REGUI,AR CONTRIBUTED ARTICLES

E. B. Muliawan,

S. G. Hatzikiriakost*,

M. Sentmanat

t^Department of Chemic'al and Biological Engineering, (.lniversily of British Columbia Vancouver, 8.C., Canada 'Senkhar Technolosies, Akron, Ohio. (lSA

MeltFracture Linear of PE
A Critical Study in Termsof Their Extensional Behaviour

In this paper we studied the melt fradure behaviour in capillary flow of a number of polye.thylenes pntdut-ed by various technoktgies. The L:riti<:al slrcar rates for the onset of both sharkskin and gross melt.fractures were.ftntnd to correlate with the high-rate extensional flrn behavictur rf the polymers. Thesefindings were.fourul b mechanistically support the generally accepted obscrvatiorts of melt frat:ture occurring at the exit (sharkskin) and entrance (gross) region.r of the capillary die- In afulition, it wa.s.ftnruL that bontn nilri.le (BN) hehaves as an energ), dissipater that sultpresses the rapid iru:rcose of extensional .strass associated with grossmelt fracture. This enables BN to o(:t os an eflcctive-prcces.sing oid. in F,stlroning gross melt fracture in the e,rtrusion of polyethylenes.

I Introduction Melt fracture is a polyrncr instability (rnore pronounced in polyethylenes) that limits thc rate of production in nrany proccsses such as profile extrusion, film casting, film blowing, blow moulding, and wire coating [],2]. In thesc processes, a polymeric melt emerging from the dit: often shows surface distortions at throughput ratcs abovc a critical valuc. As a rcsult of these instabilities, the linal products becornc unattractive and commercially unacceptable.This ellcct can range from loss of gloss of extruclate surfirce (known also as haziness) to small amplitude periodic distortions (sharkskin melt fracture) and finally to irregular gross distortions (gross melt fracture) at high extrusion rates [3 to 5]. Some of the pararneters al'fecting the degree of extrudate distortion include process temperature, flow rate, concentration and type of additive, geometrical dimensions of the die; chemical nature of the polymer, entrance geometry to the die and many others [3, -5]. There is a general agreerllent that the site of initiation of sharkskin is located at the die exit [6, 71. Howells an<] Benhow [6] and Cogswell [7] hypothesized that polymers fracture at the die exit due to high extensional stressesthat develop at this location. The melt leaving the die in the neighborhood of the wall experiencesa large, rapid, tcnsile deformation as the velocity field adjusts from the no-slip boundary condition to the + Mail address: G. Hatzikiriakos, S. Dep. of Chem. and Bio, Eng., Universityof British Colurnbia, 2216 Main Mall, Vancouver, B.C., Canada VGT 124 E-mail:hatzikir@ interchanse.ubc.ca

liee-surface condition. Polymer chains are stretched during the tensile deformation, which causes thc highly entangled polymer to respond like a nrbber. The l:uge stresses the ficc on surface cause periodic cracks that result into small amplitude periodic distortions (sharkskin). This original proposition ol fracture at the die exit as the cause of sharkskin has been substantiated by microscopic flow visualization observations reported by Migler et al. [8J. The presenceof :r fluoropolymer at the die exit serves to lubricate the surface of the exiting extrudatc thercby reducing thc extcnsional stress transition, resulting in eithcr the cornplete elimination or postponement of sharkskin to rnuch higher shear rates. Othcr works supporting thc original findings by Howells and Benbow,[6] and Cogswell [7] are cited in [9 t() l4l. Most authors also agree that above a certain extrusion ratc much higher than the critical one for the onset of the exit instability discussed abovc (sharkskin), the flow upstream of the die contraction becomes unstable. Thcse instabilities occur in the form of sudden pulsation which was confirmed by visualization experirnents [5 to l7] and birefringence measurements [81. The visualization experimcnts have shown that such instabilities are due to the high elongation stressesthat develop at this location of the die. Thcse upstream instabilities cause the phenomenon of gross melt fracture, which is often seen in the fbrm of a regular helix oscillating at the same frequency as that of the pulsations of the upstream ekrngational flow [51. Therelbre, a critical extensional stress appearsto be thc criterion for the onset of gross melt tiacture [7, 19 to 2l]. Kim aru1 Dealy [2ll reported critical extensional stressesfor the onset of gross melt fracture of the order of I to 2.-5MPa independent of tcmperature and molecular weight. These values can be significantly highcr for polydisperse polymers having a small dcgree oflong chain branching. As discussed above both sharkskin and gross melt fracturc are due to high extensional stresses,their only difference is at the site of their initiation. Therefore, it is logical to study melt fiacture phenomena and their relation to the high-rate extensional flow behaviour of polymer melts. However, to measure the extensional rheology of polymers at high rates relevant to the occurrence of melt fracture phenomena was not an easy task to carry out until recently with the development of the SER rheometer f22, 231|.The availability of this unique rheometer has stimulated this work. It is the main objective of this work to study the melt fracture phenomena of a number of polyethylenes and consequently relatc thcir processability to their extensional rheologv. This will demonstratethe relevance Intern. Polymer Processing XX (200-5) I

60

@ HanserPublishers, Munich

'.^ I t L,,o'")
E. R. Muliawan et al.: Melt Fracture of Lincar PE

Rcsin

Commercial nomenclature

Melt index (g/10 min) (Iz)

Dcnsitv i) GJr

Co-rnonomer

Catalyst type

Additive

Process technology Unipol Gas Phase Unipol Cas Phasc AST Solution AST Solution AST Solution SCLAIR Solution

Application

B C D E F

PF-Y82I-BP (LLDPE) TD-9022-D (LLDPE) FP-l 20,F (LLDPE) FPs-lI 7-A (LLl)P11) F'P-O1-5-A (LLDPE) 58G (}{DPE)

0.80 0.tt0 1.00 r.00 0..55 (16) 0.95

0.9230 95 0.9r 0.92r 8 0.9 r70 09|7-5 0.9-575

Butene Hexene Octene Octene Octene

Z-N Z-N Z-N Singlesite Z-N Z.N

1" + 2" AO, Slip, AB l" + 2" AO, Slip, AB l" + 2" AO, AB l"+2"AO l'+ 2"AO, Slip, AB t" Ao

Film Film Film Film Film Blow Molding

Notcs: l' = himary Anti Oxitlant, 2' = Sccondary Anti Oxidant, AB = Antiblock Agcnt, Slip = Slip Additive 'lhble 1. A summnry rf the moleculnr chorncleri.slirs of the polyethylene resins studied

of extensional rheological behavior of polymcrs itr the occurrencc of these phenomena and provide additional insight trr their origin. Moreover, it is dcmonstrated that the use of a polyrner processing aid (boron nitride), which has bccn reported 1tr postpone the occurrence of these plrenotttcna at higher shear rates,behavesas an encrgy dissipater (suppressthe rapid dcvclopment of extcnsional stresscs)-Such a finding provides additional evidence as to the existencc o[ a critical extensional stressrequircd for the trccurrence of mclt fracturc.

2 Experimental Six differcnt polyethylenes wcrc uscd in this stutly. The technologies used to prcducc the resins include gas phase and solution technology using either Ziegler-Nalta catalyst or a Proprietary single site catalyst dcvcloped by Nova Chemicals Corporation, The molecular characteristics o[ thesc rcsins ue summarizedin Table l. Rheological characterization in terms of linear viscoelasticity of erllvirgin polyethylene samples was performed by using a Rheometrics System IV rheometer equipped with 2-5mm par-

allel plates. The characterizationwas carried out by performing frequency sweep experiments in the frequency range of 0.0l ratVs to about 500 rad/s. All of the tcsts were done at temperatures of 170"C, 190"C, and 210"C. Time temperature superposition was applied to obtain the master linear viscoelastic curvcs at the reference tempcrature of 170"C. The extensional rheology of all virgin resins was assessed with the new SER Universal Testing Platform from Xpansion Instruments 122, 231. As depicted in Fig. 1 and further described by Sentmanal 122,231, the SER unit is a dual windup extcnsional rheometer that has been specifically designed for use as a detachable fixture on a variety of commercially available rotational rheometer host platforms. The SER-HV-A0I modcl used in this study was accommodated on a Rheometrics RDAII rotational rheometer host station platform and was capable of generating Hencky strain rates up lo 20s-r under controlled temperatures in cxcess of 250'C. In this work, the "C. Extenextensional rheology of all resins was studied at 170 prepared by compression sional melt rheology specimenswere molding polymer sample between polyester films to a gage of 0.5 to I mm using a hydraulic press. Long polymer strips ap proximately 15 to 17 mm in width were then cut from the

Fig. I. Universal testing platform accommodated on a rotational rheometer host system, and a schematic illustration of the fixnre duing operation

Intern- Polymer ProcessingXX (200-5)I

61

E. B. Muliawan et al.: Melt Fracture of Linear PE

molded polymer sheets. From these long strips, individual polymer specimens were then cut to a width of 6.4 to 12.7 mm using a dual blade cutter with an adjustable gap spacing. Typical SER extensional melt rheology specimens range from 40 to l -50mg in mass-Extensional rheology testsbegan by heating the SER unit to the desired temperature, and after allowing the unit to equilibrate at the temperature, loading and securing the polymer sample onto the preheated drums. Settings for the experiment (e. g. strain rate and frequency of data collection) were input into the software that came with the rotational rheometer. To examine the processability of polymers in capillary die flow, the Rosand RH-2in0 capillary rheometer was used. The barrel was equipped with a three zone electric heater and an adaptive PID tempcraturecontroller with an accuracy of 0. I "C. The barrel was l90mm in length and l-5mm in diameter. A stepper motor was used to drive the piston from a speed of 0. I mm per minute to a maximum speedof 600 mm per minute. A pressuretransducerinstalled on top of the piston driver measured the extrusion pressure.The rheometer also canre with data analysissoftware.Only one type of capillary die was used in this study. It was made of tungstencarbidc, with a diameter of I mm, length to diameter ratio of 16 and entrance angle of 180". No
10' Pa
1d Pa.s

Bagley correction was applied on the extrusion pressure. The length of the die was considered to be long enough so that the end pressure correction becomes insignificant. During the extrusion process, the piston was allowed to travcl down the barrel at a preset speed corresponding to a desired shear rate. The speed was maintained until an obvious steady extrusion pressurewas recorded. Polymer samples extruded under steady extrusion pressure were collected. The extruded samples were then inspected by means of both unaided eye and optical microscope to detect the presence of melt fracture.

3 Rqsults and Discussion 3.I Linear Viscoelasticity Figs.2 and 3 show typical master curves of thc linear viscoelastic moduli and the complex viscosity of resins A and F respectively, at the reference temperature of 170oC- This was done by applying the time-temperature superposition which secrnedto work very well for all resins examined in this studyFigs.4, 5, and 6 show the storage modulus, the loss modulus and the complex viscosity functions of all resins at 170'C. It
rff Pa

1r
(9 O .i 5 o ls Itr 10" o

105

.a

;
o t

(t
v;

'E o c o

' " o
E u
!

_q E O

V a A :

1o'

ResinA ResinB ResinC ResinD ResinE Resin F

;;i;;iii;;;;;ii;;
10? 10' 10o 101 10 radls 1Ol Freqrency, ar ' o)

O a

101

100

10' Frequency

1v

radls

103

F ig. 2. Master

cume of lineor

viscoeLastit: prope rties for

resin A

['ig. 4. Elustit: moduli of virgin resins A, B, C, D, E and F at ]70"C

107 Pa 105 (t ;^
o
J

tos

,,y = > o o
@

9 ro, 6
)

9 r r 9 E
c 101

! o

x
1o"E o 10"

9
3

V a A I O a

Resin A Resin g Resio C Resin D Resin E Resin F

'o'

1o.

1d

1or

1G

rad/s

103

103

Frequency, ar .0

'to1

1op

1ol Frequency

tG

rad/s

1op

Fig. 3. Master curve of linear

,-iscoelastic

properties

for

resin F

Fig. 5 Vscous moduli of virgin resins A, B, C, D, E and F at 170"C

62

Intern. Polymer ProcessingXX (2005) I

E. B. Muliawan et al.: Melt Fractureof Linear PE

can be seenthat typically all resinsexhibit similar rheological data,very little Basedon sucha setofexperimental behaviourinferred with regardto pro,cessabilitycan be for The zero shearviscosities all resinsare listed Table2' Thesewere estimatedby fitting the Crossmodel with the comexperifrom the linearviscoelastic dataobtained plex viscosity well viscosity correlates It seemsthat the zero-shear mentswith the melt index dataalso shownin Table l.

Resin

q" (Pa . s)

B C D E F

29100 221(n r8363 l7 128 3 91 9 8 23256

1o2

1or

t growlh coefficienlcun'esofvirgin resinF at 170"C 8. Fita. Tensilestress 3.2 Extensitnnl RheoktgY

2. 7-abte Ttro shear viscosilies r{the resins at 170"C

v a a I O a 101 1d

Resin A Resin B Resin C Resin D Resin E Resin F 10r

above the exlensional rheology of all the virgin As <liscussecl samples was also studied. Typical tensile stress growth coefficient, qf, plots lhat provide the characterization of the extensional mclt flow behavior of the virgin resins A and F are shown in Figs. 7 and 8 respectively-It can be seen that each of thcse resins exhibits behavior typical for linear polymers. One common characteristic of the extensional behaviour of all resins (including those not shown) is that they exhibit no strain hartlcning effect. In each of these cases' the tensile stress growth cocfficient tends to plateau to a certain level indicated by the linear viscoelastic envelop of each resin before gradually decreasing pnor to ruPture. Strain hardening is usually associatcd with polymers with high molecular weigbt components and high degree of long branching 1241.With highly branched polymers, for example LDPE, thc initial tensile stress growth behavior at low strains is dissipatedby the associativeflow and deformation behaviour of long chain branches along the polymer backbone-The strain hardening manilested by the signiticant deviation from linear viscoelastic behavior at large strains is attributed to polymer backbone stretch that is subsequently preceded by polymer melt rupturc at much higher deforrnations. With linear polymers sich as the LLDPE and HDPE of this study, although there is little deviation from linear viscoelastic behavior at low rates of extension, at high rates of extension the deformarional stressesare bome solely by the polymer chain backbone with little dissipative chain mobility, which leads to melt rupture at lower strains.

1g

radis

10r

Frequenry F-ig.6. Complex vi.sco'silie'r of virgin re.sins A, B , C , D , E o n d F a r

t70"c

u' .,,- zo 1oi'-l

3.3 Capillary Extrusion Studies The processability of the resins was assessed by determining the ciitical shear rate for the onset of sharkskin and gross melt fractures. All extrusion experiments were carried out at oC over a shearrate rang" fto.n 10 s- I to 3000 s- l depend170 ing on how easily the polymer exhibited melt fracture' The flow curves obtained from capillary die extrusion experiments are shown in Figs- 9 to 14. Several characteristics i,rrn-otr to the processing behaviour of these polymers can be

1A2

t Fig.7, 'lensile stress growth coe.fficient curves of virgin resin A at

I70"C lntem. Polymer ProcessingXX (2005) I

63

E. B. Muliawan et al.: Melt Fractureof Linear PE

100 MPa

1oo

die: D=lmm, UD=16, 20=18Oo Capillary

MPa

Die: 9=16p, yp=16, 2q='1660 Capillary ^ o- | oo@v I

oo
E 6 P ro' o 6

o
o u o o c o o

^L-o"o

^ {oo

1'
\

"

o o "

o o o
10,

| ^oo a o " o.[ \ \

\ \
Onet of gao$ melt fdure

Onset ot shafrskin mdt hature

a o

to2

st

101

t02

Apparent shearrate

Apparenl shear rale

Fig. 9. Flow cun,es of resin A in capillary die extru.rion dt 170"C

I;ig. 10. Fl<tw curves of resin B in capilhry die extr*sion at 170"C

seen. First, there is a critical shear stress for the onset of surface/sharkskinmelt fracture conlmon to high density and linear low density polyethylenes. At a second critical shear stressand within a range of apparent shear rates the flow becomes unstable a phenonrcnon known as stick-slip. This stick-slip instability splits thc flow curves into two branches, namely a low flow rate and a high flow rate one. At higher rates, the flow becomes again stable; however, the distortions becorne gross and irregular (onset of gross melt fracture). lt is noted that for some resins the onset of gross melt fracture coincides with the beginning of the higher flow rate branch (see Figs.9 and 12) and for some others there is a delay (see Figs. 10, I I, 13, and l5). In the latter eases,an apparcntsupcr-cxtrusionregirne is obtained before the onset of gross melt fracture. The cxtrudates exhibit minor streaks most o[ the time when extmded under such conditions. From the capillary die extrusion data depicted in Figs.9 to 14, the critical shear rates for the onset of sharkskin, stick-slip and gross melt fracturcs for all the polymers at l70oC were

determined. These arc listcd in Table 3. For examplc, pure resin A exhibits sharkskin melt fracture at a critical shear rate of r. 75 s This is followed by oscillating flow at 300 s-r and '. Most of the resins gross melt fiacture that occurs at 850 s exhibit similar behaviour, where the critical shear rate for the r, stick-slip onset ofsharkskin is in the range of40 to l75s ' in the range 200 to 600 s and gross melt fracture in the range ol 700to l-500s-'. As discussed beftrre, the main ftrcus of the present work is thc onset of sharkskin and gross melt fractures and their relation to the extensional rheological behaviour, A study on the origin of stick-slip phenomcnon and its relation to the extensional rheology of polynrers has been reported previously [25]. Since all of the resins exhibited very similar linear viscoelastic behavior, it was concluded that an analysis of the highrate extensional flow behavior of the resins would provide fundamental insight inkr their processability due to the fact that tensile melt behavior is believed to play an important role in melt fracture phenomena.

Sample lD

Critical shear rate (s

- t)

and stress (MPa) for the onset of Stick-slip

Sharkskin A (LLDPEPF,Y82I-BP) B (LI-DPETD-9022-D) c (LLDPE FP-120-F) D (LLDPE FPs-ll7-A) E (LLDPE FP-OI5-A) F (HDPts58G)
Apparent shear rate Apparent shear stress Apparent shear rate Apparent shear stress Apparent shear rate Apparent shear stress Apparent shear rate Apparent shear stress Apparent shear rate Apparent shear stress Apparent shear rate Apparent shear stress

Grossmelt

15 o.25 100 0.26 100 o.24 50 0.18 40 0.20 175 0.26

300 0.36 225 o.32 325 0.36 600 0.38 200 0.34 300 0.30

850 0.32 900 0.43 I 100 0.42 700 0.38 700 0.39 | 500 0.31

Table 3. Citical

shear rates and stresses for all resins in capillary die extrusion at 170"C

&

Intem. Polymer ProcessingXX (2005) I

l-

E. B. Muliawan et al.: Melt Fractureof Linear PE

'100 MPa

100

die: 3=1p6, YP=16, 2q=1960 Capillary

oo
a

+""
o

die: D=1mm,UD=16,2a=180o M P a Capillary

I n o

^oo

o o "tooo

"
o o < o 6 o 10l

"" ,oooo

\
Onset ot gross mell tradure

oo
6 o <

6o"
I \

^dpo'-

\
Onset of gro$ mell frd@

o o
101

Onsel of sha**rn relt tradure

E
o o o

Onsel ot sharkskinmelt tracture

.i t

't0,
1Or 102 103 S1 101 10? 103 s-'

Apparenl shear rale Fig. t l. Flow cunes of resin C in capillary die extrusion at 170"C

Apparenl shear rale Fig- 13, Fktw cur.tes of resin E in copillary die extrusion at 170"C

10!

1oo die:D=.lmm,UD=16, 2Q=180o Capillary MPa Capiltary die: D:1mm, UD=16,20=1Boo

MPa

o 6 o c c o o o o

o
1 Or "

o o" ooocP o J T
'\

^oo'o" +o-o"
\ \
onsel ol qros mex ftdure o

^ o o a

" ^o+"
I / /
Onsei

" .*t
\
of gross rell kadue

P ro'
o 6 o o

On*l

ol sha*skin

mell tadure

102 102

10?

st

101

1G

sr

:i

rale Apparent shear I;ig. 12. Flow curvesof resin D in copilktry die extrusiondt 170"C

Apparenl shear rale l1g. 14. FIow curves of resin F in capillary die extrusittn at 170"C

{rt
l:l

3.4 On.setof Sharkskin and lts Relation Io Extensional Rheology As previously described, die exit flow is characterized by a large and rapid increase in elastic tensile stressdue to high extensional flow rateson the surface of the extrudate upon exiting the tlie. Depending on the tensile flow and rupture behavior of a polymer melt, these large extensional stressesmay propagate a crack at the melt surface, where the extensional stress is highest, towards the center of the extrudate, where the extensional stress is lowest, This type of sharkskin melt fracture typically occurs at elevated rates of extrusion where the extrudate surface extensional deformation rates are also believed to be high. for all of Fig. 15 contains a plot of true stress versus true strain t thJ polymers at anilevated Hencky strain rate of 20 s . It "elastic modulus (slope be seen that resin E exhibits the highest of the curve at the early stages of the extensional deformation), whereas resin F exhibits the lowest. Sentmanat et al- [25] recently proposed a mechanistic explanation as to the observation of melt fracture based on the tensile melt flow behavior Intem. Polymer hocessing XX (2005) I

of linear and highly branchedpolyethylenes.Basedon extensionalrheologicalresultsat high rates,they have arguedthat linear polymers exhibit a much steeperrise in tensile stress They growth behaviorthan their highly branchedcounterpartsthat the presenceof a significant degreeof further suggested in branching the bulk polymer actsto retardtensile long-chain growth to much higher strainsdue to the dissipativeinterstress prior to the onset action of the polymer branchentanglements that the rapid of backbonestretch.Furthermore,they asserted in increaseof the extensionalstresses the caseof linear polymers leads to rupture of polymers as they exit the die. On the other hand, the tensile retardation mechanismin the case of the branchedpolymers servesto suppress rapid build up of extensionalstressand inhibit crack propagationon the surfaceof the extrudate.This is mainly the reasonthat sharkskinis not a Assuming problem in the extrusionof branchedpolyethylenes. are that the die exit phenomena closely relatedto the rapidity of elastic energy dissipation within the exiting polymer as has the beensuggested, fact that resin E hasshownthe smallestcritical shearrate for the onsetof sharkskinmelt fracturewas not

I'

65

E. B. Muliawan et al.: Melt Fracture of Linear PE

surprising. On the other hand, resin F exhibited the lowest elastic modulus and as a result fractured (sharkskin) at the highest critical sher rate. ln fact, with the exception of resin D, a general correlation exists between the critical shear rate for the onset of melt fracture with the tensile elastic modulus (see critical rates from Table 3 and compare them with the slope of curves from Fig. l5). It can be concluded that the higher the elastic modulus, the smallest the critical shear rate at which sharkskin melt fracture occurs. These experimental results agree well with the trend observedby Sentmanat et al. [25]. Resin D has shown an elastic modulus that was similar to 'that of resin C, however, resin D fractured easier than resin CThis exception could be explained by the lact that resin D was synthesizedusing a single site catalyst technology, which leads to a narower molecular weight distribution (typically a polydispersity o[ about 2) compared to all other polyrners, which possess wider polydispersities. Metallocene LLDPE's have been shown to exhibit sharkskin melt fracture at very small shear rates [27]- This in part was related t() the low degree of shear thinning behaviour. Compared to all other resins in this study, resin D indeed exhibits the lowest degree of shear thinning. Table 3 also lists the critical shear stress for the onsct of sharkskin. While all other resins exhibit sharkskin melt fracture at the critioal shear stressesin the range of 0.21 to 0.26 MPa, resin D fractures at 0.19 MPa.

3.5 Onset rf Gross Melt Fracture and lts Relation to Ertensional Rheolog.y Another important finding obtained from this study was the relationship between the onset o[ gross melt fracture with the extcnsional rheological bchaviour of thc resins. As discussed above, the extensional deformation undergone by the polymer at the entry region to the die, plays a significant role in the gross melt fracture behaviour of polymers. Rough estimates of average extensional rates at the entrance that correspond to the critical shear rates for the onset of gn)ss melt fracture listed in Tabte 3, show that the rates are higher than 20 s I ldcpending on the resin). Due to limitations with transducer compli-

ance, this rate approaches the upper limit ofHencky strain rate that can be achieved with the SER on commercial rotational rheometer host stations in tensile stress growth mode. In spite of this limitation, it is believed that important conclusions can be made by referring to Fig. 15, which compares the tensile stress, oE, of all resins as a function of time at the Hencky I strain rate of 20 s at 170 "C. It can be seen that all the Ziegler-Natta polyethylenes exhibited an obvious trend; the critical shear rate for the onset of gross melt fracture is inversely correlated with the magnitude of the tensile stress. For example, it can be seen from Fig. l5 that resin E exhibits the highest tensile modulus, which translates to a more rapid increase in cxtensional stress.The polymer melt reaches its critical extensional stress for the onset of gross melt fracture at an earlier rate. This observation is in agreement with results reportedby Sentmanat et al. [25]. The only exception that seemed to contradict the correlation between tensile stress and the onset of gross melt fracture was exhibited again by resin D. As described earlier, this was not surprising because resin D was a single site polyethylene, and as such exhibits sharkskin and gross melt fracture at unusually low rates compared to their Ziegler-Natta counterparts. To further conflrm the correlation between tensile stress growth and the onset of gross melt liacture, extensional experiment was performed using a boron nitride (BN)-hlled resin (0.1 wt.7o of BN CTF5TM supplied by Saint Gobain Advanccd Ceramics Corporation was added to the base rcsin A). It has been shown that certain grades of BN are able to postpone the critical sheiu rate for the onset of gross melt fracture 1281. Thus, it was expected that BN-filled resin would show reduced tensile stress at Hencky strain rates relevant to gross melt fracture. For this experiment, a model SER-HV-B0I was accommodated on a Bohlin VOR rotational rheometer and it was capable of performing extensional experimcnt up to a Hencky r. In order to emulate extensional rates strain rate of 22-6 s closer to those at which gross melt fracture occurs, extensional experiments were perfbrmed at a lower tempcrature of 150 "C'lhis would also show the dominant e{Tectthat BN would have on the onset of gross melt fracture. The tensile stressesfor the BN-filled and unfilled resin A at 150"C are shown in Fis. 16.

3 00e+6 1 4e+6

Virgan resin E Virgn .esin A

Pa 2.50e+6 Virgin resin A

Pa
1.2e.$ 1 0e+6 8.0e+5 b 6 0$5
1 0Oe+6

2.ooe+6

. 6

1 5Oe+6

4 0a5
5 0oe+5 Resin A + o.1 wt0/6 BN

2.0e+5 0.0
o 1 2 3 H 4 5 6 000

3
'g

Fig.15. True tensile stress- Henc@ strain curves for all resins at a Hencky strain rate of 20 s'' and temperature of I 70 " C

Fig. 16, True tensile stress- HencLry strain curves.of BN-filledarul un' antl temperature oJ filled re.sin A at a Henclqt stroin rate of 22.6 s I 50"C

66

XX Intern. Polymer Processing (2005) |

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E,.B. Muliawan et al.: Melt Fractureof Linear PE

and Control. Hatzikiiakos, S. G', MiSIer K- (Eds.)'Marcel Dekker, New York (2004) Instabilities:Under5 Dealy, J. M., Kinu S., in: Polymer Processing standingand Control. Hatzikiriakos,S- G., Miglea K. (Eds.),Marcel Dekker, New York (200'1) 'frans. Plast.Inst. 3A,p- 24O(1962) E. 6 Hrrv"'ells, R., Benbow,J. J..' Fluid Mech. 2,p.37 (1977) 1 Cogstell,,E N.: J. Non-Newtonian 8 Migler K., lnvallee, C., DiIIon, M-, Woods,5., Gettinger, C': IRheol.45(2),p. 565 (2001) 9 Bergem,N..' Prmeeding 8th Int. Congr. Rheol. Gothenberg'p.50 (19"16) l0 Piau, l. M., El Ki.ssi,N., Trenhltry,B.: J. Non-Newtonian Fluid Mcch-30,p. 197(1988) ll Vnogradov,G. V.,Malkin, A. ){.' Rheology of Polymers.Mir' MosBerlin (1980) cow, Springer, 35 Rheol. (6),p.985 (1991) 12 Tremblay,8..'J. 13 Kurlz, S. J.; hoceeding XIth Int. Congr' on Rheology, Brussels, Belgiurn, in: Theoretical and Applied Rheology- Moldenaers P', Keinings R. (Eds.), Elsevier Science Publishers, Amsterdam /|992\ R 14 Moynihan, R. H., Bainl, D. G., Ramnnathan, : J. Non-Newtonian (1990) Fluid Mech. 36, p.2-5-5 15 Piau, J. M., EI Kissi, N., Trenblay, B-.' J- Non-Newtonian Fluid Mech-34,p. 145(1990) 16 Kazatchknv I. 8., Yrp, 1".,Hatzikiriako.s'S. G..' Rheol. Acta 39, (2000) p. -583 60, | 7 .\on, Y.,M igl er K. B.: SPEANTEC Tech.Papers p- 3742 (2002) J. 18 Torutclla, P., in: Rhcology,Eirich, I-. ft. (M.)' Academic Press, New York (1969) Eng.Sci. 12,p.64 (1972) N..-Polym. 19 Cosswell,,E 20 Kim, 5., Dealy,J. M.: Polym.Eng. Sci-42,p.482 Q{n2) 2l Kim, 5., Dealy,J. M..'Polym.Eng. Sci-42'p- 485 (2002) M. 22 Sentmanat, L: SER-IIV-AOI UniversalTestingPlatform lnstrup. Instruments, 1-7-l-8 (2003) mentManual-Xpansion 23 Sentmana4M. L.: SPEANTEC Tech.Papers6l' p. 992 (2ffi3) H..'J. Rheol.2a $),p.847 (1980) 24 Milnstetlt, M. 25 Sentmanar, L, Muliawan, E. 8., Htttzikiriakos, 'l- G.-' RheolActa in press(20M) M. 26 Sentmnnat, L, Hatzikiiakos, S. G--'Rheol' Acta in press(2004) 27 Doeryinghaus,P.J., Baird, D.6.: Rheol' Acta42, p- 5aa Qm3) 28 Hatzikiriakos, S'. G., in: Polymer ProcessingInstabilities: Underand stancling Conrrol,Hatzikiriakos,S. C., MiSIer K. (Fis.)' Marcel Dekler. New York (20(X)

It can be seen clearly that the BN-filled resin showed a significantly lower extensional stress (up to about 30 7o lower) compared to the virgin resin. These results demonstrate that BN is able to suppress the increase of extensional stressesthat can lead to the initiation of gross melt fracture. Capillary extrusion experiments of this BN-filled resin at 170"C shows that this BN-filled resin exhibited gross melt fracture at a critical shear rate of 1500 r-t. Note that the virgin resin A showed a critical t shear rate for the onset of gross melt fraciure at 850 s- - Thus, the ability of BN to dissipate elastic energy associated with the rapid increase of extensional stressesat high rates of deformation is clearly apparent.In addition, this shows that BN acts as an effective processing aid to postpone the onset of gross melt fracture. This observation is again consistent with the results obtained by Sentmanat awl Hatzikiriakos 126l' who performed extensional experimeots of BN-filled and unfilled metallocene LLDPE.

4 Conclusions Six tlifferent polyethylenes (five of which are Ziegler-Natta) were used to study the effect of nrolecular structure on their melt fracture behaviour and subsequently discuss this behaviour in terms of their extensional rheological properties. It was found that the mclt fracture behaviour of linear polyethylenes (sharkskin and gross melt fraclurc) is closely relatcd to high-rate extensional melt rheology. Thc tensile modulus of the polymer obtained from transient extensional experiments was found to correlate well with the onset of sharkskin melt fracture. On thc other hand, the tensile stress was found to be indicative for the onset of gross melt fracture. This was zrlso confirmed by cxtensional behaviour of boron nitride-filled resin, which showed significant reduction of the tensile stress growth coefficient compared to the unfilled rcsin.

References I Achilleos, E. C., Georgiou, G-, Hatzikiriakos, S- G.'' J' Vinyl and 8,P.'l (2Co2) AdditiveTechnology A. 2 Ramamurthy, V.:J. Rheol.30 (2), p. 337 (1986) Understanding 3 Migler K. B-, in: Polymerhtxessing lnstabilities: andControl. Hatzikiriakos,S. G-' Miglea K. (Eds.)' Marcel Dekker' New York (20(X) Understanding Instabilities: 4 Georgiou,G., in: PolymerPro,cessing

Acknowledgements This work was financially supported by a strategic grant llom NSERC of Canada, STPGP-257907-02. Date received: October 12,2004 Date accepled: January 4,2005

Intem. Polymer ProcessingXX (2005) I

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