Polymer Processing:

Engineering activities concerned with operations carried out on polymeric materials to enhance their utility
Polymer Recycling
synthesis poly-reaction compounding adding/mixing shaping

Monomer

Polymer compound

Plastic

final product

Thermal and mechanical impact

Prof. Dr. Klaus Ruhland

Z. Tadmor, C. G. Gogos, Principles of Polymer Processing, Wiley-Interscience T. A. Osswald, Polymer Processing Fundamentals, Hanser Verlag M. D. Lechner, K. Hehrke, E. H. Nordmeier, Makromolekulare Chemie, Birkhuser Verlag B. Tieke, Makromolekulare Chemie, VCH Verlag M. Brahm, Polymerchemie kompakt, Hirzel Verlag J. Hoinkis, E. Lindner, Chemie fr Ingenieure, Wiley-VCH Verlag

Processing of Polymers
1. Introduction to Polymers 2. Thermal behaviour 3. Mechanical behaviour 4. Extrusion 5. Mixing 6. Injection molding 7. Secondary Shaping 8. Other Important Polymer Processes (Calendering, Coating, Foaming)

Historical Evolution of Polymer Processing

taken from principles of polymer processing

Introduction into Polymer Chemistry: Definition of some terms

Monomer: Smallest molecule(s), a polymer can be synthesized from Polyreaction: Chemical transformation in which monomers are transformed into polymers Repeat unit: Smallest entity, with which the stoichiometry of a polymer can be described, just by multiplication (sometimes inconsistent: PE). Oligomer: (oligos some, meros part) Molecule consisting of several repeat units. If one repeat unit is added, the property under focus changes measurably. Polymer: (polys much, meros part) Molecule consisting of many repeat units. If one repeat unit is added, the property under focus does not change. Degree of polymerization: Pn = Mpolymer/Mrepeat unit Polymer compound: a mixture of polymers composed of the same repeat unit, but with different degree of polymerization. Polymer blend: a mixture of polymer compounds, in which the different compounds are composed of different repeat units. Co-Polymer: Polymer consisting of more than one type of repeat unit Additives: External non-polymer materials, added to the polymer compound to improve its properties Plastics = Polymer compound or blend + Additive(s) Polymer processing: engineering activity concerned with operations carried out on polymeric materials to enhance their utility.

Classification of Monomers
Bifunctional acyclic:
Terephthalic acid
HOOC COOH

Monofunctional cyclic:
-Caprolactame
O

Monofunctional acyclic (multiple bond):

Ethylene
H H

NH

Adipinic acid
COOH HOOC

Laurin lactone Styrene

O

H
H

H
H

Phosgene
Cl

O
Cl

Tetrafluor ethylene
F F F F

Glycole
OH HO

Ethylene oxide
O

Vinyl chloride

Bisphenol A
HO OH

Cyclooctene Methyl metacrylate

Cl

CH3

Hexamethylene diamine
H2N NH2

COOCH3

(butadiene)

Hexamethylene diisocyanate
OCN NCO

(isoprene)

Classification of Polyreactions
Polyreaction
bifunctional monomer monofunctional monomer

step-growth reaction:
all components in the system react simultaneously

Chain-growth reaction:
growing chain reacts only with monomer

Polycondensation

Polyaddition

Polyrecombination

Polyelimination

Polymerization

anionic

radical

cationic

insertion

grouptransfer

Averaged degree of polymerization in dependence of the conversion: a) step-growth reaction b) chain-growth reaction without chain termination reaction (living polymerization) c) chain-growth reation with chain termination raction

Structure of Polymers
repeat unit

polymer (intra-chain)

polymer compound (inter-chain)

Isomerism in Chemistry
Isomerism (same stoichiometry, different structure)

constitution isomers (different types of bonds)

stereo isomers (same type of bonds, different orientation)

polymerization isomers (CH2)5 (CH2)6

sequence isomers

configurational isomers (superimposition only with bond cleavage)

conformational isomers (superimposition by rotation about bond)

chiral isomers

geometric isomers

synperiplanar
RR

synclinal
R R

anticlinal
R

antiperiplanar
R

diastereomers

enantiomers (mirror images)

A C D B B A C D

Structure of Polymers
repeat unit

polymer (intra-chain)

polymer compound (inter-chain)

Structure of Polymer Compounds (repeat unit)

H H R R R H H H H H H H R H H H R R H H H H R H H

conformational isomers
n H H

PE
H CH3

CH3

H3C

configuration isomers
n H H

PP
n H H H H n

geometric isomers

IR

( )n

constitution isomers

BR
1,4-BR

1,2-BR

Structure of Polymers
repeat unit

polymer (intra-chain)

polymer compound (inter-chain)

Structure of Polymer Compounds (polymer I)

RR
H H

conformational isomers
n H H

PE

H H H

HR H H H

HR

RR R H H H H H

R R H H H H R H R H H H H H

R R H H

L = n L0 sin(/2) L0

Random coil
<r2>0 = n L02 <r >0 = n L0
2 2

coiling takes relaxation time

(1+cos()) (1-cos()) (1+cos()) (1-cos()) (1-cos()) 2 (1+cos())

: bond angle : averaged torsional angle : empirical steric factor

(PE) = 1.85 (PS)at = 2.2 (PMMA)at = 1.9 (PMMA)i = 2.2 (PMMA)syn = 1.9 (PP)a = 1.7 (PP)i = 1.6 (PP)syn = 1.8

i: isotactic at: atictic syn: syndiotactic

Structure of Polymer Compounds (polymer II)

H CH3 H CH3 H3C H

configuration isomers
n H H

PP
n H H H H n

isotactic

Tm = 176 C

hem-isotactic

block-isotactic

syndiotactic

C Tm = 165

atacitc

Tm = 120-176 C

Tm: melting temperature

Structure of Polymer Compounds (polymer III)

CH3

CH3

constitution isomers
n

PP
n CH3 n

head to head

tail to tail

Structure of Polymer Compounds (polymer IV)

constitution isomers n

PE
n

HDPE

= 0.94-0.96 g/mL Tg = 127-135 C

LLDPE

= 0.93-0.94 g/mL Tg = 123 C

LDPE

= 0.91-0.93 g/mL Tg = 105-115 C

Tg: Glas temperature

Structure of Polymers
repeat unit

polymer (intra-chain)

polymer compound (inter-chain)

Structure of Polymer Compounds (polymer compound)

Polymerization isomers

Mn = ni Mi / ni Mw = ni Mi2 / ni Mi 2 = ni (Mi-Mn)2 / ni = Mn (Mw - Mn) : standard deviation of distribution Most probable distribution (Schulz/Flory)
0.4 0.35 0.3 Molecular Weight 0.25 0.2 0.15 0.1

Poisson distribution (living polymerization)

0.045 0.04

Mn
Molecular w eight

Mn Mw Mw 1 =1+ Mn Pn

Mw

Mw =2Mn

1 Pn

0.035 0.03 0.025 0.02 0.015 0.01

0.05 0 0 100 200 300 400 500 600 700 800 degree of polymerization

0.005 0 0 100 200 300 400 500 600 700 800 degree of polymerization

Thermal behaviour of polymers

Differential Scanning Calorimetry dQ Q = const. dt

Thermal Behaviour of Polymer compounds

QS

QR

T = 0

glass transition
solid (amorphous or semicristalline)

partial crystallization
Viscous solid

melting
Viscous solid/semicrystalline

depolymerization
melt

dQ dt
Tg
Viscous solid

Tm
Viscous solid/semicrystalline melt

Tc

exotherm

Hcrys Tcrys endotherm amorphous or semicrystalline solid viscous semicrystalline solid

Hm

melt

depolymerization decomposition

Tg

Tm

Tc

Thermal Behaviour of Polymer compounds

Tg: torsional rotation in the amorphous regions becomes excessable no phase transition heat capacity Cp increases (entropic effect, rather enthalpic) density of polymer decreases above Tg (larger free volume) value is dependent on the heating/cooling rate Tg0: Tg measured with cooling rate of 10-5 C/s

V0: mass-filled volume in the Polymer Vf: empty volume in the polymer

Thermal Behaviour of Polymer compounds

Tg(P) = Tg0 - K P-1 For linear chains Tg increases with increasing degree of polymerization

Thermal Behaviour of Polymer compounds

Tg decreases with increasing amount of added plasticizer The plasticizer serves as a poor solvent for the polymer compound

xW: molar fraction of added plasticizer

Thermal Behaviour of Polymer compounds

In statistical co-polymers Tg can be settled between Tg1 and Tg2 of the two homo-polymers by the molar composition of the co-polymer

TgPAN: 60 C C TgBR: -60 Tgco-polymer: xAN TgPAN + (1-xAN) TgBR

xAN: molar fraction of acrylonitrile in the co-polymer

Thermal Behaviour of Polymer compounds

In homo-polymers there exists a relation between Tg and Tm: T g Tm

Thermal Behaviour of Polymer compounds

Polymer PVC PP PEK Nylon 66 PS cis-1,4-BR Structure unit i Tg0 [K] 360 250 424 323 373 188 Yi Mi

Increment calculation of Tg0: Tg0 = Yi/ Mi Polar substituents increase Tg sterically flexible substituents increase Tg cross-linking increases Tg large energy barriers for torsional rotation increase Tg

[g K/mol] CH2 CH(CH3) CH(iPr) CH(cyclohexyl) CH(Ph) CHF CHCl CCl2 O-CO-O O-CO-NH O-Ph-O Ph-CO-Ph Ph-S-Ph 2700 8000 19900 41300 36100 12400 19400 22000 20000 20000 37400 84000 72000

[g/mol] 14 28 56,1 96,2 90,1 32 48,5 82,9 60 59 108,1 180,2 184,2

Crystallinity in Polymer compounds

Molten polymer compound Solid state (semi-crystalline) Solid state (fiber, oriented)

Diffractogram of a semicrystalline polymer compound

Fiber direction
Chain length: 10-5 m

amorphous

semi-crystalline

semi-crystalline oriented

Interactions between polymer molecules: Van der Waals Dipole/Dipole Hydrogen bonds No chemical bonds (crosslinking)

Crystallinity depends on prior thermo-mechanical treatment of the polymer compound

Thermal Behaviour of Polymer compounds

Viscous solid/semicrystalline melt

Tm

Tm is dependent on the heating and cooling rate, because the reorientation of the polymer chains takes time. Tm0 is defined as that temperature when Tm = Tcrys and Pn = It holds: Tcrys Tm Tm0

Thermal Behaviour of Polymer compounds

Viscous solid/semicrystalline melt

Tm

1/Tm(P) = 1/Tm0 + (2 R/Hm) P-1 For linear polymer chains the end groups serve as impurities lowering the melting point.

PE

Thermal Behaviour of Polymer compounds

Polymer PEK PP PS Tm0 [K] 415 459 450
Viscous solid/semicrystalline melt

Tm

Structure unit i

Yi

Mi

Increment calculation of Tm0: Tm0 = Yi/ Mi Tm = Hm/Sm Polarizable substituents increase Tm (H) Polar substituents increase Tm (H) Opportunity for hydrogen bonds increases Tm (H) Uniformity increases Tm (H, S) Rigidity in the back bone increases Tm (S)

[g K/mol] CH2 CH(CH3) CH(iPr) CH(Ph) CHF CHCl O NH 6000 13000 35300 48000 17400 27500 13500 18000

[g/mol] 14 28 56,1 90,1 32 48,5 16 15

Thermal Behaviour of Polymer compounds

melt

Tc

Depolymerization:
COOMe COOMe COOMe COOMe COOMe COOMe

Hp, Sp Tc = 60C

Tc = Hp/Sp

Since Sp is negative, Hp must be exothermic for a polymerization, to be thermodynamically feasable (Gp<0). As a consequence there exists a temperature Tc (ceiling temperature), starting from which depolymerization is thermodynamically favored for entropic reasons.

Cross-linking in Polymer compounds

EPDM

1,4-BR
S8
hot vulcanisation

S1.6

H2S + S5.4

Chemical bonding between the polymer molecules

Chain fixation increases

Fluidoplast
viscous solid

Thermoplast Elastoplast
solid (amorphous or semicristalline) solid (cristalline block domains)

Elastomer
solid

Thermoset
solid

TF
fluid Viscous solid

Tg
elastomer

Tg
elastomer

Tg
solid

no glass transition

Temperature increases

Room temp.

no melt transition
fluid melt

Tm
melt

Tm

no melt transition
elastomer

no melt transition
solid

TC

TC

TC

TD

TD

TF: fluid temperature, Tg: glass temperature, Tm: melt temperature, Tc:ceiling temperature, TD: decomposition temperature

Some important polymers

abbriv. SBR EPDM LDPE HDPE LLDPE PP PMMA PTFE PPTA PET SAN BR NBR IR PVC PC ABS POM PA 66 PF PAN MF UF PDMS PIB name styrene/butadiene rubber ethylene/propylene/diene-monomers Low-densitiy-polyethylene High-density-polyethylene linear low-density-polyethylene polypropylene poly(methylmetacrylate) poly(tretafluoroethene) poly(para-phenylene-amide), Kevlar polyethyleneterephthalate styrene/acrylnitrile co-polymer butadiene rubber nitrile/butadiene rubber isoprene rubber, natural rubber polyvinyl chloride polycarbonate, Makrolon acrylnitrile, butadiene, styrene Polyoxomethylene polyamide 66 phenol/formaldehyde-resin, Bakelite Polyacrylnitrile melamin/formaldehyde resin Urea/formaldehyde resin polydimethylsilane polyisobutylene monomer(s) styrene, butadiene ethene, propene, 1,5-hexadiene ethene ethene ethene, 1-octadecene propene methyl metacrylate tetrafluoroethene phthalic acid chloride, phthalic amine glycole, phthalic acid styrene, acrylic nitrile butadiene acrylic nitrile, butadiene isoprene vinylchloride bisphenol A, phosgene acrylnitrile, butadiene, styrene Formaldehyde 1,6-adipodiamine, adipinic acid phenol, formaldehyde acrylic nitrile melamin, formaldeyhde urea, formaldehyde dimethylchlorosilane isobutene low temperature elastomer low gas permeability Clothes motor housings, telephones precursor to carbon fibers tires and tubes solvent-resistent rubber, gloves tires and tubes Diverse CDs, DVDs, unbreakable bottles toys, garden equipment elastomer after vulcanisation elastomer after vulcanisation elastomer after vulcanisation thermoplast thermoplast thermoplast thermoplast thermoplast duroplast thermoplast/fiber duroplast duroplast fluidoplast/elastomer fluidoplast/thermoplast application tires and tubes aging-resistent foils transport container foils heat-resistent Lenses, plexi glass high-temperature resistence bullet-proved jackets bottles, clothes thermal classification elastomer after vulcanisation elastomer thermoplast thermoplast thermoplast thermoplast/elastoplast thermoplast thermoplast/duroplast thermoplast thermoplast

Some important monomers

HO butadiene styrene 1-octadecene F methyl-metacrylate F phthalic acid chloride HO HOOC COOH phthalic acid glycole H2N urea H2N NH2 phthalic amine Cl isoprene vinyl chloride CN isobutylene acrylic nitril NH2 OH F H2N ClOC COCl F tetrafluoroethene N N melamin O Me N NH2 Cl Si Cl Me dimethylsilylchloride ethene propene 1,5-hexadiene O Cl Cl phosgene NH2 Bisphenol-A O H H formaldehyde OH

COOMe

Some important polymers

O O O O O O O O

PP (polypropylene)

PET (polyethyleneterephthalate)
O O O O

PE (polyethylene)
O O

COOMe COOMe COOMe COOMe COOMe COOMe COOMe

Makrolon

PMMA (polymethylmetacrylate)

POM (poly-oxymethylene)
F F F F F F F F F F F F
Si O O Si O Si O Si O Si O Si O Si O Si O

F F

F F

Si

PTFE (polytetrafluorethylene)

PDMS (polydimethylsiloxan)

O HN HN N H O O

PIB (polyisobutylene)

PPTA (poly(para-phenylene-amide)

Economic importance

Plasticsproduction in dependence of time

90%

Further Modification of Polymer Compounds

post-reactor phase Polymer Compound physical modification chemical modification

preperation for processing

mixing Additives: -Plastizers -Flame retardants -Stabilizers -Fillers -Blowing agents other Polymers: Polymer blends -polymer-analogous reactions -chemical blowing

processing phase shaping

Additives

Plasticizers
-act as "poor solvent" for the polymer -decrease the operating temperature for shaping

Stabilizers

Fillers

Antistatic agents

Blowing agents

thermal

light mechanic atmosphere UV- Fibers absorbers oxygen

absorbe heat by decomposing into lessreactive products

active
color pigments anti-shrinking self-healing

inactive
extenders: fill volume lower the price

flame retardant
internal extinguishers: Al(OH)3 H2O XBrn n Br XPn "PO"coating

heat

moisture hydrophobics

Leadorganyls

Antioxidants

Mechanical behaviour of polymers

Mechanical Behaviour of Polymer compounds

solid (energy-elastic) thermoplast (visco-elastic)
Voigt-Modell: = 1 = 2 = 1 + 2
1,2

liquid (viscous)

1,4 1,2

Hook-Modell:
tension

Newton-Modell: =
solid thermoplast liquid

0,8

elongation

1 0,8 0,6 0,4 0,2 0

=E

0,6

0,4

solid thermoplast liquid

d dt

0,2

0 0 50 100 150 200 250 300 350 400 450

50

100

150

200

250

300

350

400

450

time

time

1,2

1,2

elongation

tension

0,8

0,8

0,6

0,4 0,2

solid thermoplast liquid

0,6

0,4

solid thermoplast liquid

0,2

0 0 50 100 150 200 250 300 350 400 450

0 0 50 100 150 200 250 300 350 400 450

time

time

Maxwell-Modell: = 1 = 2 = 1 + 2

Elastomere

L = n L0 sin(/2) L0

Reforming driving force: multiple microstates of random coil (solely entropic!)

Mechanical Behaviour of Polymer compounds

(b)
Tension

(c)
oriented

(d)

(a)

(e)
Rel. Elongation

Stabilization of polymer compounds towards tension by orienting streching

Mechanical Behaviour of Polymer compounds

Hook
Log(E/(Nm-2))

VoigtMaxwell
elastomer

elastomer

elongation in %

melt

Newtonlike ?!
Tg Tm

Non-Newtonian behaviour in polymeric melts

Newtonian: = d = dt d = = dt
for De << 1

Polymer:

= () = m(T) n, 0 < n < 1 for De 1

m(T) = m0 e-a (T-T0)

2 1,8 1,6 1,4 viscosity 1,2 1 0,8 0,6 0,4 0,2 0 0 2 4 De << 1 6 8

Newtonian behaviour Polymer compound

Shear thinning effect!

shear rate relaxation rate 1/

De10 1 =

12

14

16De

18 >> 1

20

shear rate d/dt

Deborah number De =

chain relaxation time processing time

tP

Non-Newtonian behaviour in polymeric melts

Newtonian flow field:
= d dt =

Polymer compound flow field:

= () = m n, 0 < n < 1

p vz(r) = 4L
4

R -r

vz(r)
p1 R

1 p vz(r) = 4Lm 1 + 1/n

R Q= 1/n +3
3

1/n

R1+1/n - r1+1/n
1/n P 1/n

R P Q= 8L

R 2mL

Hagen-Poisseuille
p = p1 - p2 radius r
-1333 -833 -333 -174600 -374600 -574600 167 667 1167
-848 -648 -448

L radius r
-248 -38000 -48 -138000 152 352 552 752

vz(r)

-774600 -974600

-1174600 -1374600 -1574600 -1774600

p2 flow Q

Reduction during extrusion

Swell during extrusion

vz(r)

-238000 -338000 -438000 -538000 -638000 -738000

Classification of Polymer Processing

Classification of Polymer Processing

1. Die forming (fiber, film, sheet, tube, wire) 2. Calendering and coating (knife, roll)

continuous

3. Mold coating (powder, rotation) 4. Molding and casting (injection, transfer, react. inj.) 5. Strech shaping (thermoforming, blowmolding)

cyclic

The Extruder

The Navier-Stokes equation (incompressible fluids)

external pressure internal pressure gravitational pressure

dv = dt
acceleration of fluid

+ v

The velocity field of an extruder

0
y

y/h
x z

ux 0 x/W

uz

external pressure

internal pressure

0 =

+ v

The Extruder

Brinkmann number: Br = =
Viscous dissipation Heat transport V02 k (Ta - Tb)

Solid bed profile

The Extruder

The die design

Rules of thumb: avoid thick sections minimize the number of hollow sections generate profiles with constant wall thickniss.

The Extruder

The coat hanger die (films, sheets, foils)

extrudate R extrudate

W
1/(3n + 1)

(3 + s)/ * h2n+1 (W-x)n R(x) = 2n (s + 2)n * sin()

for uniform flow in the land (s = 1/n) (shear thinning effect)

Characteristic curve of an extruder

die shape

m = k' P

1/n

Non-Newtonian flow

m = k P

open discharge

. 2H N, .H N,
closed discharge

Newtonian flow

.H 2 N,

N: screw rate H: channel depth of screw

p
LD die

. m

Ls

barrel with screw

DB

ps

pd

RD

Characteristic curve of an extruder

die shape

Mixing of polymers

Mixing of polymers

Compatibility of polymers
PS HIPS SAN ABS PA PC PMMA POM PVC PP LDPE HDPE

PS HIPS SAN ABS PA PC PMMA POM PVC PP LDPE HDPE

1 6 6 6 5 6 4 6 6 6 6 6 1 6 6 4 5 4 6 6 6 6 6 1 1 6 2 1 6 2 6 6 6 1 6 2 1 5 3 6 6 6 1 6 6 6 6 6 6 6 1 1 6 5 6 6 6 1 5 1 6 6 5 1 6 6 6 6 1 6 6 6 1 6 6 1 1 1

1 = very compatible, 6 = incompatible

Hildebrand-parameters Hmix = Vges x1 x2 (1 - 2)2 Two polymers mix with each other if 0.1(cal cm-3) 2 = Fi/Mi
(J cm -3)0.5 15,8-17,1 16,8-18,8 16,0-16,6 17,4-19,0 19,2-22,1 25,8-29,1 25,6-31,5 15,4-20,3
structure unit Fi -CH3 303 -CH2269 C(quart) 65,5 -CH(CH3)479 -C(CH3)2672 -CH=CH497 -OH 462 -O235 -CO538 -COOH 1000 -COO668 Mi 15 14 12 28 42 26 17 16 28 45 44

Polyethylene Polystyrene Poly(methylmetacrylate) Polypropylene Poly(vinylchloride) Nylon 66 Polyacrylonitrile Poly(propylenoxid)

Mixing of polymers Mixing mechanisms

Distributive mixing

Dispersive mixing

Dispersive mixing

not mixed

mixing = tension + reorientation

well-mixed dispersively and distributively

Distributive mixing

Mixing of polymers distributive dispersive

Mixing of polymers
Flow number: =

+
Deviatoric stress

Capillary number: Ca = Surface tension

R = s

Mixing devices

Mixing devices

Injection molding

Injection molding
D

A C B C
5. (ch Sc re w ba ck ec kv a lv eo

pe n

C/C A D C C B

Injection molding

Injection molding

Injection blow molding

Extrusion blow molding Parison programming

by die-temperature as function of t by die opening as function of t by screw rate as function of t

Film blowing

Biaxial stretching!

Film blowing

Blow-up ratio: BR = Rf R0 vf v0

draw ration: DR =

ratio of film thickness: h0/hf = DR BR

Rotational molding

Thermoforming

plugassisted

vacuum

Calendering

Calendering

Calendering

The velocity field of a calender N

R y

d2vx dP = 2 dx dy

x h0 h2 h1

h-1 h2

h0

h1

3 vx(y) = 2 NR + 2

y2

h12

h2

1-

h1 h

h1 h

h = h0 + R - R2 - x2

Calendering

n: viscosity-power-law index

Ribbing in roll coating

N Ca = s

N: roll rate

Fiber-spinning

Fiber-spinning

Extruder Spinneret

Take-up

Heater: Stretching/ molecular orientation

Final take-up

Fiber-spinning

Fiber-spinning

DR = vz/v0

. viscosity = m

De = 3(n-1)/2 (m/G) (v0/L)

(n-1)

Thermosets/Reactive molding

Thermosets/Reactive molding

curing by heat mixing light moisture

hv

Welding thermal friction