,856, 601115,
859, and 601115,857, each filed on Jan. 13, 1999. SULFADS CC Accelerator 0.75
VCM carbon fibers Filler 41
GOVERNMENT LICENSING CLAUSE 15 -
Total Parts by Weight 153.25
The U.S. Government has a paid-up license in this inven-
tion and the right in limited circumstances to require the
patent owner to license others on reasonable terms as
provided for by the terms of contract NAS 8-38100 awarded 20
Alternatively, solid rocket motor insulations are also
by the National Aeronautics and Space Administration composed of compositions employing finely divided powder
(NASA) and contract N00030-97-C-0100 awarded by the silica as a filler, with or without the added presence of a
U.S. Department of the Navy. fibrous reinforcing agent.
Exemplary silica-filled rocket motor insulations have also
BACKGROUND OF THE INVENTION 25 included NORDELB 1040 and NORDELB 2522 as the
primary terpolymer in their formulations and the resulting
1. Field of the Invention
This invention relates to a novel composition and method compositions are respectively commonly known in the
for providing insulation for solid propellant rocket motors industry as the 053A and DL1375 thermal insulations. They
and, more particularly, to EPDM compositions having 30 have the following compositions shown in Table 2:
fibrous components such as carbon fibers or powder fillers
such as silica, or also containing KEVLARB reinforcing TABLE 2
fibers and suitable for internal and external insulation appli-
cations on such rocket motors. THERMAL INSULATION FORMULATION
2. State of the Art 35 (silica filled; parts by weight)
It is generally accepted current industry practice to pre-
pare insulations for solid propellant rocket motors from a DL1375 053A
polymeric base importantly composed of an EPDM (ethyl-
ene-propylene-diene monomer) terpolymer blend and con- (Parts by (Parts by
Ingredient Function weight) weight)
taining 1,4-hexadiene (HD) as one of the diene monomer 40
components of the EPDM blend.
This EPDM terpolymer, which is commonly designated NORDEL CC 1040 Primary EPDM 80

as the primary EPDM terpolymer since it is present in a terpolymer base

higher concentration than the secondary EPDM terpolymer, NORDEL CC 2522 Primary EPDM 80
has been established as a standard for solid propellant rocket 45 terpolymer base
motor insulations due to its superior ablation characteristics, NEOPRENE CC FB Secondary polymer base 20 20
excellent physical properties and processability. Zinc oxide Activator 5 5
For instance, an exemplary carbon fiber-filled rocket Sulfur Curative 1 1
motor insulation composed of NORDELB 1040 as the
AGERITE CC Resin D Antioxidant 2 2
primary terpolymer is commonly known in the industry as 50
AGERITE CC HPS Antioxidant 1 1
the STW4-2868 thermal insulation and has the following
composition as shown in Table 1: Captax Accelerator 1 1
Tellurac Accelerator 0.5 0.5
TABLE 1 SULFADS CC Accelerator 0.75 0.75
55 HISIL CC 233 Filler 35.5 35.5
STW4-2868 THERMAL INSULATION FORMULATION - -
(carbon fiber; parts bv weight)
Total Parts by Weight 146.75 146.75
Parts by
Ingredient Function Weight

NORDEL CC 1040 Primary EPDM terpolymer base 80 60 In addition, an EPDM terpolymer comprising the HD
NEOPRENE CC FB Secondary polymer base 20
Zinc oxide Activator 5 monomer is sold under the tradename NORDELB 2722E.
Sulfur Curative 1 An exemplary silica-filled rocket motor insulation compris-
HAF carbon black Pigment 1 ing NORDELB 2722E as the secondary terpolymer is
MBT Accelerator 1
AGERITE CC Resin D Antioxidant 2 65 commonly known in the industry as the DL1552A thermal
AGERITE CC HPS Antioxidant 1 insulation and has the following composition as shown in
Table 3:
 US 7,371,784 B2
3 4
TABLE 3
DL1552A THERMAL INSULATION FORMULATION WITH SILICA

Parts by
Ingredient Function Weight

BUNA IE EP T 3950 (Bayer Corp., Fiber, Additives and Primary EPDM 75

Rubber Division of Orange, Texas) terpolymer base
NORDEL IE 2722E (DuPont Dow Elastomers) Secondary EPDM 20
terpolymer base with
high ethylene content
WINGTACK IE 95 (hydrocarbon resin) (Goodyear Tire and Tackifier 7
Rubber Co., Chemical Division of Beaumont, Texas)
IRGANOX IE 1010 (tetrakis[methylene-3-(3'5'-di-te~-butyl- Antioxidant 1
4'-hydroxyphenyl) propionatelmethane) (Ciba Specialty
Chemicals, Additives Division, Tarrytown, N.Y.)
TRYCOL IE DA-6 (decyl polyoxyethylene alcohol) Wetting agent 0.5
(Chemical Associates, Inc. of Copley, Ohio)
Stearic acid (including palmitic acid) (Hamick Standard Cure activator 1
Distribution Corp. of Akron, Ohio)
HISIL IE 233 (silica hydrate) (PPG Industries, Inc. of Lake Reinforcing filler 45
Charles, Louisiana)
Aluminum oxide C iAl-0,)
~ , ,iDegussa
Y~ Cornoration of Reinforcing filler 0.3
Ridgefield Park, N. J.)
N330 carbon black (Columbian Chemicals Co. of Marietta, Pigment and 1
Ga.) reinforcing filler
KALENE IE 1300 (butyl gum elastomer) (Hardman Division Co-vulcanizing 20
of Harcros Chemicals, Inc. of Belleville N.J.) plasticizer
HYPALON IE 20 (chlorosulfonated polyethylene) (DuPont Cure activator 5
Dow Elastomers)
AGERITE IE Resin D (polymerized trimethyl Antioxidant 0.25
dihydroquinone) (R.T. Vanderbilt Co., Inc. of Buena Park,
Ca.)
TZFD-88p (zinc oxide dispersed in an EPDM binder) Cure activator 2
(Rhein Chemie Corp. of Trenton, N.J.)
SP 1056 (bromomethyl alkylated phenolic resin) Curing agent 15
(Schenectady Int'l, Inc. of Schenectady, N.Y.)

Total Parts by Weight 193.05

35

An exemplary aramid fiber-filled rocket motor insulation

comprising NORDELB 1040 is commonly known in the
industry as R196 thermal insulation and has the following
composition as shown in Table 4:

TABLE 4
R196 THERMAL INSULATION FORMULATION WITH KEVLAR IE

Parts by
Ingredient Function Weight

NORDEL IE 1040 (EPDM terpolymer) Polymer base 80

NATSYN IE 2200 (polyisoprene) (Goodyear Tire and Polymer base 20
Rubber Co., Chemical Division of Akron, Ohio)
WINSTAY IE S (syrenated phenols) (Goodyear Tire and Antioxidant 1.o
Rubber Co., Chemical Division of Akron, Ohio)
Dechlorane Plus 515 (1,2,3,4,7,8,9,10,13,13,14,14- Flame retardant 40
dodecachloro-l,4,4a,5,6,6q,7,lO,lOa,ll,12,12a-
dodecahydro-l,4,7,10-dimethanodibenzo(a,e)
cyclooctene) (Occidental Chemical Corporation of
Dallas, Texas)
Antimony oxide (Sb,O,) (Harcros Chemicals, Inc. of Flame retardadfiller 20
Kansas City, Kansas)
%" KEVLAR IE fiber (aramid staple fiber) (E.I. duPont Fiber 20
de Nemours and Co., of Wilmington, Delaware)
VAROX IE DBPH-50 (2,5-dimethyl-2,5-di(t-butylperoxy) Curing agent 2.5
hexane on a carrier) (R.T. Vanderbilt Co., Inc. of Buena
Park, Ca.)

Total Parts by Weight 183.5

 US 7,371,784 B2
5 6
Numerous past efforts to develop effective replacements In addition, any replacement EPDM or like terpolymer
for these standard solid rocket motor insulation formulations should satisfy a number of other requirements including
have not been successful. wettability of and bond strength with such diverse filler
The only manufacturer currently Producing the foregoing additives as a carbon fiber, aramid fiber, and a silica powder.
Primary EPDM terpolymer in adequate quantities to meet 5 It is also necessary that such additives be substantially
the demands of the ~ ~ k motor e t insulation industry is homogeneously dispersed throughout the insulation compo-
DuPont Dow Elastomers of Beaumont, Tex., which markets sition as it is being produced, while mixing devices
and sells an EPDMterpolYmercomPrising the H D m m m e r can be employed in the practice of this invention, such as a
under the tradename NORDELB 1040 and NORDELB Banbury mixer, it is a common experience that substantially
2522. 10 homogeneous distribution of fibrous additives is not
However, the ability of the industry to Produce STW4- achieved, or achieved only with difficulty, with many elas-
2868, DL1375, 053A, DL1552A, R196 and other thermal tomeric compositions. Difficulties have been described as in,
insulations containing NORDELB 1040 and NORDELB for instance, during mixing of the components; it can be
2522, and NORDELB 2722% as a Primary Or secondary observed that premature vulcanization may occur as well as
EPDM terpolymer has recently been Placed in Jeopardy due 15 other problems that may impede or entirely frustrate effec-
to the annOuncement by DuPont of its intention to cease tive distribution of the various additives which are essential
Production of NORDELB 1040, 2522, 2722E and, gener- to the ultimate production of the insulation.
Other EPDM Polymers formed from ,4-hexadiene. Further, once formulated, the elastomeric composition
There is, therefore, a need in this industry, previousb not must also possess acceptable shelf life characteristics such
satisfied, to find an effective alternate or a replacement for 20 that it remains sufficiently pliable, without becoming fully
the above-described STW4-2868, DL1375, 053A, cured, until used in application to the rocket motor casing,
DL1552A and R196 and This requirement is essential because the production of a
Of a mitable primary
given lot of insulation may have to wait in storage for a
replacement is especially critical for these discontinued number of months prior to use, Typically, the insulation may
NORDELB insulation formulations. 25 be stored in large rolls in an uncured or, at most, a partially
The requirements for an effec- cured state until ready for use. Anumber of curing agents are
tive, insulation for solid propellant rocket motors are well well known and are conventionally employed but still must
known to be quite severe due to the extreme conditions to be compatible with the overall EPDM formulation to
which the insulation is exposed. These conditions not only satisfactory shelf life, This in requires a balancing of
include exceedingly high temperatures but also severe abla- 30 curing agent activity,
tive effects from the hot particles (as well as gases) that
traverse and exit the rocket motor interior, Unless the In addition, the formulated insulation should be substan-
insulation will such conditions, catastrophic fail- tially for Obvious and this can require
ure has and may occur. special adjustment of the curing agent components.
U.S. Pat. No. 3,347,047, an early patent describing asbes- 35 After application to the interior (Or, if desired, the a t e -
tos fiber-filled insulations, states that flame temperatures rior) of the ~ ~ k motore t casing and subsequent Curing
encountered in the combustion of propellants, particularly thereof, an acceptable insulation must also exhibit satisfac-
when used as the of propu~sion,necessitating the tory bonding characteristics to a variety of adjacent surfaces.
confinement ofthe gases of combustion and ultimate release Such surfaces include the internal surface of the rocket
thereof through orifices, are usually accompanied by 40 motor casing itself and the insulation must also exhibit
extremely turbulent flow conditions, ~ 1 of1 these features adequate bonding characteristics between itself and the
place considerable stress and strain upon the member defin- Propellant grain, typically With an intermediate liner surface.
ing the escape passageway. While the combustion of the In the Propellant grain in a solid Propellant ~ ~ k e t
propellant in the case of rockets and the like will usually be motor is composed of a variety of materials notably includ-
of short duration, the temperatures and turbulence encoun- 45 ing still another elastomer, various combustible materials,
tered have been found to very easily destroy even the and such additional components as aluminum particles.
strongest and most exotic alloys formed of iron, steel, A functionally acceptable solid propellant rocket motor
titanium, magnesium, silicon, chromium, beryllium and the insulation must meet those requirements and must also
like. As a consequence, the projectile structure fails, leading survive aging tests. Such rocket motors may be fully fabri-
to total destruction thereof through explosion, or in the event 50 cated even many months before actual firing and, for tactical
that only the exit passageway is destroyed, the projectile weapons especially, sometimes even more than a year or
proceeds in an erratic, uncontrollable path since its trajectory even a plurality of years. For instance, strategic missiles may
or path is, at least in part, dependent upon the contour of the be stored in silos or submarine launch tubes for decades.
passageway through which the gaseous products of com- Over that period of time, the insulation must continue to
bustion pass. That statement still remains fully applicable 55 remain fully functional without unacceptable migration of
today. its components to or from adjacent interfacial surfaces and
Therefore, any replacement insulation should exhibit at adequately retain its elastomeric characteristics to prevent
least comparable temperature-resistant and ablation charac- brittleness. This requirement also needs to be satisfied under
teristics and theological and physical properties (e.g., wide temperature variations. The vibration and physical
Mooney viscosity) at least equivalent to that of STW4-2868, 60 stress placed on a rocket motor at the time of launch,
DL1375, 053A, DL1552A and R196, yet should not other- whether a ground launch or an air firing, is exceedingly high,
wise significantly alter the formulation techniques employed and brittleness and cracking in the insulation is effectively
for the production of such rocket motor thermal insulation. intolerable, whether from premature or gradual overcure or
Additionally, due to the large and growing quantities of solid whatever cause. Even at the end of the bum of the propellant
propellant rocket motor insulation required by the industry, 65 grain within the rocket motor casing, the insulation must
any such replacement EPDM terpolymer candidate should remain substantially and functionally intact to avoid poten-
be abundantly available now and into the foreseeable future. tially catastrophic failures of the entire launch vehicle.
 US 7,371,784 B2
7 8
In tum, this means that the insulation composition must BRIEF SUMMARY OF THE INVENTION
meet the ablation limits for protection of the casing through-
out the Propellant burn Without adding undue weight to the The present invention addresses a crucial long standing
motor. need in the industry for an acceptable substitute for the
A number of past patents have been granted proposing STW4-2868, DL1375, 053A, DL1552A and R196 insula-
various solutions to the insulation formulation problem. tions by providing a reformulated rocket motor thermal
These include U.S. Pat. No. 3,421,970 (generically describ- insulation notably comprising a suitable primary or second-
ing elastomeric formulations with asbestos); U.S. Pat. No. ary terpolymer replacement for the 1,4-hexadiene-based
3,562,304 (generically describing an elastomeric formula- EPDM and one that minimizes the degree of modification to
tion with asbestos fibers); U.S. Pat. No. 3,637,576 (describ- the existing formulation methods and also as to the ultimate
ing an EPDM formulation with a norbomene component functional properties of the STW4-2868, DL1375, DL155A,
with asbestos fibers); U.S. Pat. No. 4,492,779 (generically 053A and R196 thermal insulations.
describing elastomeric f0rmulations With KEVLARB The present invention relates to a rocket motor insulation
fibers); U S . Pat. No. 4,514,541 (generically a POnt 15 formulation comprising, as a primary or secondary terpoly-
“master batch” formulation with KEVLARB fibers, but not merit base, an EPDM terpolymer formed from at least one
an insulation); U.S. Pat. No. 4,550,130 (generically describ- alkylidene norbomene, especially ethylidene norbornene
ing a moldable carboxylic acid modified EPDM to enhance (ENB) as the diene component.
affinity to various fillers); U.S. Pat. No. 4,878,431 (generi- Exemplary EpDM terpolymers that may be used accord-
cally describing an elastomeric formulation using the EPDM 20 ing to this invention comprise those having an alkylidene
NORDELB 1040, with KEVLARB fibers); U.S. Pat. No. diene, particularly an ENB diene, component including
5,364,905 (describing a technique for the in situ polycon- KELTANB 4506, KELTANB 1446A, KELTANB 2308,
densation formation of aramid fibers, but not referring to NORDELB IP NDR520, and NORDELB IP NDR-640,
rocket motor insulations); U.S. Pat. No. 5,498,649 (describ- each of which may be substituted into the STW4-2868,
ing a polyamideimaleic anhydride modified EPDM with 25 DL1375, R196 and 053A insulation for the NORDELB
KEVLARB fibers for a rocket motor insulation); U.S. Pat. 1040 without requiring significant modifications to the stan-
No. 5,821,284 (a KEVLARB fiber-filled insulation contain- dard STW4-2868, DL1375, 053A, DL1552A and R196
ing an EPDM illustrated by NORDELB 2522 in combina- thermal insulation formulation methods or to the resulting
tion with ammonium salts); and u,s, pat, N ~ 5,830,384 , multitude of functionally acceptable properties. Other exem-
(generically referring to EPDM’ with a water>>silica 30 plary terpolymers including high-thylene-content EPDM
additive for cooling purposes). None of these patents formed from an ENB diene are
address nor effectively solve the problem faced by the NORDELB IP NDR-3722p and BUNAB EP T 2370, which
may be substituted into the DL1552A for the NORDELB IP
present invention. In fact, the frequent reference to NOR-
NDR-2722E without requiring significant modifications to
lo40 Or 2522
to ‘Onfirm the 35 the DL1552A formulation. NORDELB IP NDR-3725 has
observation that these particular are the also been used but the supplier (du pant) has indicated that
standard in the rocket motor insulation industry. due to low demand, it now prefers a different formulation,
AccordinglY, the search for a functionally satisfactory NORDELB IP NDR-3722, with a lower diene content of
elastomeric insulation composition requires discovery and about 0.5% versus about 2.5% for NORDELB IP NDR-
implementation of an extraordinarily complex combination 40 3725p.
of characteristics. The criticality of the material selection is It has now been found that a small proportion ofthe
demonstrated by the severity and magnitude of the ENB diene component is sufficient for incorporation in such
risk of failure. Most insulations are of necessity “man-rated” elastomers, say from about 2 to about 10 wt. %, preferably
in the sense that a catastrophic failure can result in the loss from about 2 to about 7 wt. %, and with the balance of the
of human life-whether the rocket motor is used as a booster 45 olefin content ofthe composition composed of ethylene and
for launch of the space shuttle or is carried tactically propylene, with the ethylene forming from about 40 to about
underneath the wing of an attack aircraft. The monetary cost 80 wt. %, preferably from about 50 to about 75 wt. %, and
of failure in satellite launches is well-publicized and can run with the remainder being propylene. Trace amounts of other
into the hundreds of millions of dollars. dienes may also be present to induce branching in the
50
o n e well-known potential point of failure is the appear- elastomer. Generally, the only significant modification that is
ante ofvoids or cracks in the insulation which could lead to required involves the selection of a less-reactive curing
the penetration of the rocket motor casing itself. The result- agent to offset the higher reactivity (relative to HD) of
ant dispersion of hot gases may not only lead to destruction ethylidene norbomene (ENB). Furthermore, NORDELB IP
of the motor generally but can at least lead to its being 55 NDR-3722 and BUNAB EP T 2370 are not presently
thrown off its intended course or trajectory with several foreseen as being susceptible to obsolescence issues.
unhappy results. In such events, the vehicle itself will either Other aspects and advantages of the invention will be
self-destruct or be intentionally destroyed, or the satellite apparent to those skilled in the art upon reading the speci-
will be launched into a useless orbit. fication and appended claims which, when read in conjunc-
Therefore, one of the most difficult tasks in the solid 60 tion with the accompanying drawings, explain the principles
propellant rocket motor industry is the development of a of this invention.
suitable, acceptable insulation composition that will meet
and pass a large number of test criteria to lead to its BRIEF DESCRIPTION OF THE SEVERAL
acceptability. VIEWS OF THE DRAWINGS
Furthermore, any replacement EPDM terpolymers should 65
not be susceptible to obsolescence issues nor discontinuance The accompanying drawings serve to elucidate the prin-
in future supply thereof. ciples of this invention. In such drawings:
 US 7,371,784 B2
9 10
FIGS. l a - l h are schematic cross-sectional views of a
rocket motor depicting various regions in which the insula-
tion of this invention may be applied;
ENB Content Ethylene Content Mooney
FIG. 2 is a schematic of a char motor suitable for Wt Yo Wt Yo Viscosity
5
conducting the ablation tests reported herein; and
KELTAN IE 4506 4.5 54 40
FIG. 3 is a cut-away view of a solid propellant rocket KELTANIE 1 4 4 6 ~ 7 59 10
motor illustrating the outer case, the internal insulation layer, KELTAN IE 2308 2 74 24
NORDEL IE IP 4520 5 51 20
the propellant grain, and the insulation of the ignitor closure NORDEL IE Ip 4640 5 55 40
structure. 10

DETAILED DESCRIPTION OF THE The remaining content is propylene with traces of certain
INVENTION dienes used to produce branching in the molecular structure.
In accordance with another preferred embodiment, the
As shown schematically in FIGS. la-3, the manner in l5 secondary EPDM terpolymer idare NORDELB Ip NDR-
which the inventive insulation may be applied to various 3722 BUNAB EP 2370, which ENB as
parts of a rocket assembly is illustrated. The rocket assembly their diene and are from
includes, but is not limited to, a system tunnel floor plate DuPont and Bayer Corporation and manufactured in
shear ply 10, a LSC blast shield ply 12, a stiffener stub hole 2o
large capacities.
plug 14, a stiffener stub insulation 16, an external joint An is set forth in 5:
weather seal 18, a T-ring insulation 20, an aft dome internal
insulation 22, and a center segment aft end internal insula- TABLE 5
tion 24 (underneath the flap). Ingredient Parts by Weight
In FIG. 2, the schematic cross-section of a char motor test 25
Primary EPDM terpolymer 70-80
assembly is illustrated wherein the propellant is contained in Secondary EPDM terpolymer 15-25
the beaker 30, with low-velocity insulation test specimens with ENB diene monomer
Tackifier 5-10
located at region 32 upstream of the throat 34, with medium- Antioxidant 1-3
velocity test specimens located in region 36 and with Wetting agent 0-1
high-velocity insulation test specimens located in the region 30 Curing activator 5-10
38. Generally, such a char test motor assembly permits the Silica filler 40-50
Pigment 0-3
location of a plurality of different insulation formulation test Plasticizer 15-25
specimens about the circumference at any of regions 32, 36 Curing agent 10-20
or 38 in the conventional manner.
35
FIG. 3 is a cut-away schematic view of a typical rocket The primary EPDM preferably has a sufficiently high
motor illustrating the case 40, the nozzle 42, the propellant diene content to provide a more reactive polymer to decrease
grain 44 with its center bore 46 and the internal insulation cure time. Preferably, the alkylidene diene content of the
layer shown at 48. The insulation of the ignitor closure primary EPDM is in a range of about 2-12 wt %, more
structure is indicated at 50. 40 preferably about 10-12 wt %. Additionally, the primary
In accordance with one embodiment ofthis invention, the EPDM terpolymer Preferably has a medium ethylene con-
inventive rocket motor insulation formulation comprises, as tent Of from about 56 wt % to about 65 wt %.
a primary polymeric base, an EPDM terpolymer in which In a more preferred embodiment, the primary and set-
the diene component of the EPDM is composed of at least Ondary components, tackifier, wet-
one alkylidene norbornene and, in particular, ethylidene 45 ting agent, curing activator, pigment, plasticizer, and
norbornene (ENB). silica are the same as those set forth in Table 3 above and are
present in the concentrations specified in Table 3. However,
The EPDM be when following that formulation composition on simply a
into the STW4-2868, DL1375, 053A, DL1552A and R196 “drop in”basis, it was observed that anunsatisfactory scorch
thermal insulation f0rm~11ation(Tables 1 and 2) without 50 characteristic developed (e.g., a scorch time of about 5.9
requiring significant modification of the present techniques minutes as against an 8 minute minimum time allowed per
employed for the formulation thereof. It is a further highly specification). Similarly, substituting BUNAB EP T 2370 in
desirable feature of the present invention that the insulation place of NORDELB 2722E led to similar results of an
formulation may be composed of readily available commer- unsatisfactory scorch time of 6.6 minutes and a high
cia1 materials, provided that such compositions are properly 55 Mooney viscosity of 119. Consequently, according to this
assembled and blended together for the final insulation invention, a less-reactive brominated phenolic resin curing
material. agent, for instance, having a lower reactivity than that used
Suitable EPDM terpolymers having an ENB diene in the DL1552Aformulation (i.e., SP 1056 containing about
6 wt % bromine) was required and was selected in order to
ponent for use in this invention include, without limitation,
60 compensate for the observed higher reactivity of ENB. This
and as stated above’ KELTAN@ 4506’ KELTAN@ 1446A’ then led to acceptable scorch characteristics, and the use of
KELTANB 2308, each of which is available from DSM of
cure temperatures of about 3200 F, provided similar cure
the and IP 4520 and IP rates as were used for DL1552A. The resulting physical
4640, both Of which are and continue to be from properties were also acceptable. Preferably, the resin curing
DuPont Dow Elastomers. 65 agent of the reformulated insulation formulation is SP 1055
These materials have the following respective contents as (manufactured by Schenectady International), which con-
derived from the manufacturer’s data literature: tains about 3% bromine by weight.
 US 7,371,784 B2
11 12
It will be observed that these materials may have signifi- accelerators that may be used in combination with the
cant variations in specific norbornene content, and also in phosphate cure accelerator include butyl zimate, ALTAXB,
the ethyleneipropylene content ratio as well as in the AKROFORMB Delta P. M., and SULFADSB. While the
Mooney viscosity, yet each has been found to be effective if use of Accelerator VS was initially unacceptable because of
selected for use in production of a rocket motor insulation. 5 the foul odor problem it generated, it has also now been
Adhesion-promoting secondary polymers that may also found that such formulations can be prepared with no
be used in the formulation include elastomer modifiers, significant odor when about 1.0 phr magnesium oxide is
especially polar polymers. Among such suitable secondary added thereto.
Polymers are chloros~lfonatedPolyethylene, such as HYPA- Sulfur curing agents are preferred for the formulation. A
LON@ 20 from DuPont Daw, and PolYchloroPrene. poly- 10 suitable sulfur-curinn
u
anent
u
is AKROSPERSEB IS-70 from
chloroprene polymers are available from DuPont Dow under Akro Chem. Elemental sulfur can also be used.
the tradenames NEOPRENEB FB, NEOPRENEB TW, and Batches of insulation containing silica powder generally
NEOPRENEB GRT. may be formulated in an internal mixer with the following
An exemplary plasticizer for the inventive formulation is two-pass mix procedure. In the first pass, the mixer speed
the EPDM-based TRILENEB 67A (Uniroyal). 15
may be set to approximately 40 rpm and all of the compo-
Tackifiers may also optionally be used. An example of a nents other than the curing agents and accelerators are added
suitable tackifier is AKROCHEMB P-133. to the internal mixer. (The silica was added last in the first
One or more antioxidants are also preferably included pass.) The mixing may be performed at a temperature of
within the inventive insulation formulation. Preferred anti- about 300" F. Suitable mixing times depend on the tempera-
oxidants include polymerized 1,2-dihydro-2,2,4-trimeth- 20
ture and mixing speed, and are ascertainable to the skilled
ylquinoline (AGERITEB Resin D) and mixed octylated artisan without an undue amount of experimentation.
diphenylamines (AGERITEB Stalite S), each of which is
available from R.T. Vanderbilt Co. In the second pass, the mixer speed was set to about 40
Various powder silica fillers are well known in other rpm. In a sequential manner, half of the master batch was
elastomeric combinations and may be used, including 25 added to the mixer, then the curatives were added, then the
HISILB 233. remaining half of the master batch was added to the mixer.
An exemplary carbon fiber is VMC carbon fiber. The second mixing step was performed at a temperature of
Suitable cure activators may include metal oxides, such as approximately 180" F. to 190" F. The material was sheeted
zinc oxide and magnesium oxide (e.g., ELASTOMAGB out onto the laboratory mill and allowed to cool to room
170, from Morton Chemical Co.). 30
temperature prior to evaluating its rheological and physical
The curing package preferably includes at least one properties.
phosphate cure accelerator, including, by way of example, The shaping and curing of the inventive insulation may be
RHENOCUREB AP-5, RHENOCUREB AP-7, RHENO- performed in accordance with techniques known in the art.
CUREB AP-3, RHENOCUREB ZADTIG, and RHENO- Exemplary new formulations containing a silica powder
CUREB SIG, which are available from Rhein Chemie and 35 filler are set forth in Table 6 below with concentrations
Accelerator VS, available from Akro Chem. Additional cure shown by weight.
T.4BI,E 6
EXAMPLES OF SILICA-FILLED EPDM INSULATION FORMULATIONS

Ingredient RDL5338 RDL5342 RDL5343 RDL5347 RDL5363 RDL5255 RDL5335 RDL5201 RDL5220

KELTAN CC 4506 70.0 73.0 73.0 55.0 55.0

KELTAN CC 1446A 20.0 17.0 17.0
KELTAN CC 2308 35.0 35.0
NORDEL CC IP 4520 80.0 80.0
NORDEL CC IP 4640 80.0 80.0
HYPALON CC 20 10.0 10.0 10.0 10.0 10.0
NEOPRENECCFB 20.0 20.0
NEOPRENE CC TW 20.0 20.0
NEOPRENE CC GRT
TRILENE CC 67A
KRATON CC L-2203
AKROCHEM CC P-133 5.0 5.0 5.0 5.0 5.0 5.0 5.0
AGERITE CC Resin D 2.0 2.0 2.0 2.0
AGERITE CC Stalite S 2.0 2.0 2.0 2.0 2.0
HISIL CC 233 35.5 35.5 35.5 35.5 35.5 35.5 35.5 37.0 37.0
ELASTOMAG CC 170 0.5 0.5
Zinc Oxide 3.0 3.0 3.0 3.0 3.0 4.0 4.0 4.0 4.0
Butyl Zimate 0.50 0.50 0.50
RHENOCURE CC AP-5 3.50 3.50 3.50
RHENOCURE CC AP-7
RHENOCURE CC AP-3 2.90 3.85
RHENOCURE CC ZADTIG 0.80 1.00
RHENOCURE CC SIG 0.60 0.80
ALTAX CC 1.10 1.10 1.20 1.10
AKROFORM CC Delta P.M 0.45 0.20
SULFADS CC 0.50
Accelerator VS 2.70 2.70
AKROSPERSE CC IS-70 1.10 1.10 1.20 1.20 1.40 1.00
Sulfur 0.35 0.45 0.40
 US 7,371,784 B2
13 14
TABLE 6-continued
EXAMPLES OF SILICA-FILLED EPDM FORMULATIONS

Ingredient RDL5370 RDL5380 RDL5381 RDL5194 RDL5222 RDL5273A RDL5298 RDL5277 RDL5279

KELTAN CC 4506
KELTAN CC 1446A
KELTAN CC 2308
NORDEL CC IP 4520 80.0 80.0 80.0 90.0 90.0 90.0 80.0
NORDEL CC IP 4640 90.0 90.0
HYPALON CC 20 10.0 10.0 10.0 10.0
NEOPRENE CC FB
NEOPRENE CC TW
NEOPRENE CC GRT 20.0 20.0 20.0
TRILENE CC 67A 10.0
KRATON CC L-2203 10.0 10.0
AKROCHEM CC P-133 5.0 5.0 5.0 5.0 5.0 5.0 5.0 9.0 9.0
AGERITE CC Resin D 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0
AGERITE CC Stalite S
HISIL CC 233 37.0 37.0 37.0 35.5 35.5 35.5 36.5 38.0 38.0
ELASTOMAG CC 170 0.50 0.50 0.50
Zinc Oxide 4.00 4.00 4.00 3.00 3.00 4.00 3.00 3.00 3.00
Butyl Zimate 0.50 0.40 0.15
RHENOCURE CC AP-5 3.40 3.15 4.45
RHENOCURE CC AP-7 3.00
RHENOCURE CC AP-3 3.85 3.85
RHENOCURE CC ZADTIG 1.00 1.00 0.90
RHENOCURE CC SIG 0.80 0.80
ALTAX CC 1.00 1.00 1.20
AKROFORM CC Delta P.M. 0.25
SULFADS CC 0.82
Accelerator VS 2.70 2.70
AKROSPERSE CC IS-70 0.95 1.10 1.34 1.25 1.40
Sulfur 0.40 0.50 0.50 0.40

Ingredient RDL5319 RDL5320A RDL5350 RDL5351A RDL5367 RDL5185 RDL5186 RDL5205 RDL5276

KELTAN CC 4506
KELTAN CC 1446A
KELTAN CC 2308
NORDEL CC IP 4520 40.0 40.0 45.0 45.0 45.0
NORDEL CC IP 4640 50.0 50.0 45.0 45.0 45.0 80.0 80.0 80.0 80.0
HYPALON CC 20 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0
NEOPRENE CC FB
NEOPRENE CC TW
NEOPRENE CC GRT
TRILENE CC 67A 10.0 10.0 10.0 10.0
KRATON CC L-2203
AKROCHEM CC P-133 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0
AGERITE CC Resin D 2.0 2.0 2.0 2.0
AGERITE CC Stalite S 2.0 2.0 2.0 2.0 2.0
HISIL CC 233 35.5 35.5 35.5 35.5 35.5 35.5 35.5 35.5 35.5
ELASTOMAG CC 170
Zinc Oxide 3.0 4.0 3.0 4.0 3.0 3.0 3.0 3.0 3.0
Butyl Zimate 0.40 0.40 0.40
RHENOCURE CC AP-5 3.15 3.15 3.50
RHENOCURE CC AP-7 3.00
RHENOCURE CC AP-3 3.85 3.85
RHENOCURE CC ZADTIG 0.80 0.80 1.oo
RHENOCURE CC SIG 0.80 0.80
ALTAX CC 1.00 1.00 1.10
AKROFORM CC Delta P.M. 0.35
SULFADS CC 0.50
Accelerator VS 2.70 2.70
AKROSPERSE CC IS-70 1.00 1.00 1.00 1.00 1.00 1.05
Sulfur 0.40 0.80 0.40

In addition, individual batches of insulation formulations 2 (compared to the 1,4-hexadiene monomer of the Com-
containing silica filler were prepared with NORDELB IP parative Example A) and, accordingly, SP 1055 (3 wt %
NDR-3725 (Example 1, Table 8 below), BUNAB EPT 2370 bromine) was used in Examples 1 and 2 and SP 1056 (6 wt
% bromine) was used in the Comparative Example A (Table
(Example 2), and NORDELB 2722E (Comparative
8) in equal quantities for comparison purposes. In addition,
Example) as the secondary EPDM terpolymers having high another formulation, RDL5654 was also prepared in much
ethylene contents. However, in these formulations it has the same way, but substituting NORDELB IP NDR-3722p
been observed that there is an increased reactivity of the for NORDELB IP NDR-2722E, and SP 1055 was used in
ethylidene norbornene monomers as used in Examples 1 and place of SP 1056.
 US 7,371,784 B2
15 16
(same concentrations as in Table 3), and the mixer speed was
TABLE 7 increased to 60 rpm. The batches were removed from the
internal mixer after mixing for a total of approximately 7
Diene
Ethylene Propylene content minutes. The temperature at the time of removing the batch
Polymer content % content % % type viscosity 5 was 300" F. to 320" F. The master batch was sheeted out on
a 6"x13" Farrel Corporation laboratory two-roll mill and
NORDEL CC IP 71 26.5 2.5lENB 25
NDR-3722
allowed to cool to room temperature.
BUNA CC EP T 2370 71 26 3lENB 16 In the second pass, the mixer speed was set to 40 rpm. In
NORDEL CC 2722E 72 22 6.4lHD 26 a sequential manner, half of the master batch was added to
lo the mixer, then the curatives were added (same concentra-
nebatches were each formulated in a laboratory scale tions as set forth in Table 3), then the remaining half of the
Reliable Rubber & plastics Machinery company Model master batch was added to the mixer. After a total mix time
R-260 internal mixer having a net chamber volume of 4260 of approximately 40 seconds, the final mix was mnoved
cubic centimeters. A 3000 gram batch was prepared by a from the mixer. The actual temperature at the time of
two-pass mix procedure. l5 removal was approximately 200" F. The material was
the first pass, the mixer speed was set at 40 rpm, and sheeted out onto the laboratory mill and allowed to cool to
the primary and secondary polymer components, tackifier, room temperature Prior to evaluating its Theological and
and antidegradant were added to the mixing chamber in the Physical Properties.
concentrations set forth in Table 3 and masticated for one The rheological properties of these several formulations
minute. Subsequently, the remaining ingredients were added are reported in Table 8:

TABLE 8
RHEOLOGICAL PROPERTIES (silica filler)

Example 1 Example 2 Comparative

Propem [RDL5294] [RDL5331] RDL5654 Example A

(1) Mooney viscosity (ML 1 + 4 at 63.4 61.0 65.4 68.8

212" F.) (ASTM D 1646)
(2) Mooney scorch (MS + 1 at 250" F., 21.5 18.1 27.1 11.8
min.) (ASTM D 1646)
(3) Oscillating disk rheometer (ODR ~

at 320" F., 5" arc) (ASTM D 2084)

properties:
(a) ML (minimum torque, in.-lb.) 17.8 16.4 17.1 21.4
(ASTM D 2084)
(b) MH (maximum torque, at 2 hrs, 91.0 95.0 86.8 97.7
in.-lb.) (ASTM D 2084)
(c) Ts2 (time to 2 point rise above 2.3 1.8 2.4 1.5
minimum viscosity, in min.)
(ASTM D 2084)
(d) MC(90) (in.-lb.) 83.7 87.1 79.8 90.1
(ASTM D 2084)
(e) Tc (90) (min) (ASTM E 2084) 74.0 73.5 77.1 75.5

45
The physical characteristics of these formulations are
reported as follows in Table 9:

TABLE 9
PHYSICAL PROPERTIES

Specification Example 1 Example 2 Comparative

Properties Requirement [RDL5294] [RDL5331] RDL5654 Example A

Shore A hardness 69-79 73.8 74.2 72.4 71.8

(ASTM D 2240)
Ash content (%) 20-26 22.6 22.4 22.2 22.7
(ASTM D 297)
Specific gravity 1.04-1.07 1.051 1.058 1.056 1.054
(ASTM D 792)
Tensile strength, perpendicular 1450 min. 2420 2480 2210 2280
(psi ASTM D 412)
Elongation parallel 450 min. 703 693 643 63 6
(%; ASTM D 412)
100% modulus (psi) ~ 347 370 377 371
Tear resistance (pli) 170 min. 233 23 8 230 22 1
(ASTM D 624)
 US 7,371,784 B2
17 18

TABLE 9-continued
PHYSICAL PROPERTIES

Specification Example 1 Example 2 Comparative

Properties Requirement [RDL5294] [RDL5331] RDL5654 Example A

Specific heat (BTU (lb.)-' (" F.)-' ~

0.445 0.442 ~
0.443
(ASTM E 1269)
Thermal conductivity (BTU ~
0.134 0.133 ~
0.129
(fi)-'(in.)-'(" F.)-' (ASTM E 1225)

Measurements were also made of the resulting ablation

rates for these formulations. 15 TABLE 10A
COMPARISON OF THE MATERIAL AFFECTED RATE (MAR)
TABLE 10 OF DL1552AAND RDL5654 IN THE LOW MACH CHAR MOTOR

MATERIAL ABLATION RATE (MILUSECOND) D-5 DL1552A RDL5654

20 Mach No. Average MAR Average MAR
Range (mils/sec.) (mils/sec.)
Comparative
Test motor HPCAT-07 MIR-05
Example 1 Example 2 Example A Low velocity 0.0027 3.83 3.86
test section
Low Mach Region (0.0028) 3.00 3.13 3.40 25 Medium velocity 0.0027-0.0081 3.79 3.80
test section
Medium Mach Region 7.34 7.94 7.60 High velocity 0.0094-0.044 5.36 5.49
(0.0318-0.0386) test section
High Mach Region 19.60 17.37 20.11
(0.0397-0.0634) In the following Table 11 there are set forth examples of
3o
the new EPDM insulation formations, which now contain
carbon fibers.
The ablation tests for Table 10 were performed as follows.
Batches of carbon fiber-containing insulations generally
The tests were performed in a char motor, schematically
may be formulated in a mixer via a two-pass mix procedure.
illustrated in FIG. 2. The samples for the three velocity
In the first pass, the mixer speed may be set to approximately
regions of the motor (low, medium, and high Mach) were net 40 rpm and all of the components other than the curing
molded using conventional compression molding tech- agents, accelerators, and carbon fiber are added to the
niques. The low Mach region had space for 15 specimens, internal mixer. As the mixing proceeds, the temperature will
while the medium and high Mach regions had space for 4 increase up to about 300" F., or even higher. Suitable mixing
specimens. The thickness of each specimen was measured at times depend on the temperature and mixing speed, and are
several axial locations before and after firing. The char ascertainable to the skilled artisan without an undue amount
motor itself featured a propellant beaker filled with Thiokol of experimentation,
Propulsion Propellant TP-H1148 to a suficient depth to In the second pass, the mixer speed may be set to about
Provide for a 12-second burn with a tungsten nozzle radius 45 40 rpm, but this speed is dependent on the size ofthe mixer.
o f 0 2 4 inches. The actual action time and average operating In a sequential manner, half of the master batch was added
Pressure for the test motor were 11.7 ~ c o n d sand 936 Psi, to the mixer, then the curatives were added to the mixer, then
respectively. the remaining half of the master batch was added to the
The cure characteristics and processability of the inven- mixer. The second mixing step may be Performed at a
tive Examples closely matched those of the Comparative 50 temperature rising to approximately 180" F. to 190" F. but
~~~~l~ A, The cure rates, as indicated by the 90 percent below the temperature where the accelerator would become
cure time tc(90), of Examples 1 and 2 were equivalent to that activated. The was sheeted Out Onto the
of the Comparative Example A, Similarly, the physical laboratory mill and allowed to cool to room temperature.
properties and ablative performance of the materials pre- Then the material is dissolved in a suitable solvent, such as,
55 by way of example, hydrocarbons such as hexane, heptane,
pared in accordance with Examples 1 and 2 were substan-
andor cyclohexane. The carbon fiber was then mixed with,
tially equivalent to those of the Comparative Example and
for example, a sigma-blade mixer. The material is then
were well within the specification requirements. Thus, these
sheeted out and the solvent is allowed to evaporate at
results indicate that the new formulations have the capability
ambient atmosphere or in an oven, Throughout this process,
of being substituted for the old standard to-be-discontinued 60 care must be taken that the frangible fibers are not
insulations. themselves fractured and broken up so as to become short-
In addition, a comparison was made between DL1552A ened and less effective as a result.
and RDL5654 in a low mach test char motor using TP- The shaping and curing of the inventive insulation may be
H1148 propellant and a 30.8 second firing time at an average 65 performed in accordance with techniques known in the art.
pressure of 881 psi. The following results indicate that The following Table 11 presents a number of examples of
RDL5654 is a viable replacement for DL1552A. the novel EPDM formulations with carbon fibers.
 US 7,371,784 B2
19 20

TABLE 11
EXAMPLES OF NEW EPDM FORMULATIONS WITH CARBON FIBER

Ingredient RDL5421 RDL5420A RDL5377A RDL5444A RDL5443 RDL5436 RDL5408 RDL5409

KELTAN CC 4506
KELTAN CC 1446A
KELTAN CC 2308
NORDEL CC IP 4520 40.0 40.0 45.0 45.0 45.0 80.0 80.0
NORDEL CC IP 4640 50.0 50.0 45.0 45.0 45.0 80.0
HYPALON CC 20 10.0 10.0 10.0 10.0 10.0 10.0
NEOPRENE CC FB
NEOPRENE CC TW
NEOPRENE CC GRT 20.0 20.0
TRILENE CC 67A 10.0
AKROCHEM CC P-133 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0
AGERITE CC Resin D 2.0 2.0 2.0
AGERITE CC Stalite S 2.0 2.0 2.0 2.0 2.0
HISIL CC 233 3 3 3 3 3 3 3 3
VMC Carbon Fiber All formulations adjusted to have 26.75% VMC Carbon Fiber in finished product
C. B. N330 1 1 1 1 1 1 1 1
ELASTOMAG CC 170 0.50 0.50
Zinc Oxide 4.0 5.0 5.0 5.0 4.0 4.0 4.00 4.00
Butyl Zimate 0.40 0.40 0.50
RHENOCURE CC AP-5 3.15 3.15 3.40
RHENOCURE CC AP-7 3.00
RHENOCURE CC AP-3 3.85
RHENOCURE CC ZADTIG 0.80 1.00
RHENOCURE CC SIG 0.80
ALTAX CC 1.oo 1.00 1.10
AKROFORM CC Delta P.M. 0.35
SULFADS CC 0.50
Accelerator VS 2.70 2.70
AKROSPERSE CC IS-70 1.oo 1.oo 1.00 1.00 1.00
Sulfur 0.80 0.40 0.50

Ingredient RDL5445 RDL5410 RDL5375 RDL5395 RDL5394 RDL5435 RDL5434 RDL5376A

KELTAN CC 4506 70.0 73.0 55.0 55.0

KELTAN CC 1446A 20.0 17.0
KELTAN CC 2308 35.0 35.0
NORDEL CC IP 4520 80.0 80.0
NORDEL CC IP 4640 80.0 80.0
HYPALON CC 20 10.0 10.0 10.0 10.0 10.0
NEOPRENE CC FB 20.0 20.0
NEOPRENE CC TW 20.0
NEOPRENE CC GRT
TRILENE CC 67A 10.0
AKROCHEM CC P-133 5.0 5.0 5.0 5.0 5.0 5.0
AGERITE CC Resin D 2.0 2.0 2.0 2.0
AGERITE CC Stalite S 2.0 2.0 2.0 2.0
HISIL CC 233 3 3 3 3 3 3 3 3
VMC Carbon Fiber All formulations adjusted to have 26.75% VMC Carbon Fiber in finished product
C. B. N330 1 1 1 1 1 1 1 1
ELASTOMAG CC 170 0.5
Zinc Oxide 4.0 4.0 4.0 4.0 4.0 4.0 4.0 5.0
Butyl Zimate 0.15 0.50 0.50
RHENOCURE CC AP-5 4.45 3.50 3.50
RHENOCURE CC AP-7
RHENOCURE CC AP-3 2.90
RHENOCURE CC ZADTIG .80
RHENOCURE CC SIG 0.60
ALTAX CC 1.10 1.10 1.20 1.10
AKROFORM CC Delta P.M. 0.45 0.20
SULFADS CC 0.50
Accelerator VS 2.70 2.70
AKROSPERSE CC IS-70 1.34 1.10 1.20 1.20 1.40 1.00
Sulfur 0.35 0.45

Silica Powder-Filled Insulation Properties

Table 12 reports rheological properties measured for the

silica powder thermal insulation formulations that were set
forth in Table 6.
 US 7,371,784 B2
21 22
TABLE 12 TABLE 13-continued
RHEOLOGICAL PROPERTIES (silica powder) PHYSICAL PROPERTIES
5 Silica-Filled EPDM
Mooney Oscillating disk rheometer (ODR at
viscosity 320" F., 5" arc) (ASTM D 2084) Formulation A B C D E F G

RDL 5205 1990 729 2120 773 207 71.6 1.06

(ML1+4 ML MH ts2 (time to a Tc
RDL 5276 2270 653 2210 656 223 71.2 1.06
Silica-Filled at 212" F.) (minimum (maximum 2 point rise (90%
EPDM (ASTM D torque, torque, at 1 above ML, cure) Key:
Formulation 1646) in.-lb.) hr., in.-lb.) in min.) (min) A = Tensile strength, parallel (psi) (ASTM D 412)
B = Elongation Parallel ("h)(ASTM D 412)
RDL 5338 72.0 17.7 93.9 6.0 43.5 C = Tensile Strength Perpendicular (ASTM D 412)
RDL 5342 78.5 21.3 97.8 7.0 45.0 D = Elongation Perpendicular (ASTM D 412)
RDL 5343 78.8 19.9 98.0 4.3 44.5 E = Tear Strength (ASTM D 412)
RDL 5347 84.0 21.7 94.5 3.4 38.0 15 F = Shore A hardness (ASTM D 2240)
RDL 5363 83.0 22.9 87.2 3.3 44.2 G = Specific gravity (ASTM D 792)
RDL 5255 85.7 19.4 103.2 3.6 28.5
RDL 5335 87.7 23.4 93.4 2.7 38.5
RDL 5201 73.0 16.4 89.0 6.2 31.5
Carbon-Fiber Containing Insulation Formulation Properties
RDL 5220 71.2 16.0 110.0 5.9 40.0 Next, Table 14 lists the rheological properties measured
RDL 5370 80.0 20.3 104.6 5.6 32.0 20 according to the indicated tests for the carbon fiber-contain-
RDL 5380 80.3 21.0 107.4 7.3 56.0 ing insulation formulations set forth in Table 11.
RDL 5381 79.6 21.0 104.0 4.8 36.0
RDL 5 194 62.0 13.4 90.9 8.7 44.0
RDL 5222 61.9 13.5 92.8 6.3 45.6
TABLE 14
RDL 5273A 64.5 14.7 97.1 3.8 42.0
RHEOLOGICAL PROPERTIES
RDL 5298 51.0 11.0 91.0 7.1 49.0 25
RDL 5277 72.4 18.9 98.5 1.9 42.6 Mooney Oscillating Disk Rheometer (ODR at
RDL 5279 75.0 17.3 93.0 2.7 18.8 viscosity 300" F.. 5" arc) (ASTM D 2084)
RDL 5319 87.8 19.9 97.0 6.3 43.0
RDL 5320A 86.5 20.7 103.0 4.0 41.6 (ML1+4 ML MH ts2 (time to a Tc
RDL 5350 83.0 22.0 103.0 6.8 46.1 Carbon-Fiber at 212" F.) (minimum (maximum 2 point rise (90%
RDL 5351A 84.6 19.8 105.6 3.5 37.0 30 EPDM (ASTM D torque, torque, at 1 above ML, cure)
RDL 5367 86.0 22.3 96.7 3.2 43.3 Formulation 1646) in.-lb.) hr., in.-lb.) in min.) (min)
RDL 5185 79.5 18.7 90.0 8.4 40.9
RDL 5186 80.6 19.3 95.5 RDL
4.1 43.0 5421 72.4 23.3 111 3.5 30.2
RDL 5205 79.9 19.4 94.0 RDL
8.0 41.2 5420A 70.0 21.2 119 2.9 37.0
RDL 5276 81.6 18.5 96.7 RDL
6.2 42.5 5377A 68.0 18.8 102 2.8 36.5
RDL 5444A 67.4 21.0 110 3.2 28.0
RDL 5443 74.5 25.7 101 1.6 33.5
RDL 5436 80.0 25.8 98.2 2.6 32.0
Table 13 reports various physical properties measured for RDL 5408 83.0 29.2 95.5 2.5 16.5
the silica powder thermal insulation formulations that were RDL 5409 83.8 25.8 99.0 3.5 25.5
RDL 5445 56.0 15.8 82.0 3.4 39.2
set forth in Table 6. RDL 5410 81.0 18.0 103 4.8 34.5
40 RDL 5375 55.0 21.0 100 2.5 31.7
TABLE 13 RDL 5395 64.7 29.2 87.4 3.2 35.0
RDL 5394 67.0 25.1 89.5 1.8 36.0
PHYSICAL PROPERTIES RDL 5410 81.0 18.0 103 4.8 34.5
RDL 5434 43.7 12.1 136 1.9 18.8
Silica-Filled EPDM RDL 5435 39.0 9.1 118 2.3 19.0
Formulation A B C D E F G 4 5

RDL 5338 2280 646 2260 65 8 220 62.0 1.06 Table 15 reports the physical properties measured for the
RDL 5342 1910 588 1790 582 206 63.4 1.06 carbon fiber-containing insulation formulations set forth in
RDL 5343 2330 655 2040 619 221 63.2 1.06
RDL 5347 2100 621 2060 630 271 68.6 1.06
Table 11.
RDL 5363 2920 610 2820 608 270 72.0 1.06
RDL 5255 2430 703 2330 695 223 69.4 1.10 TABLE 15
RDL 5335 2560 725 2600 739 232 65.2 1.10
RDL 5201 2150 772 2220 779 190 70.2 1.10 PHYSICAL PROPERTIES
RDL 5220 2170 634 2020 620 194 70.2 1.10
RDL 5370 2550 700 2340 688 201 70.4 1.10 Carbon-Fiber
RDL 5380 2610 688 2300 663 206 69.4 1.11 EPDMForm. A B C D E F
RDL 5381 2420 700 2470 70 1 207 69.0 1.11
RDL 5 194 1920 734 1920 748 201 71.8 1.05 RDL 5421 1750 3.34 820 4.59 84.4 1.097
RDL 5222 2100 703 1960 653 218 71.2 1.05 RDL 5420A 1600 3.12 871 4.60 84.2 1.106
RDL 5273A 1420 612 1430 613 241 70.4 1.06 RDL 5377A 1540 3.11 814 4.03 82.6 1.072
RDL 5298 1910 592 1870 586 223 71.6 1.06 RDL 5444A 2030 5.01 884 6.30 84.2 1.097
RDL 5277 2010 614 2190 632 181 66.4 1.05 RDL 5443 2070 5.37 799 7.21 83.2 1.090
RDL 5279 2390 672 2370 687 199 64.8 1.05 RDL 5436 1500 2.48 721 4.05 84.0 1.098
RDL 5319 2440 659 2270 647 205 71.2 1.05 RDL 5408 1060 3.77 525 5.61 81.2 1.131
RDL 5320A 2250 657 2220 653 224 71.6 1.06 RDL 5409 1112 2.95 668 3.35 83.4 1.142
RDL 5350 2350 688 2420 707 233 64.2 1.06 RDL 5445 1160 3.58 725 4.71 84.4 1.096
RDL 5351A 2270 681 2250 699 226 65.2 1.06 RDL 5410 1500 2.88 719 3.85 83.8 1.063
RDL 5367 2440 621 2430 625 238 70.4 1.06 RDL 5375 2010 4.38 881 6.85 80.6 1.076
RDL 5185 2310 776 2230 77 1 208 71.4 1.06 RDL 5395 2650 4.55 1090 4.98 86.1 1.078
RDL 5186 2390 725 2290 718 221 71.6 1.06 RDL 5394 2218 3.80 982 4.84 87.2 1.088
 US 7,371,784 B2
23 24
TABLE 15-continued TABLE 17-continued
PHYSICAL PROPERTIES MATERIAL ABLATION RATE (MILSXECOND)

Carbon-Fiber Carbon
EPDM Form. A B C D E F fiber Low Velocity, Medium Velocity, High Velocity, Avg.
EPDM 0.003 Mach Avg. 0.03-0.09 Mach 0.01-0.15 Mach
RDL 5435 1690 4.17 905 6.03 83.4 1.127
RDL 5434 1470 4.41 786 5.82 83.6 1.126 RDL 5377 3.86 11.5 17.6
RDL 5444 3.29 10.7 18.4
Key: 10 RDL 5443 3.22 12.5 19.9
A = Tensile strength, parallel (psi) (ASTM D 412) RDL 5436 2.63 11.0 15.3
B = Elongation Parallel (“h)(ASTM D 412) RDL 5408 3.91 11.2 16.5
C = Tensile Strength Perpendicular (ASTM D 412) RDL 5409 4.12 10.6 15.5
D = Elongation Perpendicular (ASTM D 412) RDL 5410 3.55 10.9 19.9
E = Shore A hardness (ASTM D 2240) RDL 5375 2.97 12.3 16.0
F = Specific gravity (ASTM D792) 15 RDL5395 3.00 11.7 20.8
RDL 5394 3.05 11.7 20.2
The following Table 16 shows the results of ablation tests RDL 5435 3.90 11.4 15.1
with the silica powder-containing formulations of Tables 6, RDL 5434 3.90 11.3 15.3
RDL 5376 4.27 12.9 14.7
12 and 13. RDL 5445 3.45 11.3 18.3
20
TABLE 16
The ablation tests were also performed as follows. The
MATERIAL ABLATION RATE (MILSXECOND) tests were performed in a char motor, schematically illus-
Silica powder Low Velocity,
trated in FIG. 2. The samples for the low-velocity region of
Filled 0.003 Mach the motor were molded using conventional compression
25 molding techniques. The low Mach region had space for 15
RDL 5338 3.65 specimens. The thickness of each specimen was measured at
RDL 5343 3.14
RDL 5347 2.31 several axial locations before and after firing. The char
RDL 5363 2.82 motor itself featured a propellant beaker filled with Thiokol
RDL 5255 2.76 Propulsion propellant TP-H1148 to a suficient depth to
RDL 5335 2.42 30 provide for a 12-second burn with a tungsten nozzle radius
RDL 5220 3.66
RDL 5370 3.44 of 0.24 inches. The actual action time and average operating
RDL 5380 3.24 pressure for the test motor were 12.1 seconds and 860 psi,
RDL 5298 3.36 respectively.
RDL 5319 3.23
RDL 5320 2.81 35 From the characteristics measured in these tables, it can
RDL 5350 3.38 be seen that a special combination of properties is required
RDL 5351 3.35 for a suitable insulation. It is important to the consideration
RDL 5367 3.31 of this invention that the formulations are effective as to both
RDL 5186 2.34
of the commonly used solid additives, silica powder and
4o carbon fibers.
The ablation tests were Performed as followS. The tests With reference to the results set forth in the foregoing
were performed in a char motor, schematically illustrated in tables, it is presently considered in Table 13 (silica-filled
FIG. 2. The samples for the three velocity regions of the EPDM) that the minimum acceptable values for tensile
motor (low, medium, and high Mach) were neat molded strength (parallel and perpendicular, values A and C) should
Using COnventional compression molding techniques. The 45 be at least about 1600, and are preferably close to equal
low Mach region had space for 15 specimens, while the (within about plus or minus 10%). The elongation (parallel
medium and high Mach regions had space for 4 specimens. and perpendicular, Table 13) should be in the range of about
The thickness of each specimen was measured at several 550-850. For tear strength, the value of about 170 is pres-
axial locations before and after firing. The char motor itself ently Seen as a minimum characteristic, Similarly, an ODR-
featured a propellant beaker filled with Thiokol Propulsion 5o measured maximum torque MH (Table 12) for the silica
Propellant TP-H1148 to a sufficient depth to Provide for a powder-filled insulations should be at least about 85 in.-lb.
12-second bum with a tungsten nozzle radius of 0.24 inches. and at most about 120 in,-lb,, preferably, at most about 115
The actual action time and average operating pressure for in,-lb, is currently thou& to be appropriate, The ODR
the test motor were 12.1 seconds and 860 psi, respectively. minimum torque ML has a useful lower limit of about 5
The following Table 17 shows the results of ablation tests 55 in.-lb., preferably about 10 in.-lb. The scorch test Ts result
with the carbon fiber-containing formulations of Tables 11, (Tables 12 and 14) should be at least 1.5. For silica-filled
14 and 15. insulations, the tear strength (Table 13) should be at least
about 170. For carbon fiber-containing insulations, the elon-
TABLE 17 gation should exhibit a minimum of at least about 2%,
60 preferably at least about 2.5%, especially for measurement
MATERIAL ABLATION RATE (MILSXECOND) B in Table 15. Also, for the carbon fiber insulations (Table
Carbon 14) the Mooney viscosity ML should be below about 90
fiber Low Velocity, Medium Velocity, High Velocity, Avg. Mooney Units.
EPDM 0.003 Mach Avg. 0.03-0.09 Mach 0.01-0.15 Mach Considering the combined properties of the individual
RDL 5421 3.38 11.4 18.7 65 insulations noted in the above tables, the silica-filled insu-
RDL 5420 2.87 12.2 19.2 lation 5273A is not presently preferred nor are the carbon
fiber-containing insulations 5408, 5409, 5434 and 5445.
 US 7,371,784 B2
25 26
In addition, formulations were also made using aramid Suitable additives that may be added as functionally
fibers as the filler material. An exemplary EPDM terpolymer required or as desired include one or more of the following,
for use with KEVLARB fibers and comprising ENB as its in various combinations: fillers, antidegradants, curing
diene component is NORDELB IP NDR-4640 (available agents, plasticizers, processing aids, pigments, bonding
from DuPont Dow Elastomers), which may be substituted 5 agents, fibers, and flame retardants. Two classes of curing
into the R196 for the NORDELB 1040 without requiring systems that may be used are sulfur-based curing agents in
significant modifications to the R196 formulation. KEV- combination with organic accelerators and peroxide curing
LARB fibers are formed from fibers of poly(p-phenylene- agents.
terephathalamide). Generally, the one significant modifica- The shaping and curing of such aramid inventive insula-
tion that is required with the use of aramid fibers involves a 10 tions may be performed in accordance with techniques
reduction in the amount of the curing agent, e.g., peroxide, known in the art.
again to offset the increased reactivity (relative to HD) of the
alkylidene norbomenes. Furthermore, NORDELB IP NDR- EXAMPLES OF ARAMID FIBER INSULATIONS
4640 is not presently foreseen as being susceptible to
15 Individual batches of insulation formulations were pre-
obsolescence issues.
Thus, in accordance with a further embodiment of this pared USING NORDELB IP NDR-4640 (Example, in Table
invention utilizing aramid fibers, the inventive rocket motor 20) and NORDELB IP NDR-1040 (Comparative Example
insulation formulation comprises, as a polymeric base, an B).
EPDIWpolyisoprene blend in which the diene component of 20
the EPDM is based on at least one alkylidene norbomene, TABLE 19
such as ethylidene norbornene (ENB), in effect in place of Ethylene Propylene Diene
and without the above-described primary EPDM. The alky- Polymer content content contenvtype Viscosity
lidene norbomene content of such an EPDM may be from
NORDEL IE 55 40 5lENB 40
about 2 wt %-lo wt %. The selected EPDM terpolymer 25 IPNDR-4640
should be substitutable into the R196 thermal insulation NORDEL IE 1040 55 41 4lHD 40
formulation (Table 4) without requiring significant modifi-
cation of the formulation. In accordance with a preferred
embodiment, the EPDM terpolymer is NORDELB IP NDR- The batches were each formulated in a laboratory scale
4640, which includes ENB as its diene monomer, is avail- Reliable Rubber & Plastics Machinery Company Model
30
able from DuPont Dow Elastomers, and is manufactured in R-260 internal mixer having a net chamber volume of 4260
a relatively large capacity. cubic centimeters. A 3000 gram batch was prepared by a
An exemplary aramid fiber formulation is set forth in two-pass mix procedure.
Table 18: In the first pass, the mixer speed was set at 40 rpm, and
35
80 parts by weight of the corresponding EPDM component
TABLE 18 set forth in Table 3, 20 parts by weight of NATSYNB 2200
polyisoprene, and 1.0 part by weight of Wingstay S were
Ingredient Parts by Weight added to the mixing chamber and masticated for one minute.
EPDM terpolymer with ENB 79.5-80.5
Subsequently, 40 parts by weight of Dechlorane Plus 515,20
diene monomer component 40
parts by weight of Sb,O,, and 20 parts by weight of Y4 inch
Polyisoprene 19.5-20.5 KEVLARB aramid fibers were added, and the mixer speed
Antioxidant 0.95-1.05 was increased to 60 rpm. The batches were removed from
Halogen-containing flame 39.5-40.5
retardant
the internal mixer after mixing for a total of approximately
Metal oxide flame retardant 19.5-20.5 7 minutes. The temperature at the time of removing the batch
KEVLAR IE fiber (aramid 19.5-20.5 was 300" F. to 320" F. The master batch was sheeted out on
45
staple fiber) a 6"x13" Farrel Corporation laboratory two-roll mill and
Curing agent 1.45-1.55
allowed to cool to room temperature.
For the Example and Comparative Example B, the fibers
In a more preferred embodiment, the polyisoprene, anti- were dispersed in a two-roll mill to reduce agglomerations
oxidant, flame retardants, and aramid fibers, e.g., KEV- 50 of fibers. The dispersion was accomplished by tightening the
LARB fibers are the same as those set forth in Table 4 above nip (separation between the two rolls) to 0.030 inch on the
and are present in the concentrations specified in Table 4. laboratory two-roll mill and passing the rubber through the
The metal oxide may be present in fine powdery form so as nip a minimum of six times. This dispersion step was
to also serve as a filler. VAROXB DBPH-50 is also a performed after the first pass but before the second pass. The
suitable peroxy curing agent, although the substitution of 55 rubber was then allowed to cool before the second pass.
ethylidene norbornene for 1,4-hexadiene requires a reduc- In the second pass, the mixer speed was set to 40 rpm. In
tion in curing agent concentration to offset the increased a sequential manner, half of the master batch was added to
reactivity of ethylidene norbornene. By providing the refor- the mixer, then the curatives were added at a peroxide level
mulated thermal insulation formulation with a peroxide of 1.5 phr, then the remaining half of the master batch was
concentration in a range of from about 1 to about 2.5 phr, 60 added to the mixer. After a total mix time of approximately
more preferably about 1.5 phr, a curing effect is achieved 40 seconds, the final mix was removed from the mixer. The
similar to the properties of R196. actual temperature at the time of removal was approximately
In general, the EPDIWpolyisoprene combination may be 200" F. The material was sheeted out onto the laboratory mill
used with about 60 wt %-90 wt % of the norbomene EPDM and allowed to cool to room temperature prior to evaluating
and about 40 wt %-lo wt % polyisoprene, again with 65 its rheological and physical properties.
suitable additives being present in functionally desired Table 20 gives the measured rheological properties of
amounts. these examples.
 US 7,371,784 B2
27 28
Although the Mooney scorch time of the Example was
TABLE 20 somewhat longer than that of the Comparative Example
(R196), at the cure temperature of 320" F., the cure rates, as
RHEOLOGICAL PROPERTIES indicated by the 90 percent cure time tc(90), of the two
Comparative materials were equivalent. Similarly, the physical properties
Property Example Example B of the materials prepared in accordance with the Example
and Comparative Example B were substantially equivalent
(1) Mooney viscosity (ML 1 + 4 at 212" 58.2 51.3
F.) (ASTM D 1646)
and well within the specification requirements. Additionally,
(2) Mooney scorch (MS +1 at 270" F., 52.0 27.8 the ablative performance of the material prepared in accor-
min.) (ASTM D 1646) 10 dance with the inventive Example was equivalent or better
(3) Oscillating disk rheometer (ODR at than the ablative performance of the Comparative Example
320" F., 5" arc) (ASTM D 2084)
properties:
B (R196).
In the course of experimentation leading to this invention,
(a) ML (minimum torque, in.-lb.) 11.3 13.3 a number of other candidate elastomeric formulations were
(ASTM D 2084) 15 tried in the hopes that the path to a new acceptable insulation
(b) MH (maximum torque, at 2 hrs, in.-lb.) 61.5 55.0
(ASTM D 2084)
would not be overly difficult. In fact, such other formulations
(c) Ts2 (time to 2 point rise above 4.3 3.3 proved to be unsuccessful and this is demonstrated by the
minimum viscosity, in min.) (ASTM following illustrative unsuccessful examples.
D 2084) Rubber Component Formula RDL5 191
(d) MC(90) (in.-lb.) (ASTM D 2084) 56.4 50.8
(e) Tc (90) (min) (ASTM E 2084) 65.5 63.0 2o Total Wt.=3000 grams

Table 21 reports the physical properties of these aramid Parts by

Category Component Id. Weight Wt YO Grams
fiber examples.
25 Polymers 1 NORDEL IE IP 80.00 54.22 1626.57
NDR-4640
TABLE 21 Plasticizers 2 NEOPRENE IE FB 20.00 13.55 406.64
Antioxidants 3 AGERITE IE Resin D 2.00 1.36 40.66
PHYSICAL PROPERTIES
Fillers 4 HISIL IE 233 35.50 24.06 721.79
Activator 5 Zinc Oxide 4.00 2.71 81.33
Specification Comparative
6 2"d Pass Additions
Properties Requirement Example Example B 30
Accelerators 7 RHENOCURE IE SIG 0.80 0.54 16.27
Density (Ibs/in3) (ASTM D 792) 0.040 min. 0.0422 0.0421 8 RHENOCURE IE AP-3 3.85 2.61 78.28
Shore A hardness (ASTM D 70-85 75.8 74.4 9 RHENOCURE IE 1.00 0.68 20.33
2240) ZADTIG
Tensile strength, parallel (psi) 700 min. 1085 1050 Curative 10 Sulfur 0.40 0.27 8.13
(ASTM D 412) 35
Elongation parallel ("h) 10 min. 27.3 24.6 Totals: 147.55 100.00 3000.00
(ASTM D 412)
Tensile strength, perpendicular 46 1 367
(psi) (ASTM D 412) Mixing Instructions, First Pass:
Elongation perpendicular ("h) 109 126
40 Add NORDELB and zinc oxide
Table 22 reports the results from a test to measure the Add HISILB and antioxidant
ablation rates for these aramid fiber examples. Add NEOPREREB FB
TABLE 22 Dump about 280" F.
45
MATERIAL ABLATION RATE (MILSISECOND) 2nd Pass Additions

Comparative Mix MB with curatives in Brabender

Example Example B
Dump about 190" F. or below
Low Mach Region (0.0028) 3.58 3.43 50 Rubber Component Formula RDL5570
Medium Mach Region (0.039-0.0970) 10.55 10.83 Total Wt.=3000 grams
High Mach Region (0.109-0.140) 16.59 21.99

Parts by
The ablation tests were performed as follows. The tests Category Component Weight Wt YO Grams
were performed in a char motor, schematically illustrated in 55
Polymers 1 NORDEL IE IP 50.00 33.89 1016.60
FIG. 2. The samples for the three velocity regions of the NDR-4640
motor (low, medium, and high Mach) were net molded using 2 NORDEL IE IP 40.00 27.11 813.28
conventional compression molding techniques. The low NDR-4520
Mach region had space for 15 specimens, while the medium Plasticizers 3 HYPALON IE 20 10.00 6.78 203.32
4 AKROCHEM IE P-133 5.00 3.39 101.66
and high Mach regions had space for 4 specimens. The 60
Antioxidants 5 AGERITE IE Stalite S 2.00 1.36 40.66
thickness of each specimen was measured at several axial Fillers 6 HISIL IE 233 35.50 24.06 721.79
locations before and after firing. The char motor itself Activator 7 Zinc Oxide 4.00 2.71 81.33
featured a propellant beaker filled with Thiokol Propulsion 8 2"d Pass Additions
Accelerators 9 Methyl Ethyl Tuads 2.00 1.36 40.66
propellant TP-H1148 to a sufficient depth to provide for a 10 Monex or Unads 1.00 0.68 20.33
12-second bum with a tungsten nozzle radius of 0.24 inches. 65 11 SULFADS IE 1.00 0.68 20.33
The actual action time and average operating pressure for 12 Butyl Zimate 1.50 1.02 30.50
the test motor were 12.0 seconds and 842 psi, respectively.
 US 7,371,784 B2
29 30
-continued -continued
Parts by Parts by
Category Component Weight Wt% Grams Category Component Weight Wt% Grams
5
Curative 13 Sulfur 0.50 0.34 10.17 Plasticizers3 HYPALON IE 20 10.00 6.78 203.32
4AKROCHIEM IE P-133 5.00 3.39 101.66
Totals: 152.50 103.35 3100.64 Antioxidants 5 AGERITE IE Stalite S 2.00 1.36 40.66
Fillers 6 HISIL IE 233 35.50 24.06 721.79
Activator 7 Zinc Oxide 4.00 2.71 81.33
10 8 2"d Pass Additions
Mixing Instructions, First Pass: Accelerators 9 Methyl Tuads 3.00 2.03 61.00
10 Methyl Zimate 3.00 2.03 61.00
Mix EPDMs and HYPALONB together 11 Sulfasan R 2.00 1.36 40.66
12 Butyl Zimate 3.00 2.03 61.00
Add antioxidants 5 and 6, add silica, zinc oxide Curative 13 Sulfur 0.50 0.34 10.17
Add AKROCHEMB resin 15
Totals: 158.00 107.08 3212.47
Dump about 250-300" F.
2nd Pass Additions
Mixing Instructions, First Pass:
Mix MB with curatives in Brabender
20
Mix EPDMs and HYPALONB together
Dump about 190" F. or below
Rubber Component Formula RDL5571 Add antioxidants 5 and 6, add silica, zinc oxide
Total Wt.=3000 grams
Add AKROCHEMB resin
25 Dump about 250-300" F.
Parts by 2nd Pass Additions
Category Component Weight Wt% Grams
Mix MB with curatives in Brabender
Polymers 1 NORDEL IE IP 50.00 33.89 1016.60
NDR-4640 30 Dump about 190" F. or below
2 NORDEL IE IP 40.00 27.11 813.28
NDR-4520 Rubber Component Formula RDL5172
Plasticizers 3 HYPALON IE 20 10.00 6.78 203.32
4 AKROCHEM IE P-133 5.00 3.39 101.66
Total Wt.=3000 grams
Antioxidants 5 AGERITE IE Stalite S 2.00 1.36 40.66
Fillers 6 HISIL IE 233 35.50 24.06 721.79 35
Activator 7 Zinc Oxide 4.00 2.71 81.33
8 2"d Pass Additions Parts by
Accelerators 9 Methyl Tuads 0.75 0.51 15.25 Category Component Weight Wt% Grams
10 ALTAX IE 1.50 1.02 30.50
11 SULFADS IE 0.75 0.51 15.25 Polymers 1 NORDEL IE IP NDR-4640 80.00 54.22 1626.57
12 Butyl Zimate 1.50 1.02 30.50 2 TRILENE IE 67A 10.00 6.78 203.32
Curative 13 Sulfur 0.50 0.34 10.17 40 Plasticizers 3 HYPALON IE 20 10.00 6.78 203.32
4AKROCHEM IE P-133 5.00 3.39 101.66
Totals: 151.50 102.68 3080.31 Antioxidants 5 AGERITE IE Resin D 2.00 1.36 40.66
Fillers 6 HISIL IE 233 35.50 24.06 721.79
Activator 7 Zinc Oxide 3.00 2.03 61.00
8 2"d Pass Additions
Mixing Instructions, First Pass: 45 Accelerators 9 Captax 1.00 0.68 20.33
10 Tellurac 0.50 0.34 10.17
Mix EPDMs and HYPALONB together 11 SULFADS IE 0.75 0.51 15.25
Curative 12 Sulfur 1.00 0.68 20.33
Add antioxidants 5 and 6, add silica, zinc oxide
Add AKROCHEMB resin Totals: 148.75 100.81 3024.40

Dump about 250-300" F.

2nd Pass Additions Mixing Instructions, First Pass:
Mix MB with curatives in Brabender Mix NORDELB and HYPALONB together
55
Dump about 190" F. or below Add antioxidants 5 and 6, add silica, zinc oxide
Rubber Component Formula RDL5572
Add TRILENEB and AKROCHEMB resin
Total Wt.=3000 grams
Dump about 250-300" F.
6o 2nd Pass Additions
Parts by
Category Component Weight wt % Grams Mix MB with curatives in Brabender
Polymers 1 NORDEL IE IP NDR- 50.00 33.89 1016.60 Dump about 190" F. or below
4640
2 NORDEL IE
40,00 27,11 813,28 65 As indicated below, for various reasons, the above-de-
IP NDR-4520 scribed experimental test insulations proved to be unsuitable
formulations for production of rocket motor insulations.
 US 7,371,784 B2
31 32
polyisoprene;
TABLE 23 at least one filler selected from the group consisting of
silica, carbon fibers, and aramid staple fibers;
Unsuccessful Experimental Results a curing agent;
Rheological Properties
5 a secondary polar polymer; and
Formulation ML MH ts2 Tc(90) Rejected because: at least one additive selected from the group consisting of
an antioxidant, a plasticizer, a tackifier, a cure additive,
RDL5571 25.3 138.3 2.3 21.3 MH too high to match
existing standard insulation and an adhesion promoter.
RDL5572 22.6 173.9 2.5 25.7 MH too high to match 2. The elastomeric insulation of claim 1, wherein the
existing standard insulation 10 alkylidene norbomene is ethylidene norbornene.
RDL5570 25.6 128.6 2.7 29.5 MH too high to match
existing standard insulation
3. The elastomeric insulation of claim 1, wherein the
RDL5191 26.8 133.6 3.5 25.4 MH too high to match alkylidene norbornene is present in the primary EPDM
existing standard insulation terpolymer composition in a range of between approxi-
RDL5172 39.0 128.0 1.0 25.0 Uses the old cure system as mately 2 weight percent and approximate~y 12 weight
in Table 2, but product is
much too scorchy to be
15 percent,
useful; cures at too low a 4. The elastomeric insulation of claim 1, wherein the
temperature ethylene is present in the primary EPDM terpolymer com-
position in a range of between approximately 40 weight
As these unsuccessful formulations indicate, and faced 2o percent and approximately weight percent.
with the discontinuance of the availability of the hitherto 5. The elastomeric insulation of claim 1, wherein the
thought to be essential component for the present standard curing agent comprises a peroxide curing agent present in an
insulation formulations, the development of a suitable and amount Of from phr to 2.5 phr.
acceptable solid propellant rocket motor insulation that will 6. The Of 1, wherein the
provide the required performance criteria has not been an 25 curing agent comprises
easy task. 7. The elastomeric insulation of claim 1, wherein the
The foregoing detailed description of the preferred aramid staple fibers comprise PolY(P-PhenYleneterePhthala-
embodiments of the invention has been provided for the midel.
purposes of illustration and description. It is not intended to 8. The elastomeric insulation of claim 1, wherein the
be exhaustive or to limit the invention to the precise embodi- secondary Polar Polymer comprises a member selected from
ments disclosed. Many modifications and variations within 30 the €TOUP consisting of chloros~lfonatedPolyethylene and
the scope of this invention will be apparent to practitioners PolYchloroPwne.
skilled in this art. The illustrated embodiments were chosen 9. The elastomeric insulation of claim 1, wherein the
and described in order to best explain the principles of the elastomeric insulation consists of from about 15 weight
invention and its practical application, thereby enabling Percent to about 25 weight Percent of the secondary Polar
others skilled in the art to understand the invention for 35 polymer.
various embodiments and with various modifications as are 10. The elastomeric insulation of claim 1, wherein the
suited to the particular use contemplated. It is, therefore, propylene content of the alkylidene norbornene ranges from
intended that the scope of the invention cover various approximately 22 weight percent to approximately 26.5
modifications and equivalents included within the spirit and 4o weight percent.
scope of the appended claims. 11. The elastomeric insulation of claim 1, wherein the
What is claimed is: elastomeric insulation consists of from approximately 60
1. An elastomeric insulation cured from an ethylene weight percent to approximately 90 weight percent of the
propylene diene monomer (EPDM) terpolymer composi- primary EPDM texpolymer composition and from approxi-
tion, consisting of: mately 10 weight percent to approximately 40 weight per-
45
a primary EPDM terpolymer composition formulated cent of the polyisoprene.
from ethylene, propylene, and an alkylidene nor-
bornene; * * * * *