AD-750 5551

HTPB POLYMER IMPROVEMENT

W. D.

Allan,

et al

Lockheed Propulsion Company

Prepared for: Air Force Rocket Propulsion Laboratory September 1972

DISTRIBUTED BY:

National Technical Information Service U.S. DEPARTMENT OF COMMERCE

5285 Port Royal Road, Springfield Va. 22151

APRPI.,TR -72- go

LPC DOCUMENT NO. 625-1- 2

HTPB POLYMER IMPROVEMENT

LOCKHEED PROPULSION COMPANY REDLANDS, CALIFORNIA

APPROVED FOR PUBLiC RELEASE; DISTRIBUTION UNLIMITED

TECHNICAL REPORT AFRPL-TR-72-.89

SEPTEMBER 1972
N,,*r";t,al I['t2,,A

AIR FORCE ROCKET PROPULSION LABORATORN RESEARCH AND TECHNOLOGY DIVISION AIR FORCE SYSTEMS COMMAND UNITED STATES AIR FORCE EDWARDS, CALIFORNIA

Alt

a -

wbite 31

:I

Div.

7-AVAILCOf~W-OILF'

Then U.S. Government drawings, specifications, or other data are used for any purpose other, than 'a definitely related Government , .ocurement operation, the Government thereby incurs no responsibility nor any obligation whatsoever, and the fact that the Government may have formulated, furnishled, or in any way supplied the said drawings, specifications, or other'data is not'to be regarded by implication or, otherwise, or in any rmanner licensins the, holder or any. person o*corporation, or conveying any rights or permission, to manufacture, use, or sell any patented invention that'may in any way be related thereto. "

UNCLASSIFIED
Security Classification

DOCUMENT CONTROL DATA -R & D

(Security classification of title, body of abstraCt Ilid ORIGINA TING AC TIVI 'Y (Corporate author) inde ting agnn totiton niu.. be entered "hen the l20. REPORT -railreport Is classIfted) CLASSIFICATION i.CCURITY

Lockheed Propulsion Company

Unclassified
b, GROW"

P.O. Box 111

Redlands, California
3. REPORT TITLE

92373

HTPB POLYMER IMPROVEMENT

4. DESCRIPTIVE NOTES (Type of report and Inclusive dates)

Technical Report,
S, AU THOR450 (First name, middle Initial, last name)

W.D. Allan, W.E. Baumgartner and G.E. Myers,

0.
REPORT DATE

1 May , '72 through 31 August 1972

.ES 7b. NO. OF REFS

7a. TOTAL NO. OF P

September 1972
Ba. CONTRACT OR GRANT NO.

36]
90. ORIGINATOk '1

I
... RT NUMOERIS)

F04611-72-C-0038
b. PROJECT NO.

625-1-2

C.

9b. OTHER REPO. t ?.O(S) (Any other numbors that may be asSIgned thir report)

AFRPL 7 11-72-89
10 DISTRIBUTION STATEMENT

Approved for Public Release; Distribution Unlimited

It, SUPPLEMENTARY NOTES 1i2. SPONSORNG MILITARY ACTIVITY

Air Force Rocket Propulsion Laboratory Edwards Air Force Base, California
13. ABSTRACT

From among the laboratory preparations of modified R-45M HTPB prepolymer that were previously examined, four were produced in a pilot plant for evaluation in 90-percent solids propellant. The pilot plant samples covered a molecular weight range from 2700 to 4100 and possessed weight average functionalities between 2.0 and 2,1. Propellant processability in each case was inferior to that of standard R-45M. On tht; basis of tensile properties and crack propagation tests, no distinctive differences in propellant mechanical behavior were apparent. Detailed comparison of thermal cycling behavior will be made in the final program phase.

DD

I NOV

FORM

1473

UNCLASSIFIED
Sccur.tlrl CI.ISSIIii .ItI'.f

UNCLASSIFIED
Security Classification
14 KEY

WOROS

LINK ROLE

A WT

LINK

-B

LINK ,,C ROLE, WT

ROLE

WT

HTPB prepolymer improvement Functionality Molecular weight Processability Mechanical properties

UNC LASSIFIED
Security Classification

AFRPL-TR-72- 89

ITPC

OCUMENI' NO. 625-1-2

HTPB POLYMER IMPROVEMENT

-S,

,TUMBIR 1972

AFRPL-TR-72-89

FOREWORD This is the second Technical Summary Report issued under Contract F04611-72-C-0038, "HTPB Polymer Improvement", a program being conducted by Lockheed Propulsion Company, Redlands, California, and monitored by the Air Force Rocket Propulsion Laboratory (Robert L. Limoges, Second Lieutenant, MKPA, Program Monitor). The program is being conducted in cooperation with the manufacturer of the R-45 HTPB prepolymer: the Atlantic Richfield Corporation (ARCO), Philadelphia, Pennsylvania; and with the Government Research Laboratory, Esso Research and Enginleering, Linden, New Jersey. Participating technical personnel are Dr. W. E. Baumgartner (Program Manager), Dr. G.E. Myev8 (Project Engineer), W. D. Allan and W. E. Heikkila at Lockheed Propulsion Company; Dr. P. W. Ryan and K. C. Ramey at ARCO; and A.E. Muenker at Esso. Publication of this report does not constitute Air Force apnroval of the report's findings and conclusions, it is published only for the exchange and stmnulation of ideas.

Robert L. Limoges Second Lieutenant MKPA

-ii

AFRPL-TR-72-89

ABSTRACT From among the laboratory prep'-ratiens of modified R-45M HTPB prepolyrner that were previously exarnined, four were produced in a pilot plant for evaluation in 90-percent solids propellant. The pilot plant samples covered a molecular weight range from 2700 to 4100 and possessed weight average functionalities between 2.0 and 2.1. Propellant processability in each case was inferior to that of standard R-45M. On the basis of tensile properties and crack propagation tests, no distinctive differences in propellant mechanical behavior were apparent. Detailed comparison of thermal cycling behavior will be made in the final program phase.

(1

-iii

AFRPL-TR-72-89

TABLE OF CONTENTS Section I II III INTRODUCTION SUMMARY RESULTS I. PREPOLYMER PREPARATION AND CHARACTERIZATION a. b. 2. Analytical Results Parameter Correlation Page I 3 5 5 5 9 9 9 16 16 30 30 33

EVALUATION IN PROPELLANT a. b. c. d. Propellant Processability Propellant Tensile Behavior Propellant Fracture Mechanics Strain/Temperature Cycling of JANNAF Specimens

3. IV Appendix A

CONCLUSIONS

FUTURE WORK

LABORATORY SAMPLE CHARACTERIZATION SUMMARY

35

-iv-

AFRPL-TR-72-89

LIST OF ILLUSTRATIONS Figure I 2 3 4 5 6 7 i Prepolymer Viscosity versus Mn Prepolymer Tw versus Rn Relative End-of-Mix Viscosity versus Mn Tensile Behavior of Control Sample (90-percent Solids); NCO/OH = 0.80; 0.54 in./in./min Tensile Behavior of Control Sample (90-percent Solids); I\TCO/OH = 0.80; No MT-4; 0.54 in./in./min Tensile Behavior of Sample F-2 (90-percent Solids); NCO/OH = 0.95; 0.54 in./in./min Tensile Behavior of Sample F-2 (90-percent Solids); NCO/OH = 1.0; No MT-4; 0.54 in./in./min of Sample G-2 (90-percent Solids); Tensile in./in./min NCO/OH Behavior =0.85; 0.54 Tensile Behavior of Sample G-2 (90-percent Solids); NCO/OH = 0.85; No MT-4; 0.54 in./in./min Tensile Behavior of Sample R-2 (90-percent Solids); NCO/OH = 0.95; 0.54 irn./in./min Ten~sile Behavior of Sample R-2 (90-percent Solids); NCO/OH = 0.95; No MT-4; 0.54 in./in./min Tensile Behavior of Sample S-2 (90-percent Solids); NCO/OH = 1.05; 0.54 in, /in./min Page 11 12 14 19 20 21 22 23

"9
10 II 12

24 25 26 27

4' 4

4
[~

AFRPL-TR-72-89

LIST OF TABLES Table I II III IV ANALYTICAL CHARACTERIZATION OF PILOT PLANT SAMPLES COMPARISON OF ANALYTICAL PARAMETERS: LABORATORY VERSUS PILOT PLANT SAMPLES SOLVENT PRECIPITATION FRACTIONATION OF PILOT PLANT SAMPLES COMPARISON OF MEASURED AND CALCULATED P \RAMETERS FOR SOLVENT PRECIPITATED FRACTIONATION PROPELLANT P;'_OCESSABILITY (90% SOLIDS); VISCOSITY (KP AFTER HOURS) RELATIVE PROPELLANT VISCOSITY AFTER 3 HOURS AT 40 0 C VII PROPELLANT MECHANICAL PROPERTIES AT 9, PERCENT SOLIDS (From Instron Load/Time 15 Page 6 7 8

10 13

V VI

"-.-ace)
VilI IX COMPARATIVE TENSILE PROPERTIES TENSILE PARAMETERS FROM TRUE STRESS/ STRAIN CURVES FOR 90 PERCENT SOLIDS PROPELLANT PROPELLANT CRACK PROPAGATION TEMPERATURE/STRAIN CYCLING RESULTS

17 18

28 ?9 31

X XI

-vi-

AFRPL-TR-72-89

GLOSSARY ARCO B, C, E, F, G,K, L, M, N, N', O, P, Q EOM Esso fn fw " GPC HTPB IPDI KP LPC Mn Mw MT-4 NCO/OH p RR R-45M TSI VPO 7, 0-nE in, rm 0'b/Eb Atlantic Richfield Corporation

Laboratory preparations of prepolymer End of mix Government Research Laboratory, Esso Research and Engineering Number average functionality Weight action furnct.ionality Gel permeation chromatography Hydroxy-terminatvd polybutadiene Isophorane diisocyanate Kilopoise Lockheed Propulsion Compan) Number average molecular weight Weight average molecular weight Bonding agent Isocyanate to hydroxyl equivalents ratio poise Round Robin R-45M. ARCO HTPB. Lot 110225

Free radical polymerized

Toluene sulfonyl isocyanate Vapor phase osmometer Prepolymer viscosity in poise Stress and strain at maximum load (stress) Stress and strain at rupture (The reverse is blank) -vii-

AFRPL-TR-72-89

SECTION I INTRODUCTION The commercially available ARCO R-45M HTPB prepolymer is being extensively studied for applications in highly loaded solid propellants and possesses some advantage over CTPB prepolymers in those systems. It does have some deficiencies, however, in potlife control and in balancing mechanical properties at low and high niperatures, which presumnably are caused by the material's low molecuh,' weight (Mn - 3000), high functionality (fw 2.3), and high reactivity of its functional groups. This program was established to determine whether the available variations in ARCkAs free radical polymerization process could produce a modified R-45M possessing superior characteristics for use in solid propellants. in the program ARCO was to prepare 11 prepolymer samples under laboratory conditions/scal-, each sample representing specific variations in their polymerization process. Those samples were to be characterized by both ARCO and Esso and evaluated in propellant on a small scale by LPC. Subsequently, three of those prepolymer lots were to be scaled up to the pilot plant level, characterized, and evaluated for propellant performance. The first report under the program described the results of the characterization and evalu;.tion of the laborator7 samples (Ref 1). Those samples possessed z vide range of average molecular weight and average functionality. Their propellhnts also exhibited a wide range of procesoability, controlled primarily by molecular weight. However, propellant tensile properties generally showed relatively minor variations among the samples, i. e. , molecular weight and functionality had little effect upon tensile behavior. From the available data three prepolymers were selected for scaleup, covering the molecular weight range from about 2500 to 4000 and possessing functionalities very close to 2.0. This report describes the characterization and evaluation of the pilot plant samples.

(Ref 1).

Baumgartner, W. E. and Myers, G.E., HTPB Polymer Improvement, AFRPL-TR-72-50, LPC Report No. 625-1-1, June 197Z (The reverse is blank)

--

AFRPTL-TR-72-89

SECTION HI SUMMARY From the polymerization process conditions previously employed in producing 14 laboratory samples of R-45M type prepolymers, ARCO has used four conditions on the pilot plant scale to produce four prepolymers at the 25- to 50-pound level. These were characterized analytically by ARCO and Esso, and evaluated by LPC in 90-percent solids propellant (Oronite-6 plasticizer, IPDI curative, with and without MT-4).

The analytical results are summarized as follows:

* 0 F * Reproducibility between pilot plant and laboratory preparations is excellent. Kin varied from 2700 to 4100 with fw values between 2.0 to 2.1. Solvent precipitation fractionation took place on the basis of molecular weight and/or equivalent weight, with some indication that w increases with Mn"

Evaluation in propellant showed the following: * Processability of the pilot plant samples was inferior to that of standard R-45M. However, this may be at least partially the consequence of higher impurity levels occasioned by incomplete pilot plant cleanup. No clear superiority over standard R-45M was observed from tensile properties or from crack propagation tests. (Some indication of improved thermal cycling capability was obtained from feasibility tests of a simultaneous strain/temperature cycling procedure, but these results must still be regarded with caution.)

However, this somewhat unexpected failure of material having higher no,,lecular %eight and functionaiities close to two, to produce improved propellant mechanical behavior could b the consequence of relying largely upon uniaxial tensile tests for the mecL-w. A.t. properties evaluation. The last phase of the program will evaluate ki- :eater detail the thermal cycling capability of propellants prepared from tlhrec of the pilot plant prepolymers.

(The reverse is blank)

-3-

~AFRPL-TR-72-89

SECTION III RESULTS 1. PREPOLYMER PREPARATION AND CHARACTERIZATION

Four prepolymers were prepared in the ARCO pilot plant at approximately the 50-pound level; three of them were prepared under conditions duplicating those used for the laboratory samples F, G, and R.,, while the fourth (S-2) involved a further process modification. Initial preparations contained unacceptably high iron levels due to reactor startup problems. The repeat preparations tended toward higher iron levels than possessed by the laboratory samples but were regarded as satisfactory for the program. After preparation, all samples were stored under nitrogen in air-tight containers. Pilot plant samples have been designated F-2, G-2, R-2, and S-2 to distinguish them from the laboratory samples F, G, etc. a. Analytical. Results

The samples were characterized by number average molecular weight, analytical GPC, equivalent weight, number average and weight average functionality, viscosity, and impurities using methods described in the previous report (Ref 1). 'In addition, preparative scale fractionations were conducted by solvent precipitation at ARCO and the fractions also were characterized. Table I summarizes the analysis results for the pilot plant samples, and Table II compares several parameters for pilot plant versus laboratory preparations. The following points are noted: Kn varies from about 2700 to 4100 and polydispersities are nearly equal. fn values are all 2.0 within experimental error whereas values of fw are between 2.0 and 2.1. . * S-2 appears to be equivalent to R-2. Reproducibility between laboratory and pilot plant is excellent.

ARCO separated each of the pilot plant samples into three fractions by addition of methanol to a 10-percent cyclohexane/acetone solution at 25 0 C. Table III summarizes the analytical values for the fractions and Table IV compares the corresponding parameters for each of the original prepolymers with those calculated from the fractionation data, The fractionation obviously took .lace on the basis of both Mn and equivalent weight. Table III indicates that 1w increases with molecular weight, but some doubt is cast upon that conclusion by the comparison of measured and observed fw
':

A tabulation of analytical results obtained for the laboratory samples is included as Appendix A for reference purposes. -5-

AFRPL-TR-72-789

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-6-

AFRPL-TR-72-89

TAB LE II COMPARISON OF ANALYTICAL PARAMETERS: LABORATORY VERSUS PILOT PLANT SAMPLES Parameter(a) Eq Wt (c) 2270/2060 (-9%) 1770/1490 (-15%) 12Z0/1420 (+16%) 1.81/1.99 (+10%) 1.75/2.03 (+16%) 2.08/1.94 (-7%)

Sample F G R

n(b) 4100/4080 ( 1%)(e) 3100/3010 (-3%) 2530/2760 (+9%)

(d) 2.03/2.03 (0) 2.04/2.08 (+Z%) Z.10/2.03 (-3%)

(a) (b) (c) (d) (e)

Laboratory/pilot plant VpO TSI Laboratory samples without catalyst. Pilot plant samples with catalyst. Percent change from laboratory to pilot plant.

-7-

AFRPL-TR-72-89

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AFRPL-TR-72-89

in Table IV, which indicates that some modification of the fractions may have occurred during their preparation. Such modification, however, did not significantly affect molecular and equivalent weights. b. Parameter Correlation

The first interim report presented crossplots for a number of the measured prepolymer parameters to determine what correlations might exist. Figures 1 and 2 illustrate two such plots when data points for the pilot plant samples are included. Figure 1 demonstrates that both laboratory and pilot plant sampler follow the same 1/Mn relationship, and Figure 2 confirms that the ARCO polymerization process can vary molecular weight and functionality independently. Z. EVALUATION IN PROPELLANT

The four pilot plant prepolymer samples and a control (standard R-45M, Lot 008281) were evaluated at the 1-gallon mix scale in propellant containing 90-percent solids, 3-percent Oronite-6 plasticizer, and cured with IPDI. The evaluation was made at a minimum of two NCO/OH ratios with MT-4 bonding agent, and at one NCO/OH ratio without MT-4. Cure was at 160OF for 7 days. a. Propellant Processability

The propellants were processed in a 1-gallon vertical BakerPerkins mixer modified with a bottom discharge valve for casting directly from the mixer. A 170-minute mix cycle was employed, including 90 minutes after completing the addition of solids and 30 minutes final mix after curative addition. The end-of-mix (EOM) and potlife viscosities were determined by means of a Brookfield viscometer and a T-F bar. Table V summarizes the viscosity data. As expected, much higher propellant viscosities were observed in the propellants containing MT-4 than in those that had no bonding agent. Where MT-4 was present, all of the pilot plant samples had EOM viscosities higher than those of the control (except sample S-2 at an NCO/OH ratio of 1.05). The relationship between prepolymer Mn and the relative EOM viscosity of the pilot plant samples is presented in Figure 3, along with the previous data for the laboratory samples. Within the data scatter, EOM viscosity is controlled generally by prepolymer Mn, with deviations probably occasioned by reactivity differences. Table VI lists the relative mix viscosities 3 hours after EOM for the formulations containing MT-4. These values were obtained by smoothing the data from Table VI and are judged to be accurate to 0.05-0.J. Processability therefore is in the order of Control >F, R> G, S. It is possible, however, that the poorer processability of the pilot plant samples to some extent may be due to their relatively high iron content. As noted earlier this is a temporary deficiency that should be obviated in further production. In the present study, no casting difficulties were encountered with any of the test formulatio'ns.

-9

,AFRPL-TR-72-89

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AFRPL-TR-72-89

700

SAMPLE6 R-45 (LAB), ,R-45,(PILOT PLANT)---O-CTPB bTELAGEN HT

400 ---

-- 6
A

N, P

N'

200
0

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> 70

A SG-2

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40 D

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Figure 1

Prepolyrner Viscosity versus Mn -!l-

ii

AFRPL-TR-72-89

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AFRPL-TR-72-89

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AFRPL-TR-72-89

7 6

C1 86% SOLIDS

SAMPLE
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0 88% SOLIDS
A 90% SOLIDS

5_
4F20

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F, F

p
G-2 S-2 R-2 --

--

LQ
CONTROL K

3 .--

CG

2 O

RE M

2 3 4 5 6 RELATIVE EOM VISCOSITY (sample/control)

Figure 3

Relative End-of-Mix Viscosity versus Kn

-14-

AFRPL-TR-7Z-89

TABLE VI RELATIVE PROPELLANT VISCOSITY AFTER 3 HOURS AT Sample Control F-2 G-2 R-2 s-2 Relative Viscosity 1.0 1.3 1.6 1.4 1.7
4 0 C(a)

(a)

MT-4 formulations

-15-

AFRPL-TR-72-89

b.

Propellant Tensile Behavior

Uniaxial tensile properties at -65, 70, and 140F were measured at a strain rate of 0.54 in./in./min using the milnithirn tensile specimens previonsly described (Ref 1).

(i)

Summary of Conventional Tensile Parar,,eters

Table VII summarizes, for all formulaticris tested, the values of tensile parameters as conventionally reported. The,,e include initial modulus E 0 , stress and strain at maximum load (O/E)n, ai!d stress

and strain at rupture (o/O)b. Additionally, swell and gel measuirclnen-ts, which are indicative of binder crosslink density, are included for ach of the formulations tested. The effect of MT-4 is to "harden" the pr6dellant
at higher temperatures and to increase strain at -65 0 F. (2) Comparison at Constant 75F

%m

['

To permit comparison of tensile properties under similar conditions, NCO/OH ratios were selected that produced values for am at 75 0F between 140 and 160 psi. Resultant conventional tensile paramileters are given in Table VIII. On this basis none of the prepolymer samples is clearly superior to the control lot. (3) True Stress/Strain Curves and Parameters

Figures 4 through 12 present true stress/strain curves at a single NCO/OH ratio for formulations both with and without MT-4; the ratio chosen was that closest to the value employed above. The tensile parameters from these curves are presented in Table IX. As with the laboratory samples, no clear superiority above the control lot over the full temperature range can be observed. c. Propellant Fracture Mechanics

Crack propagation measurements were conducted at -65 and 70F in an attempt to distinguish more clearly among the pilot plant samples. Propellant strips measuring 3 by I by 0.1 inch were bonded to wooden tabs along the 3- by 0.1-inch edges and, after a 0.5-inch edge cut was made, were pulled at a rate of 0.2 in./min. Stress and strain at ini"t"-'iion of cut growth were measured, as well as the subsequent rate of growth from 0.5to 0.7-inch cut length. Data scatter was such that the only significant difference observed (see Table X) was a larger critical stress and strain, and hence fracture energy, for F-2 propellant at 70 0 F. How meaningful a superiority this may be--for motor thermal cycling, for example--is not clear, although

-16-

~AFRPL-TR-72 -89

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-17-

AFRPL-TR-72-89

TABLE VIII COMPARATIVE TENSILE PROPERTIES(a) E o/am/i m(b) Sample

Control

NCO/OH
0.80

- 65F
17,000/600/14

750 F,,
740/140/26

140F
530/120/28

(Lot 008281) F-2 G-2 R-2 S-2

0

.9 2 5 (c)

13,000/580/10 14,000/600/10 10,000/630/10 15,000/660/9

540/150/25 760/150/28 550/150/25 830/160/25

590/120/25 590/120/30 500/110/29 515/110/27

0.85 0.95 1.05

(a)

Comparison at NCO/OH ratio which has o MTT-4 formulations

at 75F between 140-160 psi.

(b)

and ( m m

at maximum stress from Instron curves

(c)

Extrapolated from 0.90 and 0.95 NCO/OHI

18-

AFRPL-TR-72-89

',

0 oo400 60040

10

20

F f-650 400 300

ILl

I-" SFC--

200-

200

70oF 0 /

-. N
01

/0
140F

100

//

S0

20 STRAIN

40 40 0

Figure 4

Tensile Behavior of Control Sample (90-percent Solids); NCO/OH = 0.80; 0.54 in./in./min

-19-

AFRPL-TR-72-89

0 600

10

20 400

-65OF 400 300

c/)

u-i

S200
I-

200

100

70'F 140' F

20 STRAIN(%)

40

Figure 5

Tensile Behavior of Control Sample (90-percent Solids): 0.80; No MT-4; 0.54 in./in./min NCO!O/Q-

-20-

1M m

mI

i I

k m

AFRPL-TR-72-89

10
0F -65

20

600

400

400

300

CIO

S200

200
70OF

/140F
0 100

0 a 20 STRAIN (,) 40

Figure 6

Tensile Behavior of Sample F-2 (90-percent Solids): NCO/OH ; 0.95; 0.54 in./in./min

S-21-

"AFRPL-TR-72-89

0 600

10

20 400

400

300

7.i

C,,

"LU I-i

w 200-

200

I-

0 S70 0F
S01-

100

140OF 0

20
STRAIN (%)

40

Figure 7

Tensile Behavior of Sample F-2 (90-percent Solids); NCO/OH = 1.0: No MT'-4; 0.54 in./in./min

-22-

AFRPL-TR-72-89

0 600

10

20 400

-650 F 400 r 300

CL

" 200
I-

200

700 F

100

20 STRAIN (%)

40

Figure 8

Tensile Behavior of Sample G-Z (90-percent Solids); NCO/OH = 0,85; 0.54 in./in./min

-23-

AFRPL.-TR-72-89

0 600 1-651F

10

20 400

400

300

LU

_200

200

0 70OF

100

T-1400F 020 STRAIN (%) 40

Figure 9

Tensile Behavior of Sample G-2 (90-percent Solids); NCO/OlI = 0.85; No MT-4; 0.54 in./in./min

-24-

AFRPL-TR-72-89

800'

10

20 500

600

400

400

300

uw

-650

200

200

S70F 0 7A
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100
140OF

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0 20 STRAIN (,4 40

Figure 10

Tensile Behavior of Sample R-2 (90-percent Solids); NCO/OH = 0.95; 0.54 in./in./min

-25-

AFRPL-TR-72-89

0
600

10

20
400

I451 F
400 300

4.)

uJ

o200 Lu

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070OF I

100

140OF

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Figure 11

Tensile Behavior of Sample R-Z (90-percent Solids); NCO/OI-= 0.95; No MT-4; 0.54 in./in./min

-26-

AFRP1 1 TR-72-89

10

20

800

500

600
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400

400
Coe)

300

I-l

200

200

70OF$

__"

100

S/
S//1/

140F

20 STRAIN (%)

40

Figure 12

Tensile Behavior of Sample S-2 (90-percent

Solids); NCO/OH = 1.05; 0.54 in./in./min

-27 -

AFRPL-TR-72-89

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it seems possible that F-2 at a lower NCO/OH ratio might possess improved crack resistance while maintaining high-temperaturo capability. d. Strain/Temperature Cycling of JANNDVF Specimens

Since neither the tensile nor the crack propagation data gave evidence of major differences among the propellants, the feasibility of a laboratory test 1zr evaluating relative capability to withstand motor thermal cycling was examined. Standard JANNAF specimens (four of each propellant in parallel) were slowly strained on an Instron tester from 0 to 15.5 percent, while the temperature was simultaneously decz eased from 140 to -65 0 F o.,er a 90-minute period. The cycle was then reversed to permit return within 90 minutes to the- original crosshead displacement and to 140 0F. Total load for the four specimens was recorded continuously. Available data are summarized in Table XI in terms of the rate of load reduction (-650 F) and qualitatdive observations of sample damage. Although these results must be considered highly preliminary, they indicate definite potential for laboratory characterization of thermal cycling capability and the possibility of improved behavior for R-2 and S-2. 3. CONCLUSIONS (1) (2) Good duplication is shown between ARCO's laboratory and pilot plant processing. Propellant processability with the pilot plant samples is poorer than with standard R-45M. This may be partially a reflection of higher contents of residual catalytic impurity (iron compounds) resulting from limited use of the pilot plant reactor. On the basis of the tests employed in evaluating mechanical behavior, no clear superiority is apparent for pilot plant samples relative to standard R-45M.

'3)

-30-

AFRPL-TR-72-89

TABLE XI TEMPERATURE/STRAIN CYCLING RESULTS Load Reduction Rate(a) 9 7

Sample Control F -2

NCO/OH 0.80 0.95

Number Cycles and SpecimenoCondition(b) 23 full cycles; 3 specimens broken and I with no cracks 36 full cycles plus 7 cycles without cooling (between 13th and 14th full cycles); 3 specimens with cracks and 1 uncracked 38 full cycles; 3 specimens cracked, failed after 30 cycles 35 cycles; cracks I specimen failed, 3 with I

R-2 S-2

0.95 1.05

4 2

(a)

Pounds per cycle. degrees)/cycle plot.

Slope of straight line through maximum load (-65

(b)

Three-hour cycle.

Visual observation of condition.

.rt

(The reverse is blank)

-31-

'1
4,'

AFRPL-TR-72-89

SECTION IV FUTURE WORK The original program plan called for final evaluation of one pilot plant prepolymer at the 10-gallon mix level with emphasis upon analog motor thermal cycling tests. In view of the results obtained to date and with the realization that different temperature cycling behavior may not be apparent from uniaxial tensil,. data, the program has been redirected to permit a more detailed evaluation of three pilot plant samples (F-2, R-2, S-2) at the 1- or 21/ 2-gallon mix level. For each of these prepolymers and control, thermal cycling capability will be compared using analog motors as well as the laboratory strain/temperature cycling test.

(The reverse is blank)

-33-

AFRPL-TR-72-89

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