Note: Descriptions are shown in the official language in which they were submitted.
~80;~4S
--1--
This invention relate~ to polymer~ with improved
performance characteristics. In particular the invention
relates to compoqition~ comprisin~ a poly~aryl ether ketone)
having intimately di per3ed therein from about 0.1 to 5%
sulfur, by weight~ based on the weight of poly(aryl ether
ketone).
Polylaryl ether ketone~) are known in the art and are
tough, rigid, high-performance thermoplastics which have
excellent mechanical and electrical properties. Articles
formed from them maintain their properties over a wide
temperature range and can be u~ed continuously at high
lS temperatures.
IN U.S. Patent No. 3,993,628 to Jarrett et al it is
disclo3ed that mixture~ of an aromatic copolyether-
ketone/sulfone, containing 3 to 9 ketone~ links per
sulfone milaago, with sulfur or a sulfur compound exhibit
an increa~e in molecular weight and the polymer cross-linked
upon heating. It is reported that the corre3ponding
polyetherketones, i.e. without any sulfone link~, do not
exhibit an increase in molecular weight upon heating. It is
further reported that when a polyetherketone was and 1~ ele-
mental sulfur were powder blended and then compre~sion moldedat 400C for lS minutes, the polyetherketone wa~ found to
havs decomposed without forming of a coherent film.
.~
-2 ~ 124~;
We have now discovered that if sulfur or a sulfur com-
pound as hereinafter defined i5 uniformly dispersed in a
polyarylether ketone the properties of the polymer are
significantly and surprisingly improved. In particular we
have found that a poly(aryl ether ketone) having uniformly
disper~ed therein sulfur or a sulfur compound exhibit
improved tensile mwdulus, creep re~istance and in particular
their adhesive properties, ecpecially at high temperatures.
The invention comprises compo~ition~ comprising a
poly~aryl ether katone) having intimately di~persed therein
f rom about 0.1 to about 5~ ~ulfur, by weight, based on the
weight of the poly~aryl ether ketone), the sulfur pre~ent a~
at lea~t one member of the class con~isting of elemental
sulfur, aliphatic and aromatic dithiols, polysulfides of the
formula -R-S-S- where R is a bivalent aliphatic or aromatic
radical and inorganic ~ulphides. These compo~ition~ are
u3eful for their high tensile modulus, their high-
temperature adhe~ive properties, and their dimensional
stability. The invention further relate~ to a composition
comprising al a poly(aryl ether ketone) having intimately
disper~ed ~herein from about 0.1~ to 5~ sulfur, by
weight, ba~ed on the weight of the polytaryl ether ketone),
the sulfur present as at lea~t one member of the cla3s
consisting of elemental sulfur, aliphatic and aro~atic
dithiols~ polyqulfides of the formula -R-S-S- where R is
a bivalent aliphatic or aromatic radical and inorganic
sulphide~ and b) a reinforcing filler. The composition
provides a stable reinforced poly~aryl ether ketone)
composition.
~ 2 ~ S
Figure l is a stress strain curve at 200C for annealed
samples of poly(aryl ether ketone) both with and without
sulfur.
S Figure 2 is a stre~3 versus time graph for annealed
samples of a poly(aryl ether ketone) both with and
without sulfur.
Figures 3 and 4 are stre~3q relaxation curves for
annealed qamp}e-~.
Figures 5 and 6 are graphs 3howing creep strain %
verses time at 2&0C for poly~aryl ether ketone~ with
and without sulfur.
DETAILED DEscRlps~o~ OF T~E INVENTION
Elemental sulfur, which ha~ an atomic w2igh~ of 32.06,
lS existq in two crystalline form~ at room temperature and
melting point of about 114C. It is inqoluble in water;
soluble in carbon disulfide. The composition of the
invention contains from about 0.1% to about 5~ sulfur on
a weight b~sis. A preferred concentration of sulfur
in the invention is between 0.25% and 2%.
,.~
302~^S
-- 4 --
In the practice of this invention the sulfur may be
dispersed in the poly(arylether ketone) in the form of a compound
as described above. Of the dithiols, aromatic dithiols of the
type HS-R-SH where R is a bivalent aromatic radical are preferred.
Preferred aromatic dithiols are biphenyl-4,4'-dithiol, 4,4'-dimer-
captodiphenyl ether and bis-(4-mercaptophenyl) sulphone. Polydi-
sulphides comprising repeat units having the formula -R-S-S- where
R is a bivalent aliphatic and/or aromatic radical may also be used.
A preferred inorganic sulphide is MoS2. The weight of sulfur is
calculated as the amount of sulfur present as elemental sulfur,
sulphide which includes mercaptan and thiol, or disulphide.
- .. ; .- , ~
-5- ~ ~80~4~'
The term poly(aryl ether ~etone) referq to polymers
having the repeat unit of the formula
-C0-Ar-C0-Ar'-
wherein Ar and Ar' are aromati.c moieties at least one of
which containing a diaryl ethe!r linkage forming part of
the polymer backbone and where!in both Ar and Ar' are
covalently linked to the carbonyl group~ through aromatic
carbon atom~.
Preferably, Ar and Ar' are independently 3elected
from substituted and unsub~tituted phenylene and ~ubstituted
and un~ubstituted polynuclear aromatic moieties. The term
polynuclear aromatic moieites i9 used to mean aromatic
moieties containing at lea~t two aromatic ring~. The rinq~
can be fused, joined by a direct bond or by a linking group.
Such linking group~ include for example, carbonyl, ether
sulfone, sulfide, amide, imide, a20, alkylene, perfluoro-
alkylene and the like. A3 mentioned above, at least one of
Ar and Ar' contain~ a diaryl ether linkage.
The phenylene and polynuclear aromatic m3ietie~ c~n
contain substituent~ on the aromatic ring~. These sub~ti-
tuent~ ~hould not inhibit or otherwi~e interfere with the
poly~erization re~ction to any 3ignificant extent. Such
~ub3tituent~ include, for example, phenyl, halogen, nitro,
cyano, alkyl, 2-alkynyl and ~he like.
~C)24~
Poly(aryl ether ketones) having the following repeat
units (the simplest repeat unit being de~ignated for a
given polymer) are preferred:
o-~c
-~o @~-o~ c-
~) o ~ r ~ o ~) 8 ~c
~ _ ~ o I ~) ~ .1 ~ c
~ - ~ D ~ C -
~ ~a OE) ~ ~3
-~_ ~7~ 1 ~ ~0~ 4 ~
Poly~aryl ether ketones) can be prepared by known
method~ of synthe~ Preferred poly~aryl ether ketones)
can be prepared by Friedel-Craftq polymerization of a
monomer system comprising:
I~ (i) phosgene or an aromatic diacid dihalide together
with
(ii) a polynuclear aromatic comonomer comprising:
(a) H-Arn-O-Arn--8
(b) H-(Ar~-O~n-Ar~-~
wherein n i~ 2 or 3
(c) H-Ar~-0-Ar~-(CO-Ar~-0-Ar~)m-8
wherein m i~ 1, 2 or 3
or
(d) H-(Ar~-O)Q-Ar~-CO-Ar~-(0-Ar n )m_H
: 15 w~erein m is 1, ~ or 3,
and n i~ 2 or 3
or
II~ an acid halide of the formula:
~-Ar~-O-t(Ar~-co)p-~Ar~-o)q-(Arn-~o)r]k-Ar~-co-z
wherein Z i~ halo~en, k i~ 0, l or 2, p is
1 or 2, q i~ 0, l or 2 and r i Q O ~ 1 or 2;
~ ox~
o~
III) an acid halide of the formula:
H-lAr"-O)n-Ar"-Y
wherein n i~ 2 or 3 and Y iR CO-Z or CO-Ar~-CO Z
S where Z is halogen;
wherein each Ar~ is independen~ly ~elected from ~ub~ti-
tuted or unsubstituted phenylene, and substituted and
un~ub~tituted polynuclear aromatic moietie~ free of
ketone carbonyl or ether oxygen group~, in ~he presence
of a reaction mediu~ comprising:
A) A Lewis acid in an amount of one equivalent per
equivalent of carbonyl group~ pre~ent, pluR one
equivalent per eguivalent o~ Lewis ba~e, plu~ an
a~ount effective to act a~ a cataly4t for the
polymerization;
8) a Lewis ba~e in an amount from 0 to about 4
equivalent3 per equi~alent of acid halide groups
pre~ent in the monomer ~y~tem;
and
C) a non-protic diluent in an amount from 0 to about
93~ by w~ight, ba~ed on the weight of the total
reac~ion mixture.
- 9 -
~0~ 5
The aromatic diacid dihalid~ employed is preferably a
dichloride or dibromidæ. IllugtratiYe d.iacid dihalides which
can bo usQd i~clude, for examplo
Clll~ ~~ ~11
''I'~B ~ 1l
Il ~
~IC~C~l Ct:~CJ ~le~ $~C-I
O O O
wher~in ~ i~ 0 ~.
-10~ 30245
Illu3trated polynuclear Aromatic comonomers which can
be used with such diacid halides are:
(a~ ~-Ar''-O-ArU-H, which include~, for example:
( b ) ~- (Ar "-O ~ ~ O--~--O--
and
~ -~
~c) H-Ar~-O-Ar"-~CO-Ar''-O-Ar~)m-H, which includeq, for
example:
0 -~ C, - ~ O ~
and
td) H-tAr"-O)n-Ar~-CO-Ar~-~O-Arn)m-H which inclùdes,
f or example:
~3 ~3 ~ (~
Mono~o~r ~ystems II and III comprise an acid halide. tThe
term acid halida is used herein to refer to a monoacid monohalide. )
In monomer 3y9t:elll II, the acid halid~ i9 of the formula-
H-Ar"-O-[~Ar"-CO)p-~Ara-O)q-tAr"-CO)r]k-Ar"-CO-Z
o~v~
Such monom~rs include for example, where k - O
~`~C~ o-~c
~~ '~--C~ C'Cl
~n~ ~her@ Lt _ 1
O
~\0/~ ~~,CIC1
.~ O
~O~ C~ Ct
O
~ ~ -12-
0~5
In monomer sy tem III, the acid halide is of the
formula
H-(Ar"-O)n-Ar"-Y
Examples of such acid halides include
o
~.0~ 1 "
and
0~ ~ r 1
It i9 to be understood that combina~ions of monomers
can be employed. Por example, one or more diacid dihalides
can be used with one or more polynuclear aromatic comonomers
as long aq the correct stoichiometry is maintained. Further,
one or more acid halides can be included. In addition
monomer~ which contain other linkages such as those speciied
above, can be employed as long as one or more of the comonomers
used contain~ at lea~t one ether oxygen linkage. Such
comonomers include for example:
~ O~ 5 ~ ~ ~ CH~
~8~)~4~i 26775-63
which can be used as the sole comonomer with an ether containing
diacid dihalide or with phosgene or any diacid dihalide when used
in addition to a polynuclear aromatic comonomer as defined in
I(ii) (a), I(ii) (b), I(ii) (c) or I(ii) (d). Similarly
~C~2\[~
can be used as a comonomer together with an ether-containing
polynuclear aromatic acid halide or as an additional comonomer
together with a monomer system as defined in I.
The monomer system can also contain up to about 30 mole
% of a comonomer such as a sulfonyl chloride which polymerizes
under Friedel-Crafts conditions to provide ketone/sulfone
copolymers.
~urther details of this process for producing poly(aryl
ether ketones) can be found in Canadian application Serial No.
450,962.
:.,
.~.
~ -i4~ 245
Additives may be included with the poly(aryl ether
ketone) compo~itions of this invention. These additives
include, for example, pla~ticizers and pigments, non-
reinforcing filler~, thermal 3tabilizer ; ultraviolet-light
stabilizers, proce3~ing aids, impact modifiers, carbon
black, and the like. The invention al~o relate~ to a
reinforced compo~ition compri~ing the composition and a
reinforcing filler such aq carbon or glass fibers or other
polymeric fiber~ ~uch a~ polyamides or relnforcing fillers
such a graphite thus further increa~ing the strength of the
compo~ition. It i9 preferred that the reinforcing filler be
present in an amount of from about 2% to about 30~ by weight
and the compo~ition. Where fillers are used they may be
blended into the poly(aryl ether ketone) compo~ition at any
convenient point in the operation.
The sulfur, in a concentration of from about .1%
to about 5~, may be intimately di~per~ed in the poly(aryl
ether ketone) by mixing or blending at a temperature of
at lea~t about the melting point of the poly(aryl ether
ketone). For example, the culfur may be mixed at the
proces~ing temperature using a me~hanical mixin~ apparatus
A preferred method of mixing i9 by extru ion. A mixture
blended at a te~perature lower than the temperature may be
heated to proce~3ing temperature, say e.g., by extru~ion
proce~, and then mixed further at ~uch temperature.
The compo3ition~ of the invention have variou~ u~es.
The compo~ition can be for~ed into high-ten3ile-modulu~
fiber3. Poly~aryl ether ketones) by them elves are dif-
ficult to use a~ high-temperature hot-melt adhe~ives
because their visco~itie~ are too high even at their melt
temperature~. However, compo3ition~ of the invention
4~
can have lower vi~cosity before curing. Upon po~t curing
at high temperature, cros~linking occurs within the
material, and thereby improves the creep re~istance at high
temperatures. Hence, thi modified material performq well as
an adhesive at high temperature Another use for the
compositions of the invention comprise~ the manufacture
of molded or extruded article 3 which would show greater
dimensional stability due to increased modulus and may be
useful, for example, in well and minin~ applications where
service life i~ critical.
The following example-~ serve to further deqcribe and
illustrate the practicing of the invention. Further, the
examples demonstrate the improvement~ and desirably useful
properties of the compo~itions deqcribed herein. One skilled
in the art would readily be able ~o make substitutions of
polymers or make adju~tment3 in temperature, mixing
condition~, etc. The example~ are not intended in any
way to limit the scope of the invention.
DESCRIPTION OF T~E PREFERRED EMBODIMEN~S
Example 1 - Procedure
~ he samples in examples 2-5 were all prepared and
tested in a similar fashion. The poly(aryl ether ketone) for
the adhe~ive was poly (carbonyl-p-phenylene-p-oxy-phenylene-
p-oxy-phenylene) FQrmula IV (vitrex~Peek from ICI Americas
hereafter PEE ~ . Elemental sulfur was added to the said
polymer in weight percentage3 of 0, 0.5, and 1.0 and
extruded on a ZSR extruder. The pellet~ were then pressed
into slabs approximately 16 in2 and 0.020 - 0.030 inches
thick. A polyimide film (commercially available as Kapton~
film from DuPont) wa~ used to prevent the polymer from
~trad~m~
-16- ~ ~ ~ox~5
sticking to the press plates. This pre~sing was done at
350Cr 10,000 lbs. ram force, and for four minute. After
the hot pressing, the slab was put into a cold press for two
minute~ at 1000 lbs. ram force. The cold slabs were then
cut into l-inch by l-inch pieces. In some instances the
raw material was Qcraped with a razor blade and wiped with
methanol. This wa9 done to remove dirt, sand and Xap~on
that had accumulated on the aclhesive ~urface.
Once the subRtrate either cold rolled steel or titanium
a~ indicated below, and adhesive were cleaned, the two
were bonded. The l-inch by l--inch adhesive slab was taped
between two substrate~ with l-inch aluminum tape. Thus
the bonding area wa~ one ~quare inch. The sample~, including
tape, adhe~ive, and two ~ubstrate~, were abou~ about 0.130
inche3 thick. A presQing window of 0.120 inch wa~ used to
bond the sample. All pre~singq were done a 371C (700F),
at pressure~ ranging from 250 psi to 5000 p~i, and with
bonding times varying from 3 minuteq to 20 minutes. After
the hot pres~, 3amples were immediately cold pres~ed at
approximately 250 p9i for four minutes. Once bonding was
fini~hed, the tape wa9 removed and any adhe~ive present on
the edges wa~ removed with a razor blade.
Room-temperature lap-~hear testing wa~ done on a
10,000~1b. In~tron. A cro3shead speed of 2 inche~ per
minute wa~ u~ed.
-17- ~ 2 ~ 4S
Example 2 - Control
LAP-SHEAR STRENGTH OF PEEX *
Mea:n Lap-
Substrate** Shear Strlen~th ~i) No. of SamPles
Cold-Rolled Steel 810 4
C~ld-Rolled Steel 910 5
Cold-Rolled Steel 790 4
Cold-Rolled Steel 980 4
Cold-Rolled 5teel 760 4
Titanium 400 4
Titanium 200 6
Overall Mean Stren~th (PSi )
S~eel Substrate, 21 Sample~ 850 + l50
Titanium Substrate, l0 Sample3 300 + ll0
5 *Cleaning of ~ub~trate - Sa~dinq, water rinse, acetone
dip; polymer ~craped, wiped with MeOH.
** Each entry represents an indepe~dent experiment.
Pressed - 10 minutes, 670 psi, 371C
~` -18- ~.2~3024~
Example 3
LAP-S~EAR STRENGTH OF_PEEX + O.5~5*
Mean Lap-
Sub3trate** Shear_Strenqth (psi) No. of Sam~les
Cold-Rolled Steel 2030 4
Cold-Rolled Steel 2470 4
Cold-Rolled Steel 2300 3
Cold-Rolled Steel 2500 4
Cold-Rolled Steel 2340 2
Titanium 1430 5
Overall Mean Strenqth (PSi )
; Steel Sub trate, 17 Samples2330 + 240
Titanium Substrate, 5 Sample-~ 1430 + 60
*Cleaning of substrate - Standing, water rin~e, acetone
dip; polymer scraped, wiped with MeO~.
** Each entr~ repre~ent~ an independent experiment.
Pr~ssed - 10 minutes, 500 - 1000 p3i, 371C
~ 19- ~ 4`5
ExamPle 4
LAP-SHEAR STRENGTH OF PEER ~ 1~ S*
Mean I ap -
SubRtrate** Shear Strength ~p9i ) No. of Samples
Cold-Rolled Steel 2220 4
Cold-Rolled Steel 1980
Cold-Rolled Steel 1850 2
Cold-Rolled Steel 2430 3
Cold-Rolled Steel 1930 4
Cold-Rolled Steel 2070 3
Cold-Rolled Steel 2240
Titanium 1930 3
: Overall Mean Strenqth (~si ?
Steel Substrate, 23 Samples 2140 + 290
Titanium Sub3trate, ~ Sample 1930 + 150
*Cleaning of sub3tr~te - Sanding, wat~r rinse, acetona
dip; polymer ~craped, wiped with MeOH.
** Each entry repre~ents an independent experiment.
Pre~ed - 10 minutes, 670 p~i, 371C
.. ,.. : ..-. . . .
- - -
- - - ~ o -
1~30Z45
Example 5
1~P-SHEAR STRENGTR OF ANNEALED SAMPLES *
Mean Lap-
Set Substrate*~ Shear Stren~th (psi) No. of Sam~l_s
M PEER - Steel 1390 4
BB PEEX - Steel 1410 5
X PEE~ ~ 1% S - Steel 2540 5
BB PEER + 1~ S - Steel 2460 6
AD PEE~ + 13 S - Steel 2540 4
3~ PEER + 1% S - Steel 2540 4
Overall Mean Strenqth (p~i)
PEER - Steel, 9 Sample~ 1400
PE~ + 1~ S - Steel, 19 Sample~ 2510
*Cleaning of ~ub~trate - Standing, water rin~e, acetone
dip; poly~er ~craped, wiped with MeOH.
** Each entry repre~ent3 an independent experiment.
Pressed - 10 minutes, 600 - 1000 psi, 371C
Annealed - 210C/18 hours -
' ~'~`` ., ~ -
~`` -21- 1 2 ~lOZ4 5
Example 6 - Procedures
Polymers of Formula I or IV (PEE~) as pellets were
mixed with elemental Sulfur in a plastic container. The
polymer pellet~ were usually clried at 150C for 4 hours
before they were proce~sed. 1'he sulfur-concentration
ranges of 0.25-2~ by weight were uced. In addition, two
dithiols (4-4' biphenylidithiol and 4-4' dimercaptoether)
and one inorganic 3ulphide (MoS2) were u~ed in the for-
mulations. The mixture~ of Formula I or Formula IV with
each of 3ulfur, dithiol, and c~ulphide were compounded
using either the ZSK or ZSE extruder. H2S wa~ evolved
during the mixing process.
It should be noticed that attachment of a vacuum outlet
at the exit of ths die would help to eliminate gases, such
as H2S formed during processing. Thu3, it reduces the poro-
sity of the pellet The re~ulting ZSK- or ZSE-compounded
pellet~ were used in injection-molding of tensile barq
(T-bar~ and in extrusion of tapY and fiber~.
Stre~s-Strain Tests
Stre~-strain test were performed on an Instron. The
tests wer~ chossn to run at room temperature and 200C. The
jaw-~eparation speed was chose~ to ba 2~/min and 0.5"/min at
roo~ temperature and 200C, re~pectively. The high test
temperature wa9 cho~en to be 200C becau~e it i~ higher than
the Tg of both Formula I and PEE~ (Tg - 145bC and 165C for
PEER and Formula I re~pectively). All the sample~ were
annealed for 4 hours at 240C.
Figure l shows stres~-strain curves mea~ured at 200C
for a ~et of injection-~olded T-bars for PEEK. Tables L and
-22- ~2~0~ ~ ~
2 summarize all tencile-elongation properties mea5ured at
room temperature and 200C, respectively, for this set of
sampleq. Two intere4ting feature~ can be observed directly
in Table 2: an increase of Young'~ modulu~ a~ well a~
elongation-at-break i5 ob erved as a function of the sulfur
concentration and the addition of the dithiolq produce~
similar effect~ a~ elemental ~ulfur does. The room-
temperature data agre~ with what we generally observe for
materials that are crosslinked--a decrea~e in elongation-at-
break and no 3ignificant increase in ten~ile dulus at tem-
perature balow Tg. However, the 200C data show a maximum
increase of 50~ both in the Young's modulus and elongation-
at-break at sulfur concentration of l~.
Example 7
~ii) Stress-relaxation and creeP measurement-~
Creep and stres~-relaxation are two important tests,
whi~h measure the dimen~ional ~tability of a material.
Streq~-relaxation, which i~ the counterpart of creep, can be
easily performed on an In~tron. The sample i~ 3ubjected to
a con~tant strain tS% ~train wa~ u~ed) and the de~ay of
stresR a~ a function of time iq observed. In a creep
experiment, a con~tant force i~ applied to the sample by a
weight and the ~train a3 a function of time i3 measured by
means of a transducer. To observe th~ effect~ both stress-
relaxation and creep expsriments were performed at 200C,which i~ above the Tg of both PEER and the polymer of
Formula I. Tha ~amples were annealed at 240C for 4 hour~
before experimentQ.
Fi~ure 2 ~how~ a set of ~tre~-relaxation curves at
200C for four ~amples: curve (A) Formula I, curve tB)
_~ -23- ~ z ~ 5
- Formula I + 0~25~ S, curve (C) - Formula I + 0.5~ S and
curve (D) - Formula I + 1% S. Curves ~A-C) appear to have
a very similar relaxation time since their gradients are
very cimilar. However; the initial and final stresses of
the Formula I ~ 1~ S are approximately 100~ higher than
thoYe of the control sample. Thi3 mean3 that the Formula I
+ 1~ S material i9 a much betl:er material for making
high-temperature ~tructural parts because under a con~tant
stres~, it would have a much :Les~ deformation (elongation).
Similar result~, but les~ drar~tic, are observed for the
Formula I 9amples with lower sulfur concentration3 as
shown in Figure 2. Figures 3 and 4 show ~imilar curves
for PEER samples. Sulfur has ~imilar effect on PEEX as
it ha~ on Formula I. The two dithiol~ and MoS2 also
improve P~EX' 3 performance in the stres~-relaxation
experiment.
Creep data, which are more useful to engineer~ than
stress-relaxation data are shown in Figures 5 and 6. The
samples used in this experiment were extruded taps of PE~K
and PE~R + 0. 25~ ~r In Figure 5 the two ~amples were kept
under a constant stress approximately equal to 1300 psi.
The initial ~train (t-0) and final strain (t-100 min) of the
PEEK + 0.25~ S sample are much les-~ than those of the
control sample. A similar trend is observed in Figure 6 for
the te~t performed at different stres~e~. In addition, at
high stress ( a-2100 p3i ), the control sample appears to
have a higher creep rate than ~ulfur-modified ~ample. The
creep re ult~ are in good agreement with the stres~-
relaxation data.
-- -24- i ~O~4-~
Exam~le 8
Mechanical Properties of sulfur-modified PEEX fiber~
Two sets of fibers ~100~ PEE~ and 99.5% victrex PEER
and 0.5~ sulfur) were extrdued. The extruded fiber~ were
aged at 260 and 300C for various length~ of time. The
room-temperature an~ 200 C m~chanical properties of thece
fibers were measured. The re3ult~ were ~ummarized in Tableq
3-6. The 200-C Young's modulu~ of the extruded sulfur-
modified PEER fiber~ i~ about twice that of the
control fibers. It is known that the Young's modulus of
Victrex PEER and Formula I will increase upon annealing at
high temperature in air. The re-~ults shown in Tables 3-S
do show an increase of the Young's dulu~ as a function
of aging time. However, the 200C Young's modulus of the
sulfur-modified Victrex PEER fibers i~ close to a factor
of two higher than that of con rol counterparts at variou~
length~ of aging time. These reqult~ indicate positively
that sulfur can increase the high-temperature mechanical
properties of Victrex PE~ or Formula I beyond what can
be achieved by annealing ths polymer~ at high temperatures
in air.
-25- ~.2~30~45
Table L
mechanical pro~erti~s of peek at R. T.
,ample ~(P i x ~oo~ (:rb(P~i % 100) ~b (%)
~5 13.8 40
2 211 14.2 23
3 204 1 3.5 ~8
4 2~2 14.~ 25
18~ ~5.1 ~7
6 216 13.5 10
7 ~98 13.7 13
8 ~01 14.5 28
9 208 14.5 25
peek~sample ~nn~aled at 240 C for 4 hr.
2 pa~k 0~.25%~i~(zse): injection-m~lded T-bar
3 pel~k 0.25~oS
4 poQk 0.5VoS
peek 1.0%S
8 peek 3~ 4-4 b~henyl dithitoz~
~r~Q,o a~e~/e ~ ~ ~'
7 pe~k 3~0 4-4 ~L=~r
8 p~ek 3~ MoS
9 po~k 3~ Mo-~ 0.2S% S
26- ~ 2802
Ta~ie 2
m@chanlcal prop@rti~s of pe~k at 2û0 C
sampl~ E sp~i XloO) Crbl~P~ x tO0) ~b(%)
2201 5~ . 160
2 2703 6.3 198
3 3~.3 $~2 220
4 3~.0 6. 1 ~0
30.4 6.~ 2~7
6 3 ~ .4 ~.2 2~2
7 25.9 6.4 210
PQek
2 pe~k Or2~
3 p~k O.S$S
4 p~k l.Oa'oS
5 p~k 3% 4~ he~nyldithitol
O .~er ~7~Od~ é~y/e7~ r
pe~k 3~b 4-4
7 pe~k 3$ Mo~3
~(Z~ inJ~ctlon-mold~ld T-bar
~samplo annQaled at 240 C ~or 4 hr.
-" ~1 2~3~)245
Table 3: Room-temperature mechanical properties of the
control and sulfur-modified Victrex PEEX fibers
aged at 260C
Aging time
5(day~) 0 1 2 5 8 14 22 30 40
_ _
Samples Young's n~odulu~ x 1000 p~i
control 240 325 318 271 261 422 386 353 377
0.5%-S 219 32~ 432 414 396 439 460 470 473
. _
Sample~ Tensile strength x 1000 psi
10control 20 23 24 24 24 23 22 2222
0.5~-S 20 24 28 28 27 27 25 2728
_ _ _ _ _
Sample~ Elongation (~)
control 160 110 105 108 107110 102 9090
0.5~-S 140 43 60 55 53 70 53 4037
_ -2~-
~.2~30~.5
Table 4: 200C mechanical propertiec of the control
and sulfur-modified Victrex PEEK fiber~
aged at 260C
Aging time
5(day~) 0 1 2 5 8 14 22 30 40
Samples Young's ~dulu-~ x 1000 pqi
control 13 39 42 42 42 36 50 51 52
0.5~-S 25 60 70 66 69 71 ~2 84 99
Samples TenQile strength x 1000 psi
10control 9 1010 10 10 10 12 14 15
0.5%-S 10 1012 1~ 11 14 13 12 13
.
Samples Elonqation (%)
control 181 137140 147 133 165 178 192 183
0.5~-S 155 97123 103 90 128 100 83 80
.. _ . . . .
., .. : ~ ~
29~ 0 2~A5
Table 5: Room-temperatUre mechanical properties of
the control and sulfur-modified fibers
aged at 300C
Aging time
tdays) 0 1 2 5 8 14 22 30 40
.
Samples Young'q modulu~ x 1000 p3i
control 240 292 308 280 418 397 374 394 352
0.5~-S 219 403 382 387 587 ~38 435 378 41
. , _ _ _ . . . .
Samples Ten3ile ~trength x 1000 p~i
control 20 2421 22 24 22 21 22 20
0.5~-S 20 2829 29 28 23 23 23 21
-
Sample~ Elongation (%)
control 160 10788 60 50 33 20 12 12
0.5~-S 140 ~058 43 2~ 19 12 9 6
.
... . . ~ ~
-30-
~.2,~0~ 4 ~
Table 6: 200C mechanical properties of the control and
sulfur modified Victrex PEER fibers aged at
300C
Aging time
5 (days) 0 1 2 5 8 14 22 30 40
.
Samples Young'~ modulus x 1000 p3i
control 13 39 40 45 53 87 187 170 167
0.5~-S 25 60 58 81 122 170 298 270251
Samples Ten~ile ~trength x 1000 psi
10control 9 1012 11 12 14 12 1310
0.5%-S 10 1314 14 15 14 13 1313
,
Sample~ Elongation ~%)
control 181 130132 95 63 38 16 10 3
0.5~-S 15~ 80 68 32 27 23 10 g 5
