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AD 286 392 kepAodttced

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ARMED SERVICES TECHNICAL INFORMifflON AGENCY ARLINGTON HALL STATION ARLINGTON 12, VIRGINIA

UNCLASSIFIED

NOTICE: When government or other drawings, specifications or other data are used for any purpose other than in connection with a definitely related government procurement operation, the U. S. Government thereby Incurs no responsibility, nor any obligation whatsoever; and the fact that the Govern- ment may have fonnulated, furnished, or in any way supplied the said drawings, specifications, or other data is not to be regarded by implication or other- wise as in any manner licensing the holder or any other person or corporation, or conveying any rights or permission to manufacture, use or sell any patented invention that may in any way be related thereto.

286 392

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DEVELOPMENT OF FLEXIBLE POLYMERS

AS THERMAL INSULATION IN SOLID-PROPELLANT

ROCKET MOTORS

Quarterly Progress Report

Contract DA-36-034-ORD-3325 RD

July 1 to September 30, 1962

0CT25 1352Ll,

October 1962

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ATLANTIC RESEARCHCORPORATION , ^ i

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I ATLANTIC RCBKANCH CORPORATION

ALCXANQRIA,VIRaiNIA

i; DEVELOPMENT OF FLEXIBLE POLYMERS

AS THERMAL INSULATION IN SOLID-FROPELLANT

ROCKET MOTORS

Quarterly Progress Report

Contract DA-36-034-ORD-3325 RD

July 1 to September 30, 1962

Contributors:

T. R. Walton

E. B. Slmnons

Submitted to:

Rock Island Arsenal

Rock Island, Illinois

Submitted by:

Atlantic Research Corporation

Shirley Highway at Edsall Road

Alexandria, Virginia

October 1962

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ATLANTIC RCICANCH CDHPORATION

ALCXANDNIA.VINOINIA

TABLE OF CONTENTS

I. INTRODUCTION

II. RESULTS AND DISCUSSION

A. EPOXY RESINS

1. Mechanical Testing

2. Static Motor Firing Tests

B. PHENOLIC RESINS


2. Static-Motor Firing Tests

C. FURAN RESIN

Ill. SUMMARY OF INSULATION WORK

IV. FUTURE WORK

APPENDIX

Page No.

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2

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10

10

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12

21

23

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ATLANTIC RCSCANCH CORPORATION

ALCXANDRIA.VINOINIA

LIST OF TABLES

i

Table

I

II

III

IV

V

VI

VII

VIII

IX

XI

XII

Title Page

Convergent-Section Motor Firing (B-72) 4 Results for Filled Epoxy Resins

Convergent-Section Motor Firings M-305 5 Results for Filled Epoxy Resins

Convergent-Section Motor Firing M-303 8 Results for Filled Epoxy

Convergent-Section Motor Firing M-104 11 Results for Filled Phenolic Resins

Polymerization of Furfural with Acid Catalysts 14

Polymerization of Furfuryl Alcohol with Acid 15 Catalysts

Polymerization of Furfuryl Alcohol Prepolytner 16 (Atlas) with Acid Catalysts

Polymerization of Furan Prepolytner (Durez) 17 with Acid Catalysts

Polymerization of Furan Prepolymer (Jet-Kote 18 X-3M) with Acid Catalysts

Co-Polymerization of Furfuryl Alcohol Prepolymer 19 (Atlas) with Epoxy Resins and Polyisocyanates

Co-Polymerization of Furan Prepolymer (Durez) 20 with Epoxy Resins and Polyisocyanates

Summary of Best Insulation Developed to Date 22 under this Program

ATLANTIC RCICAHCH CORPORATION

ALEXANDRIA, VIROINIA

LIST OF FIGURES

Figure Title

1 and 2 Photographs of Tested Specimens from Motor Firings B-72 and M-305

3 and 4 Photographs of Tested Specimens from Motor Firings M-303 and M-304

Page No.

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ATLANTIC RHCARCH CONPONATIQN

ALCXANDRIA.VINIIINIA

ABSTRACT

The preparation of flexible furan resins by the polymerisation

of furfural, furfuryl alcohol, and furan prepolymers by long chain acids

(tp serve as both catalyst jmd plastlclzer) does not look promising. However, J8LH-I*AV ^ ttjft^s^jjfat^^LxojjiM^Mars \Mir^sA furan prepolymers and epoxy resins or

dllsocyanates,resultsd tn flexible materials/

Mechanical properties were determined for two of the better ln^—^

inlnflnn matsrfsls ^tevetopitf^nnlirTMrpretgwrr-tre 40 {ft sent castor oll-

modlfled Guardian filled with 40 fa* cent of asbestos fibers and tW 1:1

phenol-formaldehyde:Syl Kem 90 resin, filled with 43 per cent of asbestos

fibers. The ultimate elongations were 6 and 0.4 per eent, respectively.

Hnwevpr, the mechanical properties of the castor oil-modified Guardian

ware- determinad on defective specimens and the elongation of 6 per cent

»epresenta..only a minimum value.

Four static-motor firings were made« during this report parted*.

-Several new-formulatlena were tested.' A char rate of 1.7 mil/sec was

obtained for an Epon 828:tetrahydrophthallc anhydride:castor oil formulation

filled with 40 per-cent of asbestos fiber.

Specimen» containing other fillers besides pure asbestos fibers

were evaluated in motor tests. The 40 per-cent castor oil-modified Guardian

filled with 20 per eent of asbestos fibers and 20 per -eent of potassium

oxalate had a char rate of 2.4 mil/sec and showed a slight improvement over

the material filled only with 40-per eent of asbestos fiber. The castor

oil-modified Guardian filled with 40 per cent of sllica-microballoons had a

char rate of 5.0 mil/sec, but a very low density, 0.71 gsJ/cc, The densities

of the 40 par cent asbestos and oxalate filled materials are about 1.45

gi/cc. The effect on the char rate of various amounts of asbestos fibers

and aslVstos fibers - potassium oxalate ratios in the phenol-formaIdehydef

Formulation was found te be small.

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ATLANTIC RESEARCH CORPORATION

ALEXANDRIA, VIRQ INI A

I. INTRODUCTION

The purpose of thermal insulation is to prevent excessive

heating of the structural parts of a missile by the burning propellent.

The insulation must be sufficiently flexible to conform to the shape of

the structural parts which strain elastically under high operational

pressure. If the insulation does not elongate adequately, it fractures,

and the hot propellent gases penetrate to the motor case to cause over-

heating and failure. When the insulation is bonded to the grain or to

the motor case, flexibility is essential to prevent fracture of the bond

and possible motor failure by side burning.

The purpose of this project is to develop flexible polymers,

which, when combined with appropriate fillers, will be suitable for use

as thermal insulation In solid propellent rocket motors. Polymeric

systems selected for investigation are epoxles, phenolics, melamines,

furans, polyurethanes, and polyesters. The investigation includes the

modification of commercially available resins, the synthesis of new

polymers, and the correlation of polymer structure with performance.

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ALEXANDRIA. VI Hü IN1 A

II. RESULTS AND DISCUSSION

A. EPOXY RESINS


The exact amount of flexibility needed In the Insulation has not

been veil-defined. Calculations show that the maximum strain of a steel

motor case Is 0.4 to 0.8 per cent during pressurlzatlon and occurs over a

period of 0.1 second (time for motor to reach full pressure). Thus, a

material having an elongation of 1 per cent under a strain rate of 3 ln/ln/mln

should be satisfactory. Greater elongation than I per cent Is obviously

desirable. It Is probably safe to predict that a material with an elongation

of 100 per cent would be usable, 5-10 per cent may be marginal, while less than

0.8 per cent could not be recommended.

Generally our resins are roughly screened by manual flexing. For

those resins found to have superior Insulating ability, mechanical properties

are determined. One of the best Insulations developed to date has been

the 40 per cent castor oll-modlfled Guardian filled with 40 per cent of

asbestos fibers. The pure resin is very flexible, but of course, when it

is filled with asbestos fibers, its elongation is greatly reduced. Attempts

to prepare thin (1/8-inch-thick), asbestos-filled specimens for testing have I

not been very successful. The average mechanical properties of 3 specimens,

visually observed to contain defects on their surfaces, were as follows;

Ultimate Elongation 6 per cent

Ultimate Stress 1500 psi

Young's Modulus 66,500 psi

The fact that the failures were observed to occur at these defects indicates

that these values represent only a minimum elongation and tensile strength

for this 40 per cent castor Oil-modified Guardian filled with 40 per cent

asbestos fibers. Attempts to prepare better specimen will be made.

2. Static Motor Firing Tests

Evaluation of flexible epoxy resins in a 5-inch static motor has

continued. Several new asbestos-filled formulations were tested as well as

old formulations with new filler combinations. A direct comparison of the

more promising materials was obtained by retesting them in the same motor.

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ALEXANDRIA, VIRGIN IA

In motor firing B-72 (Table I), four asbestos-filled, flexible,

epoxy resins were tested, along with two of the better commercially available

insulations, General Tire and Rubber Company's Gen-Gard ^-44 and U. S. Rubber

Company's 3015. Because the nitrogen quencher failed to operate at the end

of this firing, these six materials were retested in motor firing M-305 (Table II)

The nitrogen quench is used to immediately lower the temperature of the motor

and to prevent burning of the specimen after the firing is completed. The

omission of the quench can result in unreliable char rates for the specimens.

The severe alteration in the uncharred materials for specimen V-44, 3015,

and XXXXII in motor firing B-72 can be seen in Figure 1. Figure 2 shows the

tested specimens from firing M-305.

Gen-Gard V-44 appears to be one of the materials that shows a

lower char rate* if the quenching technique is not used. This behavior

is related to swelling of the uncharred material. Based on data from

previous B-type firings (6500<)F flame temperature), the char rate for the

V-44 should be somewhat higher, while the char rate for the 3015 should be

somewhat lower, than the observed values in firing B-72. Thus, since the

reliability of the data in this motor firing are in question, only the char

rates in motor firing M-305 are compared.

Because a 5600oF propellant was used in motor firing M-305, the

char rates are all lower than the values reported in B-72. The performance

of IX-A(0xiron 200-Empol 1014) is somewhat disappointing in that this

particular formulation was one of the best materials in the oxycetylene torch

screening test.** Based on previous motor firings, the char rates of the

V-44 and 3015 in this firing are perhaps somewhat lower than what might be

expected. Nevertheless, the char rate of 1.7 mil/sec for formulation XXXXII

(Epon 828;tetrahydrophthalic anhydride:castor oil) was the best of this

series. Although a char rate of 1.7 mil/sec may seem abnormally low, visual

examination of the uncharred material under the charre4 layer showed it to be

*The amount of char is determined by subtracting the thickness of the uncharred layer from the initial thickness of the specimen. If this uncharred layer swells, the measured amount of charring will be lower than actual.

**Second Annual Summary Report for this contract, July 31, 1962. Pages 16, 18,

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unchanged with no evidence of swelling or voids. Furthermore, as previously

discussed,* this formulation was expected to yield a material of superior

performance because (1) the rigid Epon 828:tetrahydrophthalic anhydride

formulation has an average char rate of 2.2 mil/sec based on several motor

firings and (2) the addition of castor oil tp epoxy resins not only increases

the flexibility of the resin but also increases the insulation performance

(lower char rate). This lower char rate will, however, need verification

in additional motor tests. On the basis of this motor firing, the char

rate X density value of 2.5 shows this insulation to be one of the best

developed to date.

In firing M-303 (Table III), the effect of several filler combina-

tions was determined. Replacing half the asbestos in the Guardian formulation

with potassium oxalate (formulation number XXI C) gave only a marginal

improvement in char rate (from 3.2 to 2.9 mil/sec). Replacing half of the

asbestos in the 40 per cent castor oil-modified Guardian with potassium

oxalate also gave only a marginal improvement (2.6 mil/sec for formulation

XXXV versus 2.4 mil/sec for formulation XXII A). When the 40 per cent of

asbestos fiber was replaced by silica microballoons (Eccospheres SI) in

the 40 per cent castor oil-modified Guardian, the char rate increased from

2.6 (formulation XXXV) to 5,0 mil/sec (formulation XXXXVI). However,

the density is significantly reduced from 1.45 gm/cc for the asbestos-filled

material to 0.71 gm/cc for the Eccospheres-filled material. Therefore, on

the basis of the char rate and density, this material (XXXXVI) is one of

the best insulations in this group with a char rate-density factor of 3.6.

The only better material was the 40 per cent castor oil-modified

Guardian filled with 20 per cent of asbestos fiber and 20 per cent of potassium

oxalate with a char rate-density factor of 3.5. The specimens from motor

firing M-303 are shown in Figure 3. It can be observed that the V-44 control

which represents one of the best commerically available insulations

delaminated with obvious swelling of the uncharred material. This swelling

indicates that the actual char rate is probably greater than the 2.8 mil/sec

value reported and that, at least in this motor firing, its performance is

not as good as indicated.

Based on the results of these motor firings, specimens filled

with asbestos-silica microballoons and perhaps even asbestos-potassium

* Second Annual Summary Report for this contract, July 31, 1962. Page 16 and 18.

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oxalate-silica mlcroballoons will be studied.

B. PHENOLIC RESINS


Since the modified phenol-formaldehyde resin having the best

Insulation performance (lowest char rate) was the 1:1 phenol-formaldehyde

"stage A" resln:Syl Kern 90, the mechanical properties of this material I

containing 45 per cent of asbestos fibers (3R100) were determined.

The average for three samples Is:

Ultimate Elongation 0.367. (177.)

Ultimate Stress 1350 psl (3290 pal)

Young's Modulus 66,500 psl ( — )

For comparison, the values for the unfilled material are shown in

the parentheses.

Since the elongation of the asbestos filled resin is low, it will

be necessary to use a filler which does not reduce the elongation so

drastically or use a formulation (for example the 407. phenol-formaldehyde:

60% Syl Kern 90) in which the elongation of the unfilled resin is higher

(747.).

2. Static-Motor Firing Tests

A series of the 1:1 phenol-formaldehyde:Syl Kem 90, resins filled

with various ratios of asbestos fiber to potassium oxalate were prepared

and motor tested. The results of this firing (M-304) are reported in

Table IV, and a picture of the tested specimens is shown in Figure 4. All

specimens in this test were found to have a char rate of 2.8 mil/sec except

for specimen 7-24B which had a char rate of 2.5 mil/sec. On the basis of

the char rate-density factor, this latter material would be rated the best

of the phenolics tested in this series, but it was inferior to U. S. Rubber

Company's 3015. It is somewhat surprising that all the specimens performed

essentially the same in this motor firing. Some of the materials will be

retested to confirm these results.

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M (0 B) rH

4J U •rl Ü

V & Q

4J d M 01 a u r-l

r-l h •H 0) to

to

oo iri CM ■

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CO CO

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o m

o m

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• • • ■ M-l IH • • ^3 4J M 4J X> u i (0 O U) 0 • • (0 O 1 id a 0) a Xi

V) id a

*< K R^ K A) (fl s^H 00 CM «N 00 m m • • • • H 8^ • • n r-l r-l en O m CM CM n i-i r-l n in <»■ CM CM

u (d a

r-l ^ c 0) /-> 0 •O *J •rl >, u 4J J: (d Cfl 

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^^ 2 ^ OJ <-t X >, to W

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u < (U V < « Ü pd to

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to a o) 0 to a O CO o 01 & X XI m 4J (U

4-1 • » «W CO V • 0 0) u T3 4-1 3 l-l U u id 01 14-1

id -o 4J O n ß c 01 q) 0) X a 4J u a S V) m S 0) M u 0> X 00

> 4J O (U •rl 4-1

4J 4J O id • id id js

rH 00 u a iw C3 id 00

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M 0) 14-1 id »

rv 0 w • • 09 0) CM TJ id •o 00 1^ c c -o

0) 00 id o) • ■ C 00 4J •rl 10 (U c id U ■o J:

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•rl V oj a -C C TS ia E 4J 3 3 oo x: r-l id o> c 4J o y u <u ■rl C 0) (U J S H PQ »

11

ATLANTIC RCICAHCH COHPORATION

ALCXANONIA.VINSINIA

C. FURAN RESIN

I I

Several approaches have been followed in our attempts to prepare

flexible furan resins. These involve (1) the polymerisation of furfural

and furfuryl alcohol by long chain acid catalysts which may act as plasticizers,

(2) the polymerisation of furan prepolymers by these acidic catalysts, and (3)

the co«polymerisation of furan prepolytters with epoxy resins and polyiaocyanates.

The results are summarised in Tables ¥ through XI.

The add catalyst referred to as diacid 150 was prepared by

heating one mole of 1,4-butanediol Wtth two moles of tnatelc anhydride at

120eC for four hours with stirring.

0

2 || N0 + HO-CH CH CH.OH.OH l20 C) CH C^ 1 l 1 I

HOOCCHzCHCOOCH.^l.CH-CH.OOCCHsCHCOOM

Titration of the product with MaON gave an experimental equivalent weight

of 142; the calculated equivale«t «eight for this diacid is 143. The

infrared spectrum of the product Showed a strong ester absorption and no

anhydride absorption.

Several commercial furan'prepolymers were studied. The exact

structures of these prepolymers are not known, but in general, they are

prepared by partially polymerizing furfuryl alcohol with an acid catalyst.

When the desired vicsocity is reached, the reaction is stopped by the addition

of base. The prepolymer can be stored for extended periods and further

polymerized by adding more acid.

Furfural was not polymerized by diacid 150 or Empol 1014 (a C», 3o

diacid). Furfuryl alcohol could be polymerized by the diacid 150, but only

to rigid, brittle resins. Empol 1014 was not effective.

Attempts to polymerize the various furan prepolymers with Empol

1014 resulted in either incompletely cured viscous liquid or foamed, rigid

12

I I


AtCXANORIA.VmaiNIA

1

materials. When dlacid 150 was used to cure these prepolymers, generally

a hard, rigid product was obtained. However, formulations 73 (Table VIII)

1 and 77, 78, 79 (Table IX) were cured to soft, flexible materials. Whether

these materials become rigid on further heating or at ambient temperature is

being investigated.

If these furan prepolymers contain two or more free hydroxyl groups

per molecule, it may be possible to cure them with epoxy resin or poly-

isocyanates. The formulations using Atlas' furfuryl alcohol prepolymer (Table X)

show some promise and will be investigated further. Both Araldite DP437

and Dow Coming's QZ-8-0914 (epoxy resins) yield very flexible but jelly-

like materials.

i

I

!

i

13 -


ALCXANORIA,VIN(IINLA li

TABLE V

Polymerization of Furfural with Acid Catp.lysts

Formulation Cure Conditions

Samples were placed in the oven for 18 hrs at 90 0C

Furfural/Empol 1014_

1A 9:1

2A 8:2

3A 7:3

a 6:4

Results

Samples were not compatible and did not cure

I

Furfurftt/Diacld ISO

5A 9:1

oA 2:2

7A 7:3

8A 6:4

Left at room temperature overnight and then placed in an oven for 18 hrs. at 50oC

Samples did not cure

14

I !



TABLE VI

Polymerization of Furfuryl Alcohol with Acid Catalysts


Furfuryl Akoliol/Diacid 120

9A 9:1

Samples were cured in an oven at 100eC

10A 8:2

UA 7:3

12A 6:4

Results

All of the samples foamed on curing and were rigid

Furfuryl Al £ßhfii/Ji iacid 150 Samples were left at room temperature over-

13A 9:1 night and then placed in

14A 8:2 an oven at 500C for 18 hours

15A 7:3

16A 6:4

All of the samples cured to hard and brittle resins

Fvrfwvyl A ICl 101.4 The samples were placed in an oven at 40"C for

All samples were syrupy and incom

17A 9:1 several hours and then pletely cured

18A 8:2 at 100oC for 18 hours

19A 7:3

20A 6:4

15

ATLANTIC RCICARCH CORPORATION

ALCXANORIA.VIROINIA

TABLE VII

Polymerization of Furfuryl Alcohol Frepolymer (Atlas) with Acid Catalysts

Formulation

1014

Cure Conditions Results

fti»n Pyw9lYrr/%9\ 43 9:1 10 hours at 120oC Very viscous liquid,

surface skin

44 8:2 it ti Foamed, cured material rigid and brittle

45 7:3 it n it tt

46 6:4 it tt ti tt

Furan FreDolvmer/Diacid 150

47 9:1

48

49

50

8:2

7:3

6:4

10 hours at l20oC

16

Cured, foamed, slightly flexible, brittle

Cured, foamed, rigid, brittle

it is n

it ii n

li

I I I I I I I I I

ATLANTIC RCSCARCH CORPORATION

ALEXANDRIA, VIRGINIA

TABLE VIII

Polymerization of Furan Prepolymer (Durez) with Acid Catalysts


Furtn Prepolymer/Empol 1014

51 9:1 18 hours at 1200C

52 8:2

53 7:3

54 6:4

Furan Prepolymer/Diacid-TiO

55 9:1

56 8:2

57 7:3

58 6:4

Furan Prepolymer/Diacid-150

73 9:1

18 hours at 120oC

74 8:2

75 7:3

76 6:4

18 hours at 50oC then 18 hours at 70oC

18 hours at 500C

ii ii

ii ii

17

Results

Empol 1014 not compatible with furan prepolymer

Rigid, foamed, brittle

ti

II

Initially viscous. On further curing, became very flexible and soft





ALCXANOmA.VmOINIA

TABLE IX

Polymerization of Furan Prepolymer (Jet-Kote X-3M) with Acid Catalysts

Formulation

Jet-Kou X-3M/gmp9l 1Q14 59 9:1

60 8:2

61 7:3

62 6:4

Jet-Kote X-3M/Diac :id •W 63 9:1

64 8:2

65 7:3

66 6:4

Jet-Kote X-3M/Diacld-150

77 9.5:0.5

78 9:1

79 8.5:1.5

Cure Conditions

18 hours at 120oC

18 hours at 120oC

18 hours at 50oC

Results

Viscous liquid

Viscous liquid

Viscous liquid

Viscous liquid

Cured, flexible, brittle

Cured, slightly flexible, brittle

Cured, rigid, brittle

Cured, rigid, brittle

Cured, flexible, soft



I

18

I I 1 I I 1 I I I I I 1

ATLANTIC REIEAMCH CORPORATION

ALEXANDNIA.VIRdlNIA

TABLE X

Co-Polytnerlzation of Furfuryl Alcohol Prepolymer (Atlas) with Epoxy Resins and Polylsocyanates


Furan Prepolvmer/OZ-8-0914 (eooxv)

8 hours 1 1:2 at 1000C

2 1:1

3 2:1

Furan Prepolvmer/Araldlte DP437 (epoxv)

4 1:2 8 hours at 1000C

5 1:1

6 2:1

8 hours at 1000C

Furan Prepolvmer/Epon 828 (epoxy)

7 1:2

8 1:1

9 2:1

Furan Prepolymer/Hexamethylene Dllsocvanate

10 1:2 8 hours at 1000C

11 1:1

12 2:1

Furan Prepolvmer/Toluene-2.4-Dll80Cvanate

13 1:2 8 hours at lOO'C

14 1:1

15 2:1

Results

All samples cured to a flexible, jelly-like material

All samples cured to a flexible, jelly-like material

Rigid and brittle

it it n

Soft and flexible

Slightly flexible, hard

Rigid and brittle

Foamed , rigid

n II

ii II

19

ATLANTIC RCBCARCN COHPOHATION

ALCXANOdlA.VimilMIA

TABLE XI

Co-Polymerization of Furan Prepolymer (Durez) with Epoxy Resins and Polyisocyanates

Formulation

Furan Prepolymer/QZ-0914 (epoxv)

16 1:2

17 1:1

18 2:1

Cure Conditions

24 hours at 1009C

Results

Flexible but soft

Very viscous liquid n ii n

Furan Prepolymer/Araldite DP437 (epoxv)

19 1:2 24 hours at 100eC

20 1:1

21 2:1

Very viscous liquid

II

n

II

II

I

Furan Prepolvmer/Epon 828 (epoxv)

22 1:2

23 1:1

24 2:1

24 hours at 100"C Rigid and brittle

it

n

n

n

II

it

Furan Prepolymer/Hexamethylene Diisocyanates

25 1:2 24 hours at 1000C

26 1:1

27 2:1

Slightly flexible

Flexible but brittle

Rigid, brittle

Furan Prepolvmer/Toluene-2.4-Dil80cvanate

28 1:2 24 hours at lOO'C

29 1:1

30 2:1

Foamed, rigid it it

it n

20

I


ALEXANDRIA, VIRdlNIA

III. SUMMARY OF INSULATION WORK

A brief sunnary of the status of this program to date is re-

ported here. Flexible epoxy, phenolic, and urethane resins were deve-

loped for insulation studies. Asbestos fiber-filled moldings were pre-

pared and evaluated for insulation performance in the oxyacetylene

torch and in static-motor firings. In addition to asbestos fibers,

potassium oxalate, asbestos fiber-potassium oxalate, silica micro-

balloons, magnesium carbonate, and asbestos powder have been investi-

gated as possible fillers for the more promising resins.

Considerable effort was devoted to the preparation of

flexible melamine resins. Although a few flexible formulations were

developed, asbestos-filled moldings have not been successfully prepared.

Studies with the furan resins have yielded several flexible materials

by co-polymerizing furan resin prepolymers with epoxy resins and

diisocyanates.

I I 1 1 I I I I 1

The best insulations developed to date in this program are

I summarized in Table XII. The better commercially available motor-cast

insulations have char rates of approximately 3.0 mil/sec in our test

| motors. In addition to the insulation performance, the density

* of the material is also an Important consideration in the selection

. of insulation for missile applications. Other properties being

! equivalent, the product of char rate and density allows a numerical

rating of the material according to over-all effectiveness, with the

lowest number representing the best material. The volume requirements

of the Insulation are neglected.*

| It should be emphasized that (1) the data in Table XII

represent only a limited number of tests; (2) char rate differences

I of 0.5 mil/sec are probably not significant when based on one or two

tests; and (3) differences In the propellent used, time duration of the

motor firing, pressure, and specimen position, make it difficult to

compare materials tested in different motors. U. S. Rubber Company's

| 3015 and 3016, and General Tire and Rubber Company's Gen-Gard V-44

were used as comparative standards and represent some of the best

commercially available insulation materials.

* This point is discussed in the Second Annual Summary Report, This Contract, July 31, 1962, pp. 40, 73.

- 21 -

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- 22

I

I

ATLANTIC RCICANCH CORPORATION

ALKXANORIA.VIROINIA

IV. FUTURE WORK

I I 1

During the next year of this program, the following general areas

■ of work will be emphasized:

(1) Continuation of the development of flexible resins of the furan,

melamlne, polyester and urethane types;

(2) Study fillers other than asbestos, or combinations of other

{ fillers with asbestos, in the best resins developed to date (epoxy and

phenolic);

| (3) Screen newly developed resins (filled type) by means of the

oxyacetylene torch test and test by static motor firings the most promising

i candidates; and

(4) Furnish the Rock Island Arsenal Laboratory approximately one

I pound samples of several of the best flexible resins developed under the contract

for use in compounding studies.

- 23 -

I ATLANTIC RCICANCH CONPORATION

ALEXANDRIA, VIHOINIA

APPENDIX

Formulary

1. Araldlte DP-437 (Clba): An Inherently flexible, liquid epoxy resin, epoxy equivalent 285.

2. Asbestos fiber 3R100 (H.K. Porter Co.): Chrysolite asbestos fibers.

3. BDMA (Miles Chemical Company): Benzyldimethyl amine.

4. Castor oil (The Baker Castor Oil Co.):

0

CH2—0. — (CH2)7CH=CH—CH2CH(0H)—(CH2)5—CH3

CH — 0— C — (CH2)7CHr=CH—CH2CH(OH)--(CH2)5—CH3

Ch^—0 —C—(CH2)7CH=:CH—CH2CH(0H)—(CH2) —CH

5. Castor oil-modified Guardian (Atlantic Research Corp.)

40% modification 1.00 part Epon 828 1.29 parts NMA 1.32 parts castor oil

6. Diacid-150

HOOCCH—CHC00(CH ) 00CCH=CHCOOH

7. Eccospheres SI (Emerson and Cuming): hollow glass microspheres

Empol 1014 (Emery): A mixture of 95 per cent of C of C-. triacid, and 1 per cent of a monobasic acid.

8. Empol 1014 (Emery): A mixture of 95 per cent of C., diacid, 4 per cent

A-l


ALCXANORIA.VIROINIA

9. Epon 828 (Shell Chemical Corp.): Liquid epoxy resin; epoxy equivalent 180-195.

A CH2 CHCH2- 0 —

CH / . OH

-c —(/ NVOOLCHOL ^3 W 2 2

li I

10. (a) Furan prepolymer (/"-.las Mineral Products Co.) - a low viscosity (800-1000 cps) furfuryl alcohol polymer

(b) Furan prepolymer (Hooker Chemical Corp, Durez) - a low viscosity UOOcps) furfuryl alcohol resin (Code No. 16470).

(c) Furan Prepolymer - "Jet-Kote" X-3M (Furane Plastics Co.) - Nature of the resin unknown.

11. Furfural («'isher Scientific Company)

•CHO v 12. Furfuryl alcohol (Eastman Organic Chamicals)

X^ .OH

13. Gen-Card V-44 (The General Tire and Rubber Company): Asbestos-filled

butadiene-acrylonitrile rubber insulation.

14. Guardian (Atlantic Research Corporation): This material was referred to previously as Standard Guardian. Its formulation is:

10 parts Epon 828

9 parts NMA

A-2

I !

ATLANTIC RHCANCH CDRPQUATION

ALCXANDRIA.VIROINIA

15. Hexamethylene dllsocyanate (Mobay Chemical Company): 0CN(CH2)6NC0

16. LP-8 (Thiokol): A liquid polysulflde with the following average structure and which some side mercaptan groups occur occasionally:

HS fC2H5OCH2CC2H4—S -flh-374C2H40CH20C2H4—SH

17. LP-33 (Thiokol): Similar to LP8 but the molecule is less cross-linked and the repeating unit occurs 6 times per molecule.

18. Nadic methyl anhydride (National Aniline):

CH,

19. Oxlron 2000 (Food Machinery and Chemical Corporation): Epoxldlzed polyolefin:

CH0CHCH(CH0) CH CH(CH.) CHZZICH^CH^CHCH^CH 2f I 2 2 "^0/ 2 2 OHO

0=0 I

CH,

2" 2T—2

-CH CH

•CH2 CH2

J" 20. Potassium oxalate (Fisher, Certified): KjCJ) «HO

21. QZ-8-0914 (Dow Corning): Technical grade of Syl-Kem 90. See following structure.

A-3

: ATLANTIC RESEARCH CORPORATION

ALEXANDRIA,VIROINIA

22. Syl-Kem 90 (Dow Corning): A liquid epoxy resin.

/A ^ PS A (»2 CHCH 0(CH2)3 Si— 0—Si (CH^OO^CH—CH2

CH3 ^3

23. THPA, tetrahydrophthalic anhydride (Allied Chemical):

A.

24. Toluene diisocyanate (Du Pont, Hylene T):

CH3

NCO

«CO

25. U. S. Rubber Company's 3015 insulation (U.S. Rubber): One of the best commercially available insulations. Used as comparative standard in this work. Potassium oxalate filler.

26. U. S. Rubber Company's 3016 insulation (U.S. Rubber): One of the best commercially available insulations. Used as a comparative standard in this work. Asbestos fiber filler.

a I! I!

A-4

I I I 1 1 [

1 I I I I

f



Office of the Director of Defense Research

and Engineering

Room 3E-1028, The Pentagon Washington 25, D.C. Attn: Mr. J. C. Barrett (1)

Advanced Research Project Agency The Pentagon

Washington 25, D. C. Attn: Dr. G. Mock (1)

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Arlington Hall Station Arlington 12, Virginia (1)

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Department of the Army Washington 25, D. C.

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Commanding Officer Ordnance Materials Research Office

Watertown Arsenal Watertown 72, Massachusetts Attn: RPD (2)

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& Packaging Lab (1)

Mr. D. Stein, 0RDBD-DE3 (1)

Commanding Officer PLASTEC Picatinny Arsenal Dover, New Jersey (1)

Commanding Officer Rock Island Arsenal Rock Island, Illinois Attn: Materials Section, Laboratory (1)

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Springfield 1, Massachusetts Attn: Mr. R. Korytoski, Research

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Agency Arlington Hall Station

Arlington 12, Virginia Attn: TIFDR (10)

Chief, Bureau of Naval Weapons Department of the Navy Room 2225, Munitions Building Washington 25, D.C. Attn: RMMP (1)



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USAF Directorate of Research & Development Roon 4D-313, The Pentagon Washington 25, D.C. Attn: Lt. Col. J. B. Shipp, Jr. (1)

Wright Air Development Division Wright-Patterson Air Force Base Dayton, Ohio Attn: ASRCEE (WWRCEE) (2)

ARDC Flight Test Center Edwards Air Force Base California Attn: Solid Systems Division, FTRSC (5)

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II

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(1)

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(1)

I I I


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U. S. Army Ordnance District, Philadelphia 128 North Broad Street Philadelphia 2, Pennsylvania Attn: R&D BR, OD (1)

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General Electric Company Rocket Engine Section Flight Propulsion Laboratory Department Cincinnati 15, Ohio (1)

Jones & Laugh1in Steel Corporation 45 South Montgomery Avenue Youngstown 1, Ohio Attn: Mr. H. Steinbrenner (1)

Arthur D. Little, Inc. Acorn Park Cambridge 40 Massachusetts Attn: Dr. Blndarl (1)

Lyon, Inc. 13881 W. Chicago Boulevard Detroit, Michigan Attn: W. Martin (1)

Manufacturing Laboratories 249 Fifth Street Cambridge 42, Massachusetts Attn: Dr. P. Foplano (1)

Dr. V. Radcliffe (1)

Massachusetts Institute of Technology Cambridge, Massachusetts Attn: Prof. Backefen (1)

Prof. M. C. Flemings (1)

Mellon Institute 4400 Fifth Avenue Pittsburgh 13, Pennsylvania Attn: C. J. Owen (1)

Dr. H. L. Anthony (1)

Norris-Thermador Corporation 5215 South Boyle Avenue Los Angeles 58, California Attn: Mr. L. Shlller (1)

Ohio State University Research Foundation Columbus, Ohio Attn: Dr. McMaster (1)


ALEXANDRIA, VIRGINIA

The Perkin-Elmer Corporation Main Avenue Norwalk, Connecticut Attn: Mr. J. Beardsley (1)

Pratt & Whitney Aircraft East Hartford Connecticut Attn: Mr. W. Dahl (1) Mr. C. Baxter (1)

Reactive Metals Corporation Miles, Ohio

I Attn: Mr. H. Lundstrom (1) |

Republic Steel Corporation Research Center 6801 Brecksville Road Cleveland 31, Ohio Attn: Dr. H. P. Munger (1)

Space Technology Laboratories, Inc. P. 0. Box 95001 Los Angeles 43, California Attn: Technical Information Center

Document Procurement (1)

Titanium Metals Corporation 233 Broadway New York, New York Attn: Mr. G, Erbin (1)

United States Rubber Company Research Center Wayne, New Jersey Attn: Dr. E. J. Joss (1)

Library Rohm & Haas Company Redstone Arsenal Research Division Huntsville, Alabama (1)

Douglas Aircraft Company, Inc. Santa Monica Division Santa Monica, California Attn: Mr. J. L. Weisman (1)

Commanding Officer Special Projects Office Department of the Navy Washington 25, D.C. Attn: Mr. Harold Bernstein SP-27 (1)

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ad 286 392 - dtic.mil · gi/cc. the effect on the char rate of various amounts of asbestos fibers...

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