/ 7<^ /

OFFICE OF NAVAL RESEARCH

Contract N00014-79-7-0012

Task NOo 12139

TECHNICAL REPORT NO. 12

FABRICATION OF PIEZOELECTRIC POLYMER FILM

Technical Work by

James M. Kenney and Stever C. Roth

Planning and Supervision by

Martin 6. Broadhurst

Prepared for Publication

in the

NBS Journal of Research

National Bureau of Standards

Polymer Science & Standards Division

Washington, D.C. 20234

September 1978

I

Reproduction in whole or in part is permitted for

any purpose of the United States Government

This document has been approved for public release

and sale; its distribution is unlimited

SECURITY CLASSIFICATION OF THIS PAGE (When Data Entered) REPORT DOCUMENTATION PAGE READ INSTRUCTIONS

BEFORE COMPLETING FORM

t. REPORT NUMBER

Technical Report # 12

2. GOVT ACCESSION NO. 3. RECIPIENT’S CATALOG NUMPER

4. TITLE fand Su6l/f/e;

FABRICATION OF PIEZOELECTRIC POLYMER FILM •

5. TYPE OF REPORT ft PERIOD COVERED

Technical Report # 12

6. PERFORMING ORG. REPORT NUMBER

7. authorc*;

James M. Kenney, Steven C. Roth and

Martin G. Broadhurst

8. CONTRACT OR GRANT NUMBERr*)

NOOOl 4-79-7-001 2 (ONR)

MIPR No. N66000177MP50030

(NOSC)

9. PERFORMING organization NAME AND ADDRESS

National Bureau of Standards

Polymer Science & Standards Division

Washington, D.C. 20234

10. PROGRAM ELEMENT. PROJECT. TASK

AREA ft WORK UNIT NUMBERS

Task No. 12139

11. CONTROLLING OFFICE NAME AND ADDRESS

Office of Naval Research Naval Ocean Systems Ctr.

12. REPORT DATE

September 1978

Chemistry Program Code 7122

Arlington, VA 22217 San Diego, CA 92152

13. NUMBER OF PAGES

24

14. MONITORING AGENCY NAME & ADORESSCi/ di//eran( itom Contr( V Ing Oftlce) 15. SECURITY CLASS, (of thle report) Unci assi fied

• 15a. OECL ASSI FI CATION/ DOWN GRADING

SCHEDULE

16. DISTRIBUTION STATEMENT (of thia Report)

Distribution Statements on Technical Documents

17. DISTRIBUTION STATEMENT (of the abatraet entered In Block 20, If different from Report)

18. SUPPLEMENT.\RY NOTES

To be published in NBS Journal of Research

19. KEY WORDS (Cmtlnue on reverae aide If neceaaaty and Identify by )>lock number)

Dielectric strength; electrets; piezoelectricity; polarization; poling

procedures; polymers; poly(vinylidene fluoride); pyroelectricity;

transducers

20. ABSTRACT (Continum on reverse e/de if neceeeery end iden/i/y by block number)

High values of pyroelectric and piezoelectric activity in fully electroded

films of poly( vinyl idene fluoride) were obtained by "conventional" (non-corona)

poling at room temperature with sufficiently high fields. The avoidance of

breakdown while obtaining high activity requires an understanding of the time

dependence of both breakdown and activity. Time-to-breakdown as a function of

field, and room temperature pyroelectric activity (7-14 days after Doling at

23'^ °C) as a function of poling time and field were obtained for 25 ym

DD 1 jAN^a 1473 edition OF 1 NOV 6S IS OBSOLETE

S/N 0102>014' 6601 I SECURITY CLASSIFICATION OF THIS PAGE flW*«n Date Entered)
•^tsL s'rmjs^a^^m^ -i

'r-ot?4-€';->fWvf

^ fa‘'vi»i^ ,oit: »^l1*r 1,^'^

V!i 'iHsi->i.;f#i,* lil^ 3T

H0JTAT«3lilD<»T«0<»3»

XWi.VT!W5|ii‘*T

$r i iioqe f6^t#'rt^T

4*4

r,

.i. jii tl^rsf .114 ..:-.cT

l»l^ >jV|t *

*'':^..'-s

' “

,

'

, <iSA WNYJM 3Tirn3 l30S3H 10 BOlliSlSaA'l

r

> i

k:h L

it* H' “*C '"/* ,tl S I; v'.'^;

.

c.

II I

I M ft '

jffi b«ilf ire*.^ :??y

10 t#

Tnsnwpprf

bOA itJoJ4 .D rtSvali $0A|{^

tritfrtbKrtS .3

i« ' •

'

' . * r

, -. nfCnT'lJ

4^ 0.'^ itntb^ifV^O utni/0 Tfinoh.fWi^

^.'^£S0S

M »IM * *3f«r^V*l»w"4 iJO** TII5^,>

.-»^Q ftfi'JiO ftvil) to 9:>IIS

f5oD jn*lCK»M v:^i^^m345

n

rjmSSf

...SI ,>4 uiTia' awytkk

‘ g»tt

-i»' ;^

fT^ Ro‘iu4HieH

n

-4;^^

.:A.

->,

.i5* fl"

* J tmm

-It ‘

! ‘ to fftfmot fl) fKl oT

ip"i

^. .3-

'Cfi

_.!ui;' .___. . _ ^

" ^ *

' '“ '

' '

' ** iv. '<!rin«»*n»» 'V«k v**.**! *mmm- rm YM

'fe '-'''

>V'-i

;ft{>MAih4r©r> ^ i,.fee=.. ^ - . >r. . X - t. k>f - .ff

•

. V'.''

i \>i f fHiaa) ,

/* '

*

( ^

ft ^hdbVtvotv )xt^ ftnt%teq^ ; i»iubio<na

...ii

vUfifhA >Hl3or^y&kq om >0 ?‘?af#v

^ to i*ar -vro tr^ft«iotnue w»o*< foq

-f4l tv> 00 UstUoTJ-t >tlNtt5s74cfrt nwooMf^'id

. 1(1 j(i<ii^it-fnrT i bfit^fwoWfidid AVotJ H

*t ^flf trt *frf) :>HI'3«(0O^yq baa ,0^0^

-

, ^ ya\ br*n oitti a io

=^fi «t :«JqhMHP « *• ' ^o iMJ^* £\|f n^Si 1 00

[.. Ji- I

‘ A* '1 I i.: . 3 i ti <' W d

t tfY4 •t|«'t#4'i >*^*
-l.(-lJW|TY classification OF THIS PAGEr»W»«n Data Entered)

Block 20 - continued

biaxially stretched films with evaoorated aluminum electrodes. The highest

activities were obtained by poling at the highest fields and poling to

breakdown. A pyroelectric activity of 36 yCK"^m"^ was measured two weeks

after poling with a nominal field of 550 MVn"^ for a nominal poling time

of 10 s (reduced by multiple breakdown). The highest activity obtained

with no apparent breakdown (31 yCK'^m"^) was measured a week after poling

with a field of 400 MVm"^ for 10 s. These values are comparable with the

highest that have been reported for this material using any poling temperature or using corona poling.

security CLASSIFICATION OF THIS PACEPWi*n Deta Entered)
^ _ I ‘ mir ~~

^ I I l—llll ^ I—II .H.O w<wr»o*y<B»f.T yrytUM*.
-IINTRODUCTION

Many authors have sought, with varying degrees of success, to account for

the pyroelectric and piezoelectric properties of poly(vinyl idene fluoride) (PVDF).

In the recent model by Broadhurst, et all, these properties are directly proportional to remnant polarization. The achievement of a given degree of polarization,

however, depends in a complex way, not yet understood, upon a number of variables

associated with the poling process. Optimization of this process to achieve

pyroelectric and piezoelectric activities that are both large and stable are

therefore entirely empirical at this time.

One of the major’ obstacles in the development of poling techniques has beer,

a strong tendency toward generalization based upon inadequate data. In particular,

the following statem^^nts have in the past been commonly accepted:

1) An elevated temperature during poling is essential for high activity.

2) Poling is virtually complete after about 30 minutes.

3) Because form II 'a-phase) crystal ites are not polar they therefore

cannot contribute to pyroelectric or piezoelectric activity.

4) ”... breakdown or electroded samples occurs at room temperature before

fields high enough to pole the material can be reached."^

The "traditional" requirement of an elevated poling temperature has been

largely demolished by the success of corona poling. Early studies^"® of the

effect of poling time seemed to indicate a saturation of activity with time after

*7 30 minutes or so, but Blevin has shown how activity continues to increase (at

100 MVm”M over a long period, with faster poling rates at higher temperature.

X-ray studies^ of corona poled PVDF have indicated that form II (a-phase) crystal

ites can be converted to a polar form, since the molecular chain does have a

dipole moment. That ful ly-electroded PVDF can be "conventionally" poled to high

activity at room temperature was first reported, to our knowledge, by Sharp and

Garn^ who obtained 25 yCK-^m”^ with a field of 300 MVm“^ (in 6-ym biaxially oriented

PVDF with nichrome electrodes). A fuller exploration of the room temperature poling

of fully-electroded samples is reported here.
'.1 -.M ( '*''• '•’/'?« 'iWV'

p. ; ,' ",

' : .. I>.. m

"Hf.

* Tf" ** • »

' J ij[|8 ^ !iv«rt ^lodJuis xnaM’

f :c > (iav^) »r»»bHxnlv)xroq ta farjrrw^OKj aHfD^fooxalq bn| 3h?p^»T«crtxct

tU* 19 4«-»u^A<r»^Hd rdbon 3rmo»n>‘^

^ .-Cl

‘ -«'' ' -

‘

.

' '!» .i5f>?^la5>t#ioq ^0 95!^Tp«b nt(T ^A0>laif*<«roq InsfMWT

.mg f: w

istifehfcr S« i»if»»fii » rteq»?',l»OoJ«!i«b''<< »»t Jon .'few xsfqntM'**' n» ?lin»09b ,i»v«'ii

r* ~'r^ +?.."«“ “ 41 : ?•? S$ ^ »wrq e qq^as fwllqO . Tcxj

r« v»^“»i:rtisl? 'bna ^qiar rtJod' ^Hl39r»osflrq bna 3M>9fWfV

r; f4!59., 'V

'

v». „»'

«b4 insmofs^fih bi\3

^ '

,

' i!!S C*'" 'jr . ^

.'I'* 'iV'. ® '’^' ," *'^''

I

il.

w^te|l-»dq «i . ftlfitJ 9lBu|«JbiC*-» 'noqij^ bd^i^ no IU%1 T/sninfl® br®^^ '

i

' , ' '0'V#r ,

, nf »VfiH ^nf^UoJ

^^Wm& rirfeo8?9 aVjwtfoo e^Hub

p.,89lubm 'Cl 9l*rqmo3 xHiottiv al>pnUoaj

9noYint<<livf»ii x4%j,^on^''9nfi I n W’B fW ^ ^ rw \ ^arnr^-o*^ -^, • Hft- wSot .,-.w 02 u60MI|

^h^>«^•os»^q KO oHl^qfoonxQ'o:^ ^ludhlft(>^^^Onn»D^.^^^

9X0^«d iWJOf-li a-ToObd \(5

«br«H

.1

Til ^19lfi^» a<11 9 r CC|‘ 0l,^c uor» dsM

rr#9d i«i< »"iwi fog bdl* v5>tt OS to immi topdn * ( tnof l J

' ., :,

'

' ':'0‘" "i' ‘'A.

'

' iflir io *'^«9fboit ih®3 onoToP to eeWdue

1

'

*^T' ol bprtjosia

ol oaonUnda nwoS^&iBrt ^ nivofS Iqf

' "'ijS S .- .mHan9q»93 "lortprd, forf^ illlw ,boK»q poof i'Sovo

f

^ -IftntP (0?aHq*») 11 Km b«r(K|‘''Anoico>o /eotbolt"^

WlHlr . ,:fc .-' te, « ovort EOOJI nKftrto tBruoofow flrtf opflftj ttinot ^Ino^mop od n*o e«R

fivM 01 boTcw) *'xrrRqo11aovn<»“^d niD IQW bobo-^lSorq^xf fut^

I

rHT

bBR qnidi xd XlNMJ

'

n '^'n

' >r- V' !^'

' '

'i - '"I bff^iftfo xNin»4d iOu^ ooe to ?fni

-,‘t “ BrtMw 9^«}ri*<t«l}*'BioOT’»«^ tO noM»iOlqWji*r«f firt A ,(W!>oij9»r» !>(«oii<DfB ititv 1

* *.«' ^ * . . - 'J

^-•‘ -''^A

t O0'9"r 1 1

‘ Edfoott^ bobo^o,9lo-x f

.

!.!'l4.'''^

,'' ',i:H -C^il
-3-

PROCEDURES

Initial attempts to increase the pyroelectric and piezoelectric activity of

ij PVDF made apparent the importance of electrical breakdown as the limiting factor.

I Flashover to the walls of a brass sample cell used for elevated temperature poling,

and large thermal inertia of the cell, were experimental difficulties which were

' eliminated with room temperature poling, for which no cell was needed. Large

j unelectroded margins of PVDF around the electrodes, to prevent edge flashovers,

I and the use of grease or oil over and around the electrodes, permitted very high

voltages to be applied, resulting in higher pyroelectric and piezoelectric activity

than was generally obtained by elevated temperature poling. Breakdown, however,

appeared erratic, making difficult the achievement of high activity in undamaged

I samples. It became apparent that the breakdown at a given voltage depended on

the time of application of that voltage, so a study was made of time-to-breakdcwn

as a function of field.

Circular electrodes, generally aluminum 100 nm (1000 8) thick and 37 mm in

diameter, were vacuum deposited by evaporation onto 25 ym (nominal) films of

biaxially stretched (blow molded, as supplied) "capacitor grade" PVDF from Kureha

Chemical Co., Ltd.* A large "tab" extension of each electrode allowed tinfoil

leads to be attached with silver-filled rubber cement. Orientation of the taos

180° apart kept them out of the field, so that self-healing of the electrodes

by evaporation of the aluminum during breakdown would not be inhibited by the

I attached leads.

j A grounded guard ring, 136 mm inner diameter, was applied to the film around

j one electrode in order to intercept surface leakage. One electrode Was connected

to ground via a combination current and charge meter (designed for this work to

have very low drift) which drove a dual -channel chart recorder.

I *Identifi cation of a commercial product is made only to facilitate experimental

I reproducibility and does not imply endorsement by NBS.
' %

bfifi >Hl3f«l9cy»>ccr srti a?R9"i3n| ffitilni

' . *^ 13. ; " A C 'M

^Wlisrff aHi u itwobjlftytd to eonejnotjml JwiBoqo sb«H

'^A %

,OKtMoi» 9*<ktf*’.7ocsn3^ l>a|Byof« not I>obv fClOf 9Fqn»* b % >ff«w orti od i

'.V ' ,*“: . ,•*> ... .'''*•!' * J ,.

' I W« ' ' - 'W • I

' •

. W>: » . '' I'ijn

' ' - rBib3«H«tx» iiitw trfSib sitf to remod

> :

: / -. 'VI' „ Ofv ', ''" c "T*-'

' ooibJ til* tfso cm -idt s^itf fi^oqmai taocrt d|.»^

jg'“ .'

. ^

"

K* ar

'*5 tc! V10V boJifrWi^^ «e3boTiDaf#,^ feoiuoiB boe novo Uo to tatsiB* to a^u a»1l

oiTtbatarrtq rit ,bofrqq6 od odTJagi^l

' b,

'®**' ‘.

, ai£V5»wi>d ,n^i4iiOt8 .Cdf fOq ?"tu3fTEqp»ad b5^^^«^0 bao^Bldp 'tf rfl390fl(f ^fl)Hr^

' % «

•to., wit, tfooltttbvgialrjiiw

• • *

•

, ') •* pr*4^-

. bobnoodb #9»4l0v woyip If tB <iiMOb46and adt tBdt^inwiBgOB. s«B I .i»ti

. jf

' > -

'v ", >

' “'

ii o« .scfitfov iBdt to noht|3Hq<^, to^awf,

' L:

'' ''‘•;br$tt t0.no^t.'>^"|

5 U8iSE^\. ^ * MB^H fir, .'«„. v:!»^ B

(^f m Tf tmjiol3r»^ OOOfjf'fe OOf .esbBitooro

“ " Fl^' m-fi ii<W^ (bOtfqqua 2B # bob lorn ^ofd)^b^t9'tt4

f 'V ‘.I \'-f; ”— ^ tS-no)tit9txs '‘dBJ’*

2tii a tt to jioft^faHO taddin btfrrt-i9vf>2 «bi

-? 0 --.pt'-

' -- .ri- E, e JOOf9 Brtt >0 ,bf9^t odt to too

' - m ^a, s?tt xd b*?NMnt od ion bluow nwobiti9*tcl aiinlw^fi edl tofno^lBioqfiXj

^

,,,h«i.cno oJ ?BW »^oltT«Blb g^tval «iw dff ,ooH ,b^6ilip'b9b«^

’’*'^5 f. .% l^j

h»l33fino*j iff# ot»oil>tr»^9nO ibitw? Iqa^ytoJdt ol *^»bfO m a

'"^1

' "'' w- 'S -

'^' ' Cl not bob? f 2»b ) 1 01 9«M son* b bn* vi» ri f <»ta> »^ ® hv;3n i

* " T’:-/ vv!s-' ^ns^ooan, Itstb .r^Oftsdo-tsub B avotb dofrtw (l|^Hb w^oT t'^V

. _ iki^S^ i,''.

^ V . .. \ *>-

|( : x.tbo ablif ib-tiubonq .'Totoiffl^a #• tb notlBO^tbi

I ^ .... .. r^„..«*e fi "••' li5

A. IW

.ZW xd 4n9fW>2^0bna lOB 2^ bn» x^^fOtauboni

, v
-4-

To avoid instantaneous sample breakdown initiated by external flashover, it became necessary to immerse the samples in a light paraffin oil (Saybolt viscosity 125/135)

i when poling at high fields. The samples were later cleaned with methanol.

Following the breakdown study, other samples were poled with a wide range of

i| fields for specific lengths of time using a microprocessor-type controller to

i program the poling voltage source. As one second was the minimum ramp time for

I this controller, the shortest poling time used was ten seconds at the nominal

' (constant) field, A different sample was used for each combination of poling time

ji

I and field. Pyroelectric specimens of 28 mm diameter were punched from the poled

I samples and stored within folded tinfoil prior to their measurement between 7 anc

j 14 days after piling. When breakdowns occured, they almost invaribly took place

I at the edges of the electrodes, except after many breakdowns (when damage proI gressed inward). The smaller diameter of the punched area, therefore, allowed

the areas damaged by breakdown to be excluded from measurements. The pyroelectric

activity of the punched specimens was determined hy measuring the (reversible)

' current resulting from ramping the sample temperature over a range of about two

kelvin at close to room temperature, as described by Broadhurst, et al A small

irreversible component of sample current was compensated for by measuring curren:s

] for both increasing and decreasing temperatures and taking the difference between

i I

I these at the same temperature. The assumption that the small temperature cycle

j did not alter the , irreversible current was verified by comparing the pre-cycling

I and post-cycling currents of several samples at the same steady temperature.

j

I

ij Previous to these measurements a number of samples, poled at room temperature

!l

jj at 100 MVm"^ and 200 MVm"^, had been measured for pyroelectric activity using the

I same current amplifier and also using a low-drift charge amplifier. These samples

I were also measured^ for hydrostatic piezoelectric activity in the same sample cell,

;l .

|| using the charge amplifier, with the cell temperature monitored to permit a

!| correction for pyroelectric charge.

I|

;!

i
;*f«f-,- ;jr* r-i _ m«^|r«3^r

;

' J '^'^"' •* ^'3" ^9d ,i^(wl2 in f^m9tji» vd baJBtiM^ nwob?»o«rid 4fqffiif ’iuosttsirttiinl btovi oT .

Jgf IB ~

B nt 29fQtti{ Bdd snidinf oS yiezsftDfd

enffcKj

>0 jfiB't sbtw I ddt'# b^fon esTqrast 'iidio iXbull awt;f 6dfwofro*t|j

(d£r\^S( x^fzcDIfV Modvf2) tto

^ . fortBdJBflt ddlw bBnfiBfs srtaw sti&lQnsi BdT

.dJ.- i oj KdffcHJflt© wjvt-*<oa?^bo^dipftt e^gnliu *>0 zdisnsf ot^b^qe iQT>BbTf <

* o

'id^ Bwft Qflui*i muwtn^ro drti zbw bnooBz Btw^A .«:>*»uo2 »pB>Tbw (^tfoq ?djr.(Kdr*i|joi

Hi finiwcwT sft^^ dB ifift<»#s nai 2»sw 6etw swI J jdltoq dzftdiorti 3dl. »isffontntjdtalijl

.’' ,, iM*'' 'v. a ^., , uv,.,v: ,' --

. *P:i|itw,

3mfi pnHoq .^o doUifiidAoar niBS *io1 bwu lew »rq»«« ^ff9is’t^m,A ,bl«tl (doididlMi

'^4 PL

^

'J|t ^ bdfoq sdl cxn^ )l>»d>mM| new ifJedteb m 6S >o 2fij«tW»,,.3hJ3BrMTYS^

JiHi t n»*»dtBd nBfe3*YuiB9« if9d.ro3t *»ohq b»b^o1 dtditW^bB'foli bWi iffq^

j;

93»fq ^ 00^ iiomfs ^bflrfiDOO ?fiWQ6jlft»nd ;pdtt»N|:i9}ta

.•fL « J.i '

'

>1**' VJi

. f**® 1^' j: "'li»2i ' ,5^^'

-e^d »p«4f!ib «fdw' ,s3bo*td3dU arti 1d«u9piS%Bfli 3

i ,.M ).'< •'» ^'-

bBwqrffc ,&nOTr»9rtl .edit :* itiS to T9d9Wdh> 'T»rre««1hfT bfic9

/

«oi^ beby bxd ad oJ nwobdedid x«t ^ ’96mb

1,

7i tmiur ' la w

artl- 'p^ff-fwiesi^d banfenaieb zfw ?n9»f39qi bai^jfidq

^ owJ iuode fo ogtei « *i«vo Ttv^enwiu^i dfqn«t odi potqnte^ diyi#! uw inWi

.“75 -7. =i, . 'i*:b ' IfW-# \ rremi A fa J« ^lAdbso^fl bddnoadb le B^eiunnaqmsi Qi iedra'tT nNN

f*n9*nf«3 enHoiB*!# \d^iot bB^efijd^«oa saw ^(I9*tl03 sfqflasa to 1n9ncK;fi!ba^dfd^«f.->^

n»3wS Ml Bmisfl th pq Nfii' b'dfi MitsuiAiBQindS I leanoBb bn| en> b dic4

: '^ ”" S -"‘St

' '****'',.

, 8Tqy.j B'tiiJe-tsqfRSl frewi adl tedJ no^^qwoetB adl ^qai^ fimea ^4 a« pnUo^-9^q 9iiJ pnhBqraaa x4 i'aw Iddtivn sfdfnavdnnfHI WJi ^oil^b,

s4 tiJ ^^,7C ''^ Jii-' 5^" .3'tuJ6’»9qff»l v.bj5»t2 amsB ll asfqettt 4 »i»v 91 Id «i«9’niD gntfo^^^fiaiq

, ’ *

' '' ', It, ^

.•'*4.

"

5“TWJ6'«»q*fjo3i fiKxh. jfi bafoq , lflfq‘?^^6i^ to ifdwon e ltif»»WilM 2 i®flj BiartJ o4 iifOlfvaYl'

' '

‘ V- i».ft4w ^lybtOB aHlobfsoifxq lot bdtwfeBfci n»»d bad O0S bne IrniVKiOdr )

99Mfl JtHb-^oT B pdfib Offs bne lattUqwe 4«07Tv3

9lq<7B« 9«W8 t.li «t DHloafooSatq 3liB4207by,ri ^bo^wieaft oar?^

e iVindq o4;,b37l(^>U^o%»7«4r»9qma| f f^b fdJ dilw Seted?

1 ' O

, fl 07» ^ b H1.0# f 307 V 7qt qg U
-5-

RESULTS

As time did not permit the measurement of piezoelectric activity for most

samples, it is useful to have a conversion factor between the pyroelectric

coefficient, Py, and hydrostatic piezoelectric coefficient, dp, for this particular material, poled and measured at room temperature. As shown by figure 1,

the ratio of dp to Py is quite consistent to within the precision of measurement.

The lower group of points represent samples poled at 100 MVm~^ , and the upper

group samples poled at 200 MVm"^, with poling times ranging from 50 seconds

to 3 hours. The average ratio of dp to Py is 0.478 yKPa"^, with a sample standard

deviation of 0.0157. Dropping the single most deviant datum (which also represented

the lowest activity), the average ratio is 0.474 yKPa"^, with a sample standard

deviation of 0.0081. These ratios, are in good agreement with the predicted val jei

of 0.5 yKPa"^. It must be noted, however, that subsequent poling was done at

much higher fields. Virtually identical values of pyroelectric activity were

obtained by measuring charge as by measuring current.

The breakdown data for aluminum-electroded samples is shown in figure 2;

most of the data fit a straight line with a slope of 100 MVm"^ per time decade.

At the lowest field strengths there is an upwaro deviation, as would be expected,

but the testing was not continued to fields low enough to closely approach a

vertical asymptote (limit of time dependence). A comnon line seems to fit the

data for both air-poled and oil-poled samples, although the later appear to have

a slightly longer time to breakdown at the same field. Above 420 MVm"^ breakdown,

even under oil, appeared to be instantaneous, probably occurring in most cases

before the nominal voltage was reached. Subsequent poling of other samples for

fixed times shorter than the breakdown times of figure 2 resulted in some raoid

breakdowns at fields below 420 MVm"^, perhaps due to contamination of the oil

from previous breakdowns or from exposure of the oil to the air. Improved techniques,

such as oil degassing, or the use of a more suitable type of oil, may extend
aTJU2;

tern THtoalWsefq *V© in^nmUtzm «fti lfflna*| jo« blt> amH eA

TP r^' n^9wl9d no^z*i»vno3 * 9vid ot M»®u Sf

J» " -a * ' •' V

' .. -3^t1^q tf-iU ‘tqt ,-b *K):

MifeU* ^£((f mmf\B .^uia-tsiqaiat bni b^toq rahsdffli 'ittr ' '“ 'V -'^

' ''' ' “ V ,

: ^. ' Ilf' .lnsrooWft»flr’tOjjt»?ebriq^^dd dnsJzUnod' altop xl', jo ol ^

i ®

®' ' .^' ^ '

‘Tftqqu bnfi OOr 1ft bd|oq' ins 2s^ zitsioq tq, *qycr%,l

zbnooft? t«)en»x zw^l^Rntf-bq flip, JK)S »rqoa*A;QWi

a :'

•'SB*" •t:!h>“-;ip' _

'®- ’’^"T

' 3

-. 5 M

b*Y5bftal2 if^iisz fi dj N , ftgftnsva^ftd^

iWl! M -1

IT'

C’

SifeitV la

L „ bftiRc>i®'»cr5ii o«7* fm);tj5b|^lnAWftb :^lcwi ftfqnU wi-iftH

, 4

' " ' ^

iWi?

-'cfc; iftt^fa^X*., bftj 3 tbftrt q ^ ^']tuMin e»j1T , ffiCXK, 0 ' io rStlSFv^bi

’ '))' Si?.-. :&|L.V'. ,

'

'., V

i w

%-m ftrti

ffi^., -i«-

- ')*^

> “'" ' '‘ff‘ sno^ «iit^ enHi^ swi 2#0

^**>,: , „ » , ^

.!«w-«** “

p ,. " » ' <v>

• '.»: ytftw ' Z^Ml.ftv., f63t^7m»b7.;

B,. *5^

‘^'t- pnMvae b«f

'

' ^ 55

snupM'^l ;»Twod2 ^fnufft;' ^of rtwob^figld. a^T

'.

'' ij. S,T '«

, ftbfiDftb 9f(«M' 'taq,-' OOT to

^o,

s- fiSN mti SdQ f «tii ft

,'

' 'M Jz(

V. V fr>

>*3- ,i? _^^b3l39qxft &d fti&rtl,, zfilq^wla b^9^Vl^a^»

^ rl360^qqft:"'tf»20i3'-«51, f<e&W» i^o^ tblqM-ill' ^wnHqoa|lo«;>ft7MM 1

'3,^... ^ ‘4a..(93f^brtaq^b' ibxj'T?'

. "i«5 ft ra'^rf^tlpwodirfi''- ,z^tqu»t bsT:pq*,:r to, , bn*. . bftfoq^'i M' rt3o4;;}bt

^

4ff^t)^&Tf4 i“«VM70SA bv^4A^'->bfftU,-.Om62;

?9e6i. pnH-iiDio; qj *'b3iftftqq» 'ilto^i»bbo'

:!'

‘tot eftFt^z Tftrtjo tq pof foq fftrtfp3h.9fii s'lbt

pidi'.' jt, iL. btaa^ anK>2 nt tq": ^qtl nwob^tft^'id »dl wdl isixorfa

:P0&. '

, ^ ym , " I , iito artxHo^ftO>|:ftoJ;mftloqOj,-,ci5j'9vJb :aqBrtriqq,:.,,Jf^q»VW'^^^^

jL'

ftffJ',oi'S qo -znwofedftO^d zboM

: 'f * t

bn9^x9,j'iftir »7td: ^o m^JM4ztht -fiotf jMiq qo ,fft;-..i34if|

U

,p'’V"

,

A-
- 6 -

the straight portion of fi,gure 2 to higher fields or at least provide better

consistancy

A number of samples with electrodes of metals other than aluminum were poled

to breakdown in air at 300 MVm”^ . The results are shown in figure 3, which is

an enlargement of the area outlined near the center of figure 2. Four aluminumelectroded samples were also poled to breakdown at this fields all of which,

including one poled in oil, had unusually short breakdown times. There appears

to be too much scatter to generalize about these electrode differences with regard

to breakdown time. With regard to current during poling, however, the results

are more conclusive, .as shown by figure 4. As the field was first applied there

was a large current v'hich gradually dropped to an almost constant value, which

t'

'•

is plotted in Figure 4, before gradually rising monotonical ly until breakdown

occured. The currents at breakdown and at fixed intervals after applying the

field were also noted, but did not provide any more precise prediction of time

to breakdown than does figure 2. Comparing work-fjnctions^° with the ordering

of metals in figure 4, the higher currents correspond to the larger work-functions,

except for gold which is badly out of sequence (but which does not bond well to

PVDF). Superimposed on the slowly varying current were small and very narrow

spikes, usually positive but frequently negative. The frequency (average spacing)

of these spikes was reduced when poling in oil, so they are presumed to be associated

with corona from expf)sed leads; this has not been studied, however.

The pyroelectric activity as a function of field strength of samples poled

(generally) for times shorter than those of the curve in Figure 2 are shown in

figures 5 and 6, the latter using decibel notation (20 log^yp^) of arbitrary

reference (0 dB; 1 yCK'^m'^) to provide a better indication of the significance

of activity differences. The decibel increments should be the same for piezoelectric and pyroelectric activities. There is a discontinuity between data

for air-poled and oil-poled samples, probably as a result of a smaller temperature
(i - i’V'fe _i««»<l »b»*oiq Ji«»r 1» na abtart lartcti) oJ^'S »-i»ipf1 >o ^o^^'n)q JitsUllaJ -il

"' Vv^y a^'

' *^'-" ;

•

^ ’*,...3*TMi . J . ^ W bafo^ 9*i«^ mytttBWfB tttffi *lw^iO ef«t«W to ritlw “^o

m

ef f* 5trtw ,E f^iiDj^rtt flworte UfcaM'Wr . ^“j»itK O^E t< ila ffl ftwobl^jo

Hifttntim/fs iiiio\ at 9iti»B^t 9/tl iiai^ biifif fiuo irt$ fn^m^ijti

~S -% -•„ a; •'“ •'- *’•''

. ' I Yo-fis .bfilh liMt rtwob)*j»n>»o^*litiroq »^9W wTqjJwe t)3btf|4D#r

_ ..iJis. Jtap- nB

j|y .

' "* ' * ' - ''’ '& fc

"

'

- rtisqqB 9^d<fT ' itwOhMsrfd liodi tfCitiiiunu bftH < f^0;^> baroq ano.

Inep©^ njhf efonr»9lttb abo^iatft

Pi %o

a|fy«n 9(^ ,i»v9¥toii gnt^iib^Ji^rivp aSiuH ^ob^s9*^^

ijnfl s$w bf»n^^riA \d nwode 9to»

'-.ft' u A .

,«urfcv insienoo m 0%biW|<|oYb

a«»{>jlasid fUntt'»rtoftroJiuW.enf«fl 'cftkibs'is 'a^^ad .aJaaujfT (it baJiof<( i

i-vs-, «,:•!!:. / >,.4. ,c%'-

' " .. ^

.:il^s’''*‘!r.-!Ol

%rtl ^nh^Fq^ “Yilt* oiiufe^isoKl tfc "‘V':.

'' 3 ® Jl '^

' '"T"' 1

Yo ^9iQn ozFb W»i

&nH»bYo^iw?J rttf^wryl/znol-^^^f-inw ^'1®^ ^

* 1(10 Wontfti;ltow'"!aDYdr b<tpt«»"Ytjcb ii(ia-(Kij> i»rtpldi 5?l^ 1

i YO'.' a^-<,b^f1Vl €-

6S flaw vbdod dofi 2^^ t1

wonftfi V19V tm» f fadiw ®dJ wo/baioqml'- aqiij^ *(Ytl

^•1 J*p «

' 't' W-- wr . *•• '.«<# r .1 f . v'.; '

, '.y It' (pn^Aqs 9 e 5*i 9Vfi) t^fWVP^Yt

ad ol bsAiwe^tq sia

‘.'.

' # , .vIl. "-iw- '‘^ .' iiavawod ^bafbu^t dwt^ssrt’^isetrtt

^bafoq isiqw ir1b dis^andi bftlfY

nmwodi . 9^ S 9 -fveB avYio 92»d?fc|iBd|^i 9d^ort 4 2 s«|l idt

m'

.€1

isa X^fi’TdtdiB noFi^b|n^^fo9b id-bn«k^i^

atjnBomKipli arid >0 ftoldedJb nr Haddad e ab^ViG^ir 0 t^(^V*;<3 q T . 9?>*?s|

‘ " . v;,'

' '".V:*^" . '

- oiofc ifot aAy,! id bfooHe idflsqfflBTsnj T td { afftb iwtT looniHgYt tb 1

• e}«? aaaaJsd xJf4tdfldp»tN» ;*t marfpP^UI-'VtJjjfc sHJMlsrixn bn* iFnJb

gTud'AYgqjwd Y9r r$flia a to dfdSst § »aarq««?a b9foq*f b bsloq-ifb

_. .

' -aj. »»\ - *»4-- iJC".-

' ',

r V

i¥- ' i

r,-.
-7-

rise in oil due to heating of the sample by the poling current. Considering

; separately the data above and below this discontinuity, there appears to be no

abrupt saturation of activity with field in figure 5, although, as shown by

figure 6, the relative increase in activity due to po‘ling above 250 MVm“^ is

I only about 3 dB, and may not be large enough in many applications to compensate

I for the problems of poling at higher fields. The highest- field sample (550 MVm"^)

j experienced almost continuous breakdown, reducing the average poling field below

I the nominal value for most of the poling time; this may account for the relatively

i

I small increase in activity relative to 500 MVmT^ Breakdowns in other samples

j were generally isolated and probably caused little deviation from nominal conditions,

I

j especially for poling times of 100 seconds or more. The pyroelectric activity of

I these same samples as a function of poling time is shown in figures 7 apd 8, the

I latter using decibel notation. As with field, there appears to be no abrupt

saturation with time although at 100 MVm" ^ and above there is less than 1-dB

I change in activity frr each decade of poling time. At the highest fields, a

scarcity of data and possible errors due to breakdowns preclude generalization.

By interpolation and extrapolation from the (unsmoothed) activity dependence

plots, constant activity values were derived and combined with the breakdown cun-e

(with extrapolations; of figure 2 to produce figures 9 and 10. (Values derived

from extrapolations are connected by broken lines). Of significance here are :he

intersections betwee i the breakdown curve and the constant-activity curves. It is

i readily apparent that the highest activity is obtained at the highest fields, even

1

I

j though poling time may be severely limited by breakdown. The optimum poling

I conditions and the maximum obtainable activity depend upon the highest field strength

that can be reached without an "instantaneous" breakdown and which, in turn, depends

upon the precautions taken to prevent external flashovers that seem to initiate

I breakdowns. For the particular breakdown curve shown, with the "instantaneous"

i breakdown limit a vertical line, optimum poling time would be about 100 seconds.
Ww *^ft9ina5'i>ftfToq viS to^nflewl o3 wb f^o nt. si1

";

' -

. f \ "i.l4j'

<ifl Bd W rffisiqqB siferti itdi nofBd bdi tvods BJfib Bdi: vf^^n

Y<i «i«od? 2i ,1

>i

(i^uortdfs *2 bfeh diN\jh*WH 1o Sqim

. r.^ '!.. ,. . 5' . . V'

'' ^ ^ C- -3

1' ^ m-

' ^ ^ :, '^ i. ', ^

.<» , „'jp,

«d* 2 n©dmcp,oi 2n0i:tB3t fqq« yBis« r»f dgu'^riB »d ioft yBiQ bn$ «ab C iuc

fW^

(^‘'isiVM 032) srpmea ifi irtffdei to ?ro©l<joyCs^i^|

wofod br©n pniroq spetavs 5rtJ ^ft^Dob©7 ,©wo5)ie®ifd atioti^

f ::^

. ^ . 1. . sss . -s-,, 'il. * .

***

._

' i*/^t ..t'yC . fMm‘ ©ftf 7ot jiuioooft ytm ?>fttfoq odd to i;?o* lot lia^reV Fan^«^i

zalqci©? irBddo nl effwot>j|A97l 003 ^eftBidnU rnal

. ,«n^Fbnoo fsotimj© rnott no^isrvBU ©fid'lrbbzuao botblo^t yff

©;yltv?fo» *»d^^b<iq£)»i' OOf,

tl!' jtt {l!s F-©rttr,B |»Cft t* nt e^F/oq to'^ol^odw^ earq/nii^'a&t’^ss^

-A

JV f It.' sn ^qwldl prt ©d or t7BBqq«i

, ^b-f nidd tz^r *raiiBdi+|®5 Mjr^.in\/W«Oor

? '

"'

' '^i. M ' '-'*'

'^' '¥'.^''' ,,®”'*^^. 'Vi" 1."' ' '/»

&J

f. , :^ 'l&

H

I

bf9tV' ' d.4 N '4A«-' :.'rtdlted«^ W'

.... '•41.. I

' ..iAi f e(rj©bd6'^'”S B'fdfi'ao©' bq©

' *''

!f' Vk.., 83 ,.,,.irffl .. ' i;'''Ji^~ Jro^

' * ^

s^' v**>rlBbn9qBfe _xd^/t^^a®s^d^ ff>6^' nofriroqfi’^^^

»\nu3 ^n[wob)»daNd odd 0|tf:No!-cte0O',Db©'O©vF7©b"' 9t9Vi'- '»• ' . ;»' ^’\,*®*''. ^ , 'J*„- . .

•3s- ''^''®,.p^ a*.

‘ .4»sA?Lt. ' ® ^

bsvF7©b“' 9tjv*- incui

b©vl'*tF zOBf fiV !

'

' :'50 f brtft ' Ft'^idBbq^q.^Od S K.u^l't ttf'''.''(ino F Jb roq»yix9:'% F 4;. .^" Biart

' 93060 .:l'(itqK: rtiMcnds xd b' 3to,s0

'00i) 97:j- ‘^noll6 foqa7Jic|^nio

^^B9vw xdfvtto6*do^^t(!^ sdr tMii,BV7uo' w-abiw^ ©d^'^avpfbt,

nov9 ^, 2bF 9 ?t UsdoFd W f€ bawtda j7 xtlvF^qe iaswtefd era^.tfid^ iqa-j&qaiTxFiN

. 'l^. '^''•iM-^ ^^V‘ ’ ^nHoq iimi»fJqo »dT .owob:l6ind x3 bafFmtf yfativax sd v4«i ,©®M enffoq dguo

rid^Trle- bfalt j"29dctrt adr Tioqu hnsqab ,x^lVFrk'''»T'daiT'F6rdo ©di b'fi''2n^Firb<<

^bdaq©tl ,n3iid ofc, .fbirtw itvfObdfioXr db dUodiN' bsd^es** ©<f wio

."'Jwj)- - Jv;^:'«'' sddrd FbF qt m»«« dbitt’'Z’F©'<^od2fifT ro©yb‘’iq <w najFii jnotdUfiDByq 9rt3S ^‘>1 V “

' .fi

'

. .,-

,

BV7wa owob^ ©itt io^ ^fiowpbdc ii V^;4r- '

' 'F

“&L

'^,'.:.:,,v'.'

', '^:7ibao0©^^ ^ffoq miHW fftoFrtav B^fiaFf rtywbdi^

* "• I'tJw'

.^Ir- ®"

'l*.''#'^::'''’ M nii> J-;.

'

' • ' ,' i,i

' '^‘^

'-Wf 'm
-8 -

I since the small slope in the constant activity lines reduces the activity by a ver-y

! slight amount for sho> ter poling times along the (vertical) limiting portion of the

!; breakdown curve. For practical applications one may wish to avoid breakdown damage

ji by poling outside the breakdown region by a reasonable safety margin. Pyroelectric

activities approaching 30 uCK"^m“2 without breakdown appear to be possible. (In

oils Py > 30vCK“^m"^ was actually obtained with 400 MVm'^ for 10 s, and in air,

! ^

!| Py > 29 viCK"^m“2 was obtained with 250 MVm"^ for lO'^s.) If breakdown damage can be

!| tolerated, as when damaged areas can be trimmed off, even higher activities are

|| possible, (py > 36 yCK"%~^ was obtained with 550 MVm“^ for 10 s, in oil, although

I damage was extensive, and p^ > 35 yCK^^m"^ was obtained with 450 MVm"^ for 100s, in

I oil, with only one small hole).

I Theory predicts^ a linear depenjdence of pyroelectric (and piezoelectric)

I activity on remnant polarization. In figure 11, pyroelectric activity has been

I plotted against the total irreversible poling charge, i.e., the net charge that

i| had passed through tne external electrodes of the sample after the poling field

had been reduced to zero and after the current transient had disappeared. This

I represents the remnart polarization plus the integral of the leakage current and

I instrumentation (error) currents. For many samples, this charge was not determined

I due to saturation of the first ( current- to-voltage) stage of the current and change

j meter by transients during either turn-on or turn-off of the poling supply, or to

i saturation of the integrator. When breakdowns occured, a correction was made fo''

I charge lost (the usual case). Because of scaling oroblems and the need to avoid

|| overload, the accuracy of the poling charge measurement was frequently poor, even

|| neglecting error currents. It may be seen from figure 11, however, that the

P activity of the samples poled at low-fields is reasonably proportional to charge.

l|

:j Notable exceptions include a 200 MVm“^ sample where a poling time of 10“* seconds

p

I

[ may have allowed a sizable charge accumulation from error currents. The other

I badly deviant samples were all poled at 300 MVm”^ and above, and all experienced
r; '.'."'Sij

t»»v i ia^tvttaii. 9rf^ tv »>*:-»((** it»3 ' 9<(.t nl- ’»qaf» f f snw

lornb j^nHoq

qwbWwd btovft^ot »/m* tnofJfiaffqqi *®v-»u>'

3Hi3®rso*tY<^y' *nfr^6fl> ird$fw?8flrt * y<^ «o^c9^ m#dbifir*4

nl) ft(?(Ifi«oq 9<SoJ tfi3qQ*rn»iS);(s9id ju^li ^»»-XDii* « -pnMjeo-iqq*

>! .. K y ,** ^ .y ft. i: ;=. ‘.Ttft af tide ,i®0r W*i-(«VH W» rtJlAs^ vJIdWat m« *'»<'*a;(>e'

sd ns3 »ew«> n»^bto«g4Tr »'i«yN OSS fOty“b»qffil*> eew Sas^-X

.-» ^ gy

.,^,y .:.r M ' 'r- T\ 'uJI __. . gfis (I9V& 9d"^ifrSi iB9lM

ITguoia r« . ito n|,, 9« '<1 vqfi^

Ti.-. ' ' l(tf.r«:i ,.r--4te *ta»

*5tBi! «*M( "lo"? JfTnVH OJb rtjh< b9nftA#iq?*iw

• .,

''

a G^r (3hd3S r sossfq bfls )' s Nj3S?ieqx4'3«» s'5n9^9fr®-i«9af|^%''^« , ’^3i3S“ .

rtssii »

' iisii

' ‘X../

'

;

' .-^

' J&fiS sqiiifa srfi,^ir, 9,r ertfioq

AO

19^:'' br«,« o^^a' o#.

.;

r bnft inan-utt mlq n6Uiitfu(oq^iunin^^^

bshfitrtfttsib icm^ifitt .einari^a Aptif;

tny

Bf 9fll iarfB 94f4rto' ndf,:^i*iui£|'.t

M "»o-. ,Yfqqua *T»rtit#,-;BnHtib>U^V3|^

'^' •: «*.,.

i^Ji' zm. mUs^r^Qo %

bfovi: Ojo thm »/« ba#

A', ;’IS!u“ T;. "> "
-9-

breakdown. Total current, however, was not visibly changed by breakdowns, following

recovery, and a correction was made for any charge disturbance, as has been mentioned.

Large error currents should result in a clear separation of points by poling time (and

by field, for large leakage currents) but there is only slight evidence of such separation.

CONCLUSIONS

High pyroelectric and piezoelectric activity can be obtained with biaxial ly

stretched PVDF by poling fully-electroded samples at room temperature using a

sufficiently high field. Time-to-breakdown and constant-activity plots can be

used to optimize activity while avoiding or minimizing breakdown damage. Highest

activity at other poling temperatures and for other materials can be obtained

in similar fashion — oy determining the time and -"ield dependence of both activity

and breakdown.

For the particular material investigated, poling at room temperature does

not yield a hard satur-ation of activity with either field or time, although theri

is little practical benefit in using either the highest fields or the longest

times. The lack of hard saturation maybe due to the gradual alteration in crystal

packing of TGTG" polymer chains from antipolar form II (a-phase) to polar alignment,

as recently proposed^ and perhaps at the highest field to a conversion tne ’all -trans

polar form I (3-phase).

There is no evidence that breakdown per se alters sample activity outside

the damaged area, but it does limit both the field and the poling time.

I Although room temperature is particularly convenient for poling, and may

I have commercial importance in the large-scale production of poled material or

I in the fabrication of large "monolithic" transducer arrays, etc., higher activity

may be attainable at some other temperature, although it has yet to be demonstrated

j that the improvement would be significant. A detenrii nation of the long-term

j stability of activity as a function of poling conditions would probably be more

j important than a small improvement in initial activity. Higher activity might

i

I

I

1
•T/'" wiw onlwffo^ ^cm ^iw iJos-wp la^oT ^nmi

5 ,b«rrotl«9rt fT)!i$ftf l6Tt** 2* alwfli «tw iwtlismoj' t bft»

2" '^' ' ^T. _ • . '^i _

bne) sfliw pnVfolci^ytl *Vo rtofJsHr&c^iz it«lA isjrtifuw woa<t2 ^Jnsrfita wi

;,:,f"^' :-f t*: ,_f m y , ® , -,^ t»tt<9onftbtV9 i#<ifre\rito 4'«4 (m^ma i^H9l lol; ,iiff»l

. '. #• # 0-^ atS^-

.f!'E,',i:

©'

^fflT!'

' <i: fsr

3' '..A,

SI^ V " ,; , ''.-(?lw . ^ . ,n .. W • . V

_• ^

*

, Afljp—

m

£ Pf??>u ^nH^M y:4 10V«t,^

IV'

, 'Tfr , —if ,,..-. ,.

' ''f. ^'J! .v, :. ^ ‘i-’^

mi n£3 ^#»vr:r;5ii^lR»j2<wa .bf9?t

t4i ... m

.tiftffbfH .sfeBtrmb m«H)Ma9td »f

bdbii^do dd nab «r£HaJ8n(j -lartip teV b«« *tt dio, i?j S

^ \JT;y n3 £ Utad^o sfmbn^ bT^|:^brt< ' § rttrt t'wiatab

'

r'lfeJWMb .:':.4-¥. :...7?^:;.»SHHHH ' *^':.''>:.ffi^^ .. ..nuAKiTi

m, rfiri

.Kl^'i

,,i^"

*iS» -J

'to, ' bfei^i:iafrt J Ft- Uba^to ' naW'Sftut »« tjF

a

*nwoW69'»dj

9(^3’ 10^

^ Kl(

,, ip »rfJ. rri iiadvlri: srifsi isHdFj

'

' r«i>Fi?£i<jj9Fj| F:

/iF HoFlfiTsifar tifi3U'ba*jp^9d*;# tut apb' ad'^yt* f«jFdi'*f:tJ!ia5? biif-4 To ^loaf sdT'

fc %Foq r'mOl'''iWoq'Fl.r»'-.woit*|'nF

enau-FFa'artJ noFzjsvaob o od bfalt^ftaH^Fd aitoib jqad^iBO^^ iboioocnt^ftr

' #A*

4S’ 41

: f

:Sfi

^bizluo \Sfvti9i afqafj&a zi

nrioT83 ?#d^'tWo^a»bd.'iarii aa^-FvO. 'twi - _

-TM. . 'i&v.-., sr— ..j# ; ,8i . .

« awFi ontFoq add brt* bfaFT OftrddtJd IFiai I aaob Jh^dud^^aa-ro bilBswa ^ ' ,. .

' •-.. '-mi it. ,. fik. ... .431. - '<‘*

. vl 4!i

*J 'jll'

iffii . .l£s'."' -•'I'4i JfsT*'. -'fi i,L. ' if xew boa^'etnlfaq *to^ 2:t.^£b»li^B?p^f«ooi

-. 1^' &v ffl >. :". .;.?

- OT"^ j..„'#r,.

no laF^aJalii bafoq To mjltittoonq add riF lonadiwxiaF faFbn^Hr«80b;i

a Tt Jtf' ' „ "^r,'T. . ii..

.'"

- -rf '.^^'r'"..' -

' .r -'v

iJ5 jjt-.. ff,^ „ ;rp‘.|| *' •..‘i. ”,T3 -. * ,i«r ; “ Jiw-i

y^FvUbfi nadgid ,«bt9 *2x«nna ^aoubertait i%»ldtTrodadr

,b«)£7d«ow»b 'flid ,o.d iii^"2adsj.l dgooddfa 8coe,\d» tfdAfiFfidia.o*

^!^' •' ft ' EJ* r, '*:®L

«ti.is ffTfsd-gnoF artJ Tt: do>dbflFtfni^!^b4.;;. *Hiaoi!TiagF> acl4fuo»F dnamavtnqCTf' 9^;"l|

jUt

‘ ^ .4 - K.rj,

' ' '"

'«fc TM »anoo» dd^fdfido^fl pniFTof to 00F4 wmT a u ylFVF^oa To^dfTIr '

'

^ ^'"*«*' '

' -. 4- rdo.Fm yJfV Fdoa dot .Fa'H'hri^ n-la 5fl»iiivonqfltF f f waf , ..s- nadl-

^ a... ...

' ' ^

VIW.'f '. )ll
"lobe obtained by the use of much shorter poling times, which may allow higher

fields to be applied. The large current needed to rapidly charge and discharge

a sample of reasonable area, however, presents experimental difficulties. Finally,

' the dependence of activity on electrode material needs to be better understood.

i

I

I

I

I ACKNOWLEDGEMENT

Partial support of the experimental work by the Naval Ocean Systems Center

and of the planning and supervision of the work by the Office of Naval Research

1 are gratefully acknowledged. ' I
-or- I

3T '

, O".-

'

• ^ PK5,.ww “

• <• 3 . '. ..' . / .'' XLi ijy’ iMgN vK>rf$ \y5« fi>tr^ ,29(nf%^rr6q' *T$^ode rtdutu \o «^u bsjnffiicbT

9^4/f9trb trti ©CT^fto itfbrqA'i bsbwn ?nmtt» tgitr 'sffr .^»trqq6

.^rfiwM fiJhsffihrs^ zinszstq ,*<fV5^ort ,i9mi •fdif?o^t9^ ^o srqSiat

,bood«if»rfa ^ #boii30r* f»b Ytrv.rj^i to 33 >n

I

'• ' '

. » '.

jPL

Ji^

.V|-

, V -A <«

''l*S

' '^1 v^^^'''

FTirffe .

' » ’i''^

‘

' -• *5 1 4^.." _ • ' £

' "iOinQ

,^.^3 .|•.p

•

. ^' '; V

4' ?;. ^ "" -M

; *'^ft

' '' W;

'• -jg'-'’ ^ ^;;S

RiJa*»

,:..4

i«,'V

.'V.;- A

r-nM# . ?

r^

i' ‘cr. -

» ivr w r .1

3 .r-. ' :4r‘l. % t?,\

' * '^'*- ^ i’? "*^‘1

’1^1..

"i '%1| •V.

>' i

.. .''4^,4

'V^'" 13J

.zmsU'eY'S 'n 60i>O TiRvflH

(S.

d3i652i83l ffivftM to 0^ bo* gornne/q ®fU to'bf

* If- i&’ ..-I^

' »;¥. w. - :1

bfl^arwoft;t3 a ^J^Tuts^rig;

t i; 4s> J^v m

'*iU' ' \

^ ,'3' ^ .

?if-3

1^.-.

.! .,, >,t

m :i.

('•\'-.» «-i

• -V
FIGURE CAPTIONS

Figure

Figure

Figure

Figure

Figure

Figure

Fi gure

Figure

Figure

Figure

Figure

1. Determination of the ratio between hydrostatic piezoelectric activity

and pyroelectric activity for samples poled and measured at room

temperature.

2. Time to breakdown as a function of field strength.

3. Enlarged portion of figure 2 with added data for samples electroded

with various metals, as shown, and poled in air,

4. Minimum pcling current density as a function of poling field.

5. Pyroelectric activity as a function of polina field with poling

r V time as a parameter.

6. As in figure 5, but with the pyroelectric activity expressed in

decibels.

7. Pyroelectric activity as a function of poling time (on a log scale)

with poling field as a parameter.

8. As in Figure 7, but With the pyroelectric activity expressed in

decibels.

9. Constant pyroelectric activity curves, taken from figures 5 and

7, and breakdown, taken from figure 2, as functions of poling

field and poling time.

10. As in figure 9, but using pyroelectric activity expressed in

decibels taken from figures 6 and 8.

11. Pyroelectric activity as a function of poling charge density.
If V- »’

••»> iv

W# -f ’^01 'HAS'

'V, fjS, VI

-'“T' >? ;

' jfioon 55 bs-ninfilw bh« b»Taq sdfqwn 3t*»^D$f 9snx«

a' Ml .diuJrt90 <»5,'

6 & nwobjfiOidciJ *«M

* • ^ -_ , fV •’ bSlKrtMl# 29rq«6« 19’> «<Jj’t4ttbt ;(Pn's «l4rt W>Htw“ b9gTgfa^l^^^

’®.'’ ' .: \< H'

‘

'®')|^• , ...Kb' ^

'* ^'

‘ , .it* 'nf b»'roq bn* .nworie .*» , tlfcJsm iuohs»

,bf»W entrcK) lo’ hoMSnut- s *» '(i^an9b Insri^un f

enflofl nJtv. bfsH anHoq ’lo^n^tJanirt f^*

^ >T,rf w • 7,

' • : « -fi

... i if ^ .in'. .JiSK' ..or’P /?!

^

53df»on^ 9ttf rtJtw 5w^ *8 df

^ - '"•" ;i”*wr

.^6rf! .. PMKUfllK^TvUMi

:£ <;-

"f-/

a

t:'

>sr7

^'

y

.T^5^a(ninjq grtHc^ (It

ni A yi jgR

' ;<U ' _ M-: -* ; .'i.„

i/i ^

S,

, V ^H5 e n9i5i *®ervnw>|,x:;t>vfbB oh5^^r»<nx<?r-*^^;;

'MmKm

r - • onHoa ^0 znofJnnuV « ,S riujiK mint n»)UJ .nwobiJfnd bn*-.,^

'" , _ tr ' ^. fum. -^~

.e

nt b92a»1dx9\5tvfbWdHJ»9f9ortx'9

/ai' •

iiif!'jSP —Mgff^ *8>bnfi 3;'2r»wnji1 rtsieJ i

i{J tfin5b ^Tfiib nor 53111^ ft 25 Y4'f'^^b!^|Pb535f9cN^

•V# : *
Figure 1

Figure 2

i
= 4k

<1 r»*

a.- , ,. ...4 fl

V

f.

' t-i

%•'•» U!^

•or

JB' m

::p- m

^0 8TIMU

S'*/ cd

a3at^iA«5ix3

TRAHO ®

D

OO

m ui3

WOH f

^

' h’>

r f.t

' '!

t'tf: 1 wr

'('C*

'*’ is - -/ fr

IC^'.

1^

§

ut

3ft. ca< m

; n -a^

.''i 't^-

:«i -fl #!*

,:.74

—i

,

‘ « a” ‘t :,?7«Z7r' Jfca&ti..

i1 ;

!'-fiii": i'-^

• I!; '1

‘I ^

RiA Ml aa^'i i

jio Mi aauo^ -A

,-5TT' v ^^civg rni| as

i

0*«£Sl».

- 'IS

*or

£

4

IL. .

or

(X^ Si^ OOf <s

'

»s Qi3R OMUOT^

' '.\

I

j

. ’'fOHHH''
TIME

TO

BREAKDOWN

-

SECONDS

~TTf
•or.

} m

, ^ ,

f

' w*.. !<!.,. . .ii^f ,Jr

4-** *-*’

I J . ! / U^l

mi

0-i0&-

ajdf»-

• ^ £ a.«j0

//•

's.

' *-‘jW ^V-

,;;^i ^'S A4il! A

— ^ .y fliA irti'oajb^ - o

^ , —«3«t<lOO « JIO *^1 '33Jp‘1 - A -iT

jWUlMOHHO

W!U»MO.!i-o-^ :-v«T ; H3*H03'^ A i . £ ; 83ao?rr03J3 WlUtllWlUJA

^ ^ ^

^ Q3TAOIOI/U 2A r*l30X3 , /oJO.D^-^ '5i ^

WIT --5

dm:

fia'isoo—

o

Q££

' f.

•ffi

Oti£ (^ oos

mVM - aJ3«3 OMUO*l

• V'5 I ' ?>J’ w.ii' .!^ ’- ^-"‘

'

' W, '

1- • •Jfl»

. *7: V''M

-A..,-, '! ><tj I
500

200

100

50

20

10

5

T“^ TTTT

CHROMIUM^

COPPER"^^^

TINGOLD

SLOPE = 4.4

O POLED IN AIR

A POLED IN OIL

25 /tm PVDF

23 V2 °C

ALUMINUM ELECTRODESEXCEPT AS INDICATED -

J I I I -I,., I L I 00 200 500 1000

POLING FIELD ^ MVm-’
:';ac

KT

' ‘^ '

,:# w rr

**'

t'

l'»-i

ift^

jL ' i'?‘:''',.i^

!'

, : .. ' '"'f-.

1 .r^

00^

Ml'

jK'-'. V'" ?

jwuilflbflHo

rSl-qgqqSo ’ ^ i'.'V V-

’TTr''

i

' y,.

>0... K

;;V '. '• 1.:

V'

.’

m

liV W- jf M^;:,,,

*'* fc -A

|OJOO;%J ..

.r’ " !»

, ... *

''ait.:;' Wli’tH* ^"’' -if-n

'

'

' .-4^'

"j:'; ..'fei'-i/.'

„ 4|i

'

O ,i*y.:T:.

2^:.

iiM m

jio m,a$j0^ A>

qavqrts_%,,|S,

o^^Kssa

ifij .

..*4

•?Cfi

laaOflTOaJ^MUWlMUJA,

^ ^

ti^TADfcivM ..gA^Tqat^aSlla^,• ^

.L.JI iji

^

Bfeisia. 05

..5' S

or

om oor

m

D»<-

!’ ''^'

'?S'' mVM«^P^3J=C OWU^

toM.< %
POLING FIELD - MVm ’

PYROELECTRIC

ACTIVITY

-

DECIBELS

ro 1

|jCK

’

0 100 200 300 400 500 600

POLING FIELD - MVm ’

Figure 7

1

I

I

t

i

ii ' y

. i

[ t

•

I

I ^ '

t >
9

f'

4i. < •V/

-

RIAVHOTjCW-O 1

jIo m aaiCM - a oa^ a >\poa ai

MwoQyfAsaa - a

- Ni

0(ie Bfs Om 8i

lOV^ rmi 3S

0® «£S

*« *or *or *or ^

*or or

i:aM0D38- awirr Dnuoa M
Figure 8

i

t

1

Figure 9

1 WEEK

1 DAY

1 HOUR

1 MINUTE

POLING FIELD - MVm ’
£ «i uen

)iS9w rt# '

.

‘ r'

Y.W1 r

» RUOH r

. i

,

MlmQ

Mm

'

^BCQiAO?
figure 10

WEEK

DAY

HOUR

MINUTE-

^rv
8fCQ«tD8
35

30

25

20

15

10

5

0

Figure 11 II I

I III

400

r~]

\

I I T 1 T I '

' L

A 450 B

0 450 B

V300 B

,300 c/a a300 B

3500 B/O300 B

350 BV200

SLOPE = 3 X 10“k ’

SLOPE = 4 X IO ^K

’

" /O10!) MVm

JQP I I I I I i r I I 1

O 10 SECOND

A 10^ " V 10" "

10^ ''

B- BREAKDOWN

25 |im PVDF

23 V2 °C

» I I t I i i 1 » 1 i

I 50 100 150 200 250

POLING CHARGE DENSITY - mCm-"
1

r t T \ 4 r,|~n

.7a oe;

-It'

W 1:'

li

•i

ai/iob^ et o

*or A

•or V f

•or a r _ wwGcxAaaa -a •

I .^avaimias:

, .:‘4i o*«€S

["•Wj . _jii •jjr

..

' i&l

L..I. t-X LJ-J

o^s DOS oar oor H 03

^niOmi YTjaMaa aonAHO owyos
- 11—

REFERENCES

lo M. G. Broadhurst, G. T. Davis, and J. E, McKinney: Piezoelectricity and

pyroelectricity in polyvinylid ene fluoride - a model, J. Appl. Phys. A9 , 4992 (1978).

2. P. D, Southgate; Room temperature poling and morphology changes in pyroelectric

polyvinylidene fluoride. Appl. Phys. Lett. 250 (1976).

3, G. T, Davis, J. E. McKinney, M, G. Broadhurst, and S, C. Roth: Electric-fieldinduced phase charges in poly (vinylidene fluoride). J, Appl, Phys. 49 , 4998 (1978).

4. N, Murayama, T. Oikawa, T. Katto, and K. Nakamura: Persistant polarization

in poly (vinylidene fluoride). II. Piezoelectricity of poly (vinylidene fluoride)

thermoelectrets . J. Polymer Sci. , 1033 (1975),

5, R. J. Sh'ford^ A. F, Wilde, J. J. Ricca, and G. R. Thomas; Characterization

and piezoelectric activity of* stretched and poled poly (vinylidene fluoride).

Part I; Effect of draw ratio and poling conditions. Polymer Eng. & Sci.

16, 25(1976)

6. G, W, Day, C, A. Hamilton, R. L. Peterson, R. J. Phelan Jr., and L, 0. Mullen:

Effects of poling conditions on responsivit' and uniformity of polarization

of PVF

2 pyroelectric detectors. Appl, Phys. Letter. 24 , 456 (1974),

7, W. R. Blevin; Poling rates for films of po?.yvinylidene fluoride, Appl. Phys.

Letter. _31, 8, (1977).

8. E. J. Sharp and L. E, Gam: Effects of aging on thermally stimulated currents

in poly (vinylidene fluoride). Appl. Phys- Lett. 29_, 480 (1976).

9, M. G, Broadhurst, C. G. Malmberg, F. I. Mopsik and W, P. Harris: Piezo- aid

pyroelectricity in polymer Electrets. Electrets, Charge Storage and Transport

in Dielectrics, M, M. Perlman, ed., Electrrchem. Soc., Princeton, N. J.

492-504 a973).

10.

Handbook of Chemistry and Physics, 47th ed,, Chemical Rubber Co., Cleveland,

Ohio, E67.

I

i

f
.. a

/

' ;.(. / , »*»> A"

':3jS

,f£ fitrft .IqtjA ,1 J«Noit f

-

t. •.

' a j

. m' .8 iiaJ' *#bi:'KH*ll

-hXikil-olTJoaiS t^t:$o5I

*5.. V

c«^ijklJtTEJtlocj J<uui»l.a'3*t,:: ro't«ca^i>)|^,^ bm «o:t4iJr .,T;^ftW»j|ifc<Pk^,T

'

. ’Jps*; ^*‘

' TM,*, ,V‘‘''|f ..if:..'. ^ ;($t«x)V££or’"«ei‘^<i38'

»i»bfrM9l^ #n»]^Jtlxo^')^<!t4' J^»Xp«!r:>n8 b'prfsJMii* Tfco' XJX;viipji'':tfi:a

' '•4o3"x*ibxIo1^ • VAflixtaX'feiKip tnOiox/XuaMi oX3f^' v*7*» " #: . - . r-f

"

:

^ ,3't ' Ait'

'

,«o»^ ,npXlij*»B

.BoliflS'l^feloX' 50 :WXai3b^Jtmr' hni, :^vJt»floq»»?l, 'BO wiPlflbxioo IflfiXiJtj. if/

»iqqA ,irfj4-i(wX8; onBbJtlx«X^©9 lo^ aBtfil toj »»^f:i C |y .8^*!

^‘'aj/TiTiiJa' b»3aI«trJi'a tc» iKjp*li8 '•*•,

,

'^' '

' . 6^ ?i) :.'’08A ., .3'3^, |^x#« • “tqUiA:^ .. .>< jtna^Tolvj

': .

' ’ ,. r* - '-^Vt

' .mC’''''

''' ' .TMi . " , __ , V

ft'p# H34taXt i ;#‘8a4' ^ •;> ^

' • -^ '

. tiip' '0. ' ' •*- iW_ ^Xfc fUt ' I 'jASJ' * JTPq«OB37 ivua. S8«t«3?

X '4 nbajji. %8i4aA3Jff^ **'*®^'**

wp> ^

^ Jiff

'

!bfT»loy«ia, ,;io!) <£33ti<«ad:>_ 5f J’ - .

<,'6f V Xti
472:CAN:716: tarn 78u472-608

•TECHNICAL REPORT. niSTRIBUTICm. LIST. GEN

•Copies

of Naval Research

5m North Quincy

Arlington, Vtrginia 2221/

Attn: Code 472

ONK Branch Office

536 S. Clark Street

Chicago, Illinois 60605

Attn: Dr. George Sandoz

'ONR Branch Office

715 Broadway

New York, New York 10003

Attn: Scientific Dept.

ONR Branch Office

1030 East Green Street

Pasadena, California 91106

Attn: Dr. R. J. Marcus

ONR Area Office

One Hallidie Plaza, Suitfi 601

San Francisco, Californi^i 94102

Attn: Dr. P. A. Miller

ONR Branch Office

Building 114, Section D

666 Sununer Street

Boston, Massachusetts 02210

Attn: Dr. L. H. Peebles

Director, Naval Research Laboratory

Washington, D.C. 20390

Attn; Code 6100

1 The Assistant Secretary

of the Navy (R,E&S)

Department of the Navy

Room AE736, Pentagon

Washington, D.C. 20350

Coomander, Naval Air Systems Command

Department of the Navy

Washington, D.C. 20360

Attn: Code 310C (H. Rosenwasser)

Defense Documentation Center

Building 5, Cameron Station

Alexandria, Virginia 22314

U.Sc Army Research Office

P.Oe Box 1211

Research Triangle Park, N.C. 27709

Attn: CRD-AA-IP

Kaval Ocean Systems Center

San Diego, California 92152

Attn: Mr. Joe McCartney

Naval Weapons Center

China Lake, California 93555

Attn: Dr. A. B. Amster

Chemistry Division

Naval Civil Engineering Laboratory

Port Hueneme, California 93401

Attn: Dr. R. W. Drisko

Professor K. E. Woehler

Department of Physics & Chemistry

Naval Postgraduate School

Monterey, California 93940

Dr. A« L. Slafkosky

Scientific Advisor

Commandant of the Marine Corps

(Code RD-1)

Washington, D.C, 20380

Office of Naval Research

800 N. Quincy Street

Arlington, Virginia 22217

Attn: Dr. Richard S. Miller

Naval Ship Research and Development

. Center

'Annapolis, Maryland 21401

Attn: Dr. G. Bosmajian

Applied Chemistry Division

Naval Ocean Systems Center

San Diego, California 91232

Attn: Dr. S. Ya.namoto, Marine

Sciences Division

No.

Copies

12

Cwc? I r" 1
Si,, m^lXAuBX

p: ^'^j.,. ,v.-'

; f’

’ 't

* ^ 9

J1oi:»BJa!Nt£i/90^ »BO»1a4 ^i4*32 ao9%a»g7 7 r—--- .e jftiiliiii^

•91150 rfTt»9t8)I t«nA ^,0

mxs WVVS 3 w / € f »X2n»xiT (fair«t«9f

Tr*'M'-0JE>

m -

•

iu»;>0 ifcv«0 ‘ SfilSe tJtcno5i:iftD , 03*^0 •»*

“

• 9fjn*D «ijo<i^ftt0 i«v«ff

" 1 WliiO'’

. '-:a

' '^fcA'" 4 70’^^-''^'^

. 4*.

'

OJl»4ia .w , ajjit

''3J^'SO«W50Tf

ff r*>«w»rfO

.ifl,-

'iniianiV

m‘

»9)tm

99ia»|^ ^rtS Totl

,

‘ -5 "

lallK

'' ,' 7^

,,'jjji tOOOl -iTo1r.:»»

' 'Sk.

MilV.

if —J-.- .... -

' Jf' ' ' ft.

'

.§•: "':^,'«90^v!bA :3ili,jo»i98-

.^„ i«'tili^'jni^»:i

dOtXf 4*ifl^o5xii

tJy.:*T«t:i',t. .r

B9n

102 a ,'*‘‘tinoii|A0 ^03

TbiXilJ

:iV i:S|V3inc

'

V. ^:m^'

»irxo3 ^ ^ / 4 Af ''ijf j

t

'" m"'

' '.- s.i^*''. \f .«> ‘fjilP

^9^1'

TSiliHf' «.27b3A4‘>X3\90

iamtaqt^h^n^ »«A <t^dZ I«y*9

o»l lAmnoS ,0 ,10 jtttiU

,4 .V, 9»3nt0 t#93e^3 nft|t90 lairaM

• ^ r9 #' ip!i . . -^ «r - .«^. f!; ^ !mi> aM ..^ c3o35C/r.aY" '4 Z • :n$ J

? . * -

, w _ v,„jL^...

‘\'i -r

01£S^ t43*Mutfi)at

rf3T4i^^4'"isvi

^Pg£0t *070

::]iil^ . OOU

a- Tr^,JX^ ,Jj

30

yYfJr ijrf^T' 5d

^

O0|4 3:09l|.

a-

_ho»ffiiaoO , Mii,j 8t04l lA X»vTh> ^ , ,-,.r 'I - .,, yV80 #43 lo‘

'02CO£ _ <3*itAl^fr««oJl .H) OOn 1 ,4

Apjr livi’Q

^ ••jtaaXaA,:
A72:GAN:7l6:tani

78u472-608

TECHNICAL REPORT DISTRIBUTION LIST, 356A

No.

Copies

Dr. Stephen H. Carr

Department of Materials Science

Northwestern University

Evanston, Illinois 60201

Dr. M. Broidhurj

Bulk ProperVies

National BurWu

U.S. DepartmAt

Washingtony'D.

Section

of Standards

of Commerce

20234

Dr. T. A. Litovitz

Department of Physics.

Catholic University of .America

Washington, D.C. ,20017 »

Dr. R. V, Subramanian

Washington State University

Department of Materials Science

Pullman, Washington 99163

Dr. K. Shen

Department of Chemical Engineering

University of California

Berkeley, California 94720

Dr. V. Stannett

Department of Chemical Engineering

North Carolina State University

Raleigh, North Carolina 27607

Dr, D, R. Uhlmann

Department of Metallurgy and Material

Science

Center for Materials Science and

Engineering

Massachusetts Institute of Technology

Cambridge, Massachusetts 02139

Naval Surface Weapons Center

White Oak

Silver Spring, Maryland 20910

Attn: Dr. J. M. Augl

Dr. B. Hartman

Ur. G, Goodman

Globe Union Incorporated

5757 '.orth Green Say Avenue

Milwaukee, Wisconsin 53201

Copies

Picatinny Arsenal

SMUPA-FR-M-D

Dover, New Jersey 07801

Attn: A. M. Anzalone

Building 3401

Dr. J. K. Gillham

Princeton University

Department of Chemistry

Princeton, New Jersey 08540

Douglas Aircraft Co.

3855 Lakewood Boulevard

Long Beach, California 90846

Attn: Technical Library

Cl 290/36-84

AUTO-Sutton

Dr. E. Baer

Deparl;ment of Macromolecular Science

Case Western Reserve University

Cleveland, Ohio 44106

Dr. K. D. Pae

Department of Mechanics and

Materials Science

Rutgers University

New Brunswick, New Jersey 08903

NASA-Lewis Research Center

21000 Brookpark Road

Cleveland, Ohio 44135

Attn: Dr. T« T. Serofini, MS-4y-'

Dr. Charles H. Sherman, Code TD 111

Naval Underwater Systems Center

New London, Connecticut

Dr. Will iam Risen

Department of Chemistry

Brown University

Providence, Rhode Island 02192

Dr. Alan Gent

Department of Physics

University of Akron

Akron, Ohio 44304

1

1
V .V

•'f.

, r 'fj.ii eoi^VikuST ,

, mi^ .g ; ;; « \ 'It. Mtt .Taij.»iotTg<tiijrtTn r»OTM jAntitm|^

,0t- i ,,

•' ^

Un»titA v/tni

' " -

9noiMhk ,A ^ ttttak

SBe^jsa iz' . .»

'

>'K

i” Q' A ;3fl

j90Ja5«rJit1L

to in>arfTr*q3<!

80 ic»n wffiT , aol«t^ff

M

,/ V

''

oD,

a.'a

’ 11*3 ..iff.Trtsii

IfitOd {

S*1M,

m

S ' mo 3%-..;Vi' •»>• 4^’

Ibitbntia Jo '*

“1.

„ *3i v4'lsi»v|wU,^

-Wiisig

’ a^A 1 i^io«J o©oii*#< 5 ft Jut arxtTJiqaia 1

X*^^r»»vioU,,9^ ^ ,

u

.' ji)l ^' ' .?

• ‘ ii'"'''*-

' 4 , .*8 ®

j'-'j^s''^-, , ’ '' ‘ ••

' ':'>v ’' '*,®'

E. '^A--

t

* »'X»ii»3iik V^’

.:^- %' ,4' 'til afStrlall^ :. tO^BQ . vftfti.'fL 'Woli v«3C

i»m/'to~ v.J^BiovXiru.i ^

liooti .oidK^na

15, ^SlVl#yinIifaa9|tia'iJi

Jl *

' itdte€

*r

^ ,r 'Wi-'fli-, ijs »*3f|

Zairwmtlsittt lunHatO

lo' x?

OtU?

_-, , asm'ktt

)tKf J.1

, S3' ta3/j>0 i ilMK, tO^jX-r .. ,*viiXcr»ftjJ>'rtJi<iV'

, _ ...Sf J9k5,,,4^

,2<u3Io‘ct®;-' MriO - i iti jA ,j i»l»j»Jr>i brrm -Jn

. . fu' ' na :Sgtr~'

:,rUij*o- '

m dT' abo3 '; -jajssaO' 'xft jjftvaft’bCTU; f444«'

'"

. *i<l'

^ X^j J©.; 4*nM3iitftq,#«l 4;^;:’:./^

ffi • V, fiatixiM,' : ovoiKI ’

' - » ‘H'W »v ,, ' Sft. 1 ^bsb.l v«id'

* ,, '•' "^ •:«P o

mi. :

^ .;rtl ta

tlol6jrrfft4T ,1ft tel;' '^£i£0' ,' KJJ ©ajrfbfa »*li

iir

^ - •^;| ^ ® 1;,

; -'-^apr 'b»X^

noiifA Isf '‘V,:.. , -sIvSi v^.;- .'anpM^' '-y.;7fi„ ''j/f' .v',,*'' , '„, - ' ijinr'

y.nB

mriT' Jt'/^'

,

• -ft',

'J' rm'Mk.. bft j |7ftqioftfl 1 7-.^roi

,

ftwn-ftvA 'X#4 ' n'^ftiO

iOICC
TECHNICAL REPORT DISTRIBUTION LIST, 356A

A72:GAN:716 ; ta78u472-60&

Copies

i

Hr. Robert W. Jones

Advanced Projects Manager

Hughes Aircraft Company

Hail Station D 132

Culver City, California 90230 1

Dr. C. Giori

IIT Research Institute

10 West 35 Street

Chicago, Illinois 60616 1

Dr. M. Litt

Department of Macromoiecular Science

Case Western Reserve University

Cleveland, Ohio >410 3 1

V

I Dr. R. S. Roe

Department of of Materials Science

and Metallurgical Engineering

University of Cincinnati

Cincinnati, Ohio 45221 1

Dr. L. E. Smith

) U.S. Department of Commerce

National Bureau of Standards

Stability and Standards

Washington, D.C. 20234 1

Dr. Robert E. Cohen

I Chemical Engineering .'Department

Massachusetts Institute of Technology

Cambridge, Massachusetts 02139 1

No.

Copies

Dr. T. J. Reinhart, Jr., Chief 1 Composite and Fibrous Materials Branch

Nonmetallic Materials Division

Department of the Air Force

Air Force Materials Laboratory (AFSC)

Wright-Patterson Air Force Base, Ohio 4543.

Dr. J. Lando

^ Department of M.Tcroxolecular Science

Case Western Reserve University

Cleveland, Ohio 44106

Dr. J. White

Chemical and Metallurgical Engineering

Uni^'ersity of Tennessee

Knoxville, Tennessee 37916 1

Dr. J. A. Manson

Materials Research Center

Lehigh University

Bethlehem, Pennsylvania 18015 1

Dr. R. F. Helmreich

Contract RD&E

Dow Chemical Co.

Midland, Michigan 48640 1

Dr. R. S. Porter

University of Massachusetts

Department of Polymer Science and

Engineering

Amherst, Massachusetts 01002 1

Dr. David Roylancr

Department of Materials Science and

Engineering

Massachusetts Institute of Technology

Cambridge, Massachusetts 02039 I

Dr. T. P. Conlon, Jr., Code 3622

Sandia Laboratories

Sandia Corporation

Albuquerque, New Mexico 1

Dr, Martin Kaufmann, Head

Materials Research Branch, Code 4542

Naval Weapons Center

China Lake, California 93555

Professor Garth Wilkes

Department of Chemical Engineering

Virginia. Polytechnic Institute and

$tate University

Blacksburg, Virginia 24061 1

t Dr. Kurt Baum ^

' Fluorochem Inc. ! 6233 North Irwindale Avenue

Azuza, California 91702 1

Professor C. S. Paik Sung*

Department of Materials Sciences and

Engineer

Massachusc: t.s Institute of Technolcgy

Cambridge, Massachusetts 02139

1

1
aod*t'C4^t^

k*S^

S 'J* A^<€, .T^IJ yioiTi>y^^ n»iQ Tfo<?3n jAaiH«a>T ‘

^ *C .T !« ai4hfi*M auolttfJI l>aa *iiio^

B^iiivia laAiia:**)* 3>iUj««uoi

txA »4ji )o

/A>A

t'S*WA’T4Xf&|

C.ACA 0/«K> «***^ AdTOlt llA COtlt13ji9«i^2-^

• . •

^ obiSjiJ ,*ia

i»iu3fXu<t<nr3BM *(;> Inatiiiaqsd

dOlAA oidO «bafi»v«i3

••TqoO

ifph

% n-t

£*n&V .tf *3 9 •(oil M

Xa*q&oO SlAiMtAij

*£^<2 nojaaii

Ottoc *iinoiiU3

,.' 'M ,' ' '^

' itoioi

jtsX ddWftt

i*tT32^et* a

aidO^. ,«{

1 ^ - ‘‘ir •3irt»

bn* Uai«»d&

3 8*tt««mxfrT io

ai9T£ ««ll8dff*T «8lilir7tO«i3l

:;^S

. v#i '-'^, 43i4',',

»9A«iaB 7Alu3»icao33aK Id iQ»|

X3i«T*riff^J osrtMjiJIfnitii*

:!t <aiA. oii<0^,bflfc

I

f.''p>, - %

‘S' ,A >(r . ia

7*3nf» ddMtatA iiUjaJidf’

, f r . C108X

''

’ .*' fbis-rivf^ j| <jtl

ia*x4%»9

,'';*t>'3__.Xda$«nirR) tfddf OAd«A d»ji;gi|4 ,boAlbm

•4t

V..‘'

»3jj»i‘ae •Xaitrtiili; )J» Sd?Tf!t«

ania^tnijia iix>8iwiil4,K

iiuioiaaiO

litt^ oXdO i«3A4|'

lojtof „i ,f ,ia

?c t3t*7aviu9

l‘rti ftXAdlaa imAX^h*! Jd 3aMtjlx»4^

^ miO MaMdrtdaaiWf ,3tt*rt«4

t

9^3 90X03 io' Jn*«37*f*-

•bxtbaiaa So 8 9 id|'i 4

•biAboaja- kff* vai

AiTfU* 1

rik

*

, lijxfN^ xo«%»So7^

pl3»JM3f*o3 Uaitt84to !d j!i»o4x8^i9^'

bi». 8 3413 xaaal oi«da#3rtlo^ axnl|flf

,

TXi»7*vXoy •3*31

IdOAS ,13ud«3l38|I

, , Y. ,

, rj.

'

;'v' u,SAt £^d>030i«|1[

•tftssrirA •Uhnivil 'A3 i 0is UU

%i«3o5 jM^aA

eX

•w.tas .D^av,i,o4^

t a»ff<a* .1, 319<

ait8833*q9ll salxatfolsaS^lf

ao*«srfpftT So *:funuiiX Mu»m

^tltO 433*iucf3»at*||^«|t

•»3fliXtot^tXv

bfl* So" 3«^

, adiiasw

TIOionrdoaT So •3ii3i3i^#l •3i^#«i;rif

?XOtC c3 7»«u4»tt«&M\otb

-.^ s

*2 •3.*70tfoSo3f

t52t *br30 ,.it .oofrsoO '^911 ••ii03»WcJ

4^ia*io^7di3f,''" o ai w0M , 8up3 »i

•XaiadJaX So ifl%a3;roq#a

io fjw3i:*nl .irc.4y»i9**»iK Uno «33»tgHa8ata3< ,*ibiidi»3

. «

' ^v'r'

• >1

b*»H .xin^uzX aiir

XAtA abo^ ,daA*Xff dsisaasa

’ arinaa aocqabW

Wlt2 ainxoSilaS

r .:.

t • c\

•’.,?^ -

ik:l; m

rt

VJAS

7

1^1. .A... m-Ik^ ' iSi