Polymer blend formulation and processing,

with reference to the nature and the

behaviour of pigmented polycarbonate -
poly(butylene terephthalate) (PC-PBT) blends
K E Fagelman and J T Guthrie
Department of Colour and Polymer Chemistry, University of Leeds,
Woodhouse Lane, Leeds, West Yorkshire, LS2 9JT

Keywords
Polymer blends, additives, additive interactions, polycarbonate, poly(butylene terephthalate), blend
properties, phase partitioning

Summaries
Polymer blend formulation and processing, with reference to the nature and
the behaviour of pigmented polycarbonate - poly(butylene terephthalate) (PC-
PBT) blends
Polymers, and even more so polymer blends, are selected for their particular properties and pro
cessing characteristics. It is oflen necessary to include additives in the polymer formulations, either
to facilitate processing, or to extend the life of the polymeric product that is created Colourants are
additives that are principally used for aesthetic purposes. However, the addition of a colourant to a
thermoplastic system can lead to unexpected and sometimes detrimental changes in the material
properties of that system
In this review, the general characteristics of polymer blends and the processes involved in manufac
turi ng them are discussed. Additives that may be included in the formulation and the interactions that
can arise among the blend components are also described. The relevance of these components and
processes are then discussed in regard to blends o[ polycarbonate and poly(bulTlene terephthalate).
Formulation et production des melanges polymeriques, par rapport a la nature
et au comportement des melanges de polycarbonate pigmente - poly(butylene
terephthalate) (PC-PBT)
Les polyrr0res eL,encore plus les rrOlanges polyrr@riques, sont choisis pour leurs caract@ristiques
de production et leurs propri@t@sparticuli@res. II est souvent necessaire d'inclure des additifs dans
la formulation des polymeres ou pour faciliter la production, ou pour rallonger la vie du produit
polym@rique qui est ainsi cr@@Les colorants sont des additifs qui sont ajout@sprincipalement pour
des raisons esth@tiques Cependant I'addition d'un colorant ~ un syst@me thermoplastique peut
mener ~ des changements impr@vus eb des lois, ndastes, dans le domaine des propri@t@s
materielles de ce syst@me Dans cet article on discute les caracteristiques g@n@ralesdes m@langes
polym@riques et les proc@d@semploy@sdans leur production. On d@critaussi des additifs qui pour
raient @tre inclus dans la [ormulation et les interactions qui pourraient se produire parmi les com-
posants du m@lange On discute ensuite la pertinence de ces composants et de ces proc@d@spar rap-
port aux m@langesde polycarbonate et de poly(bulTl@net@r@phthalate).
Die Formulierung und Verarbeitung yon Polymermischungen mit Blick auf die
Eigenschalten und des Verhalten yon pigmentierten Polycarbonat-Poly(butylen
Terephthalat) (PC-PBT) Mischungen
or correspondenceconta( Polymere, und insbesondere Polymermischungen, werden fur ihre Materials und Verarbeitung
J T Guthrie seigenschaflen ausgewShlt. Es ist often n0tig, den Formulierungen Additive hinzuzufugen um die
Verarbeitung zu erleichtern oder die Lebensdauer des Endproduktes zu verl3ngern Pigmente ~erden
Departrr-ent of Colour and Polymer Chemistry, Universil7 of aus rein 3sthetischen Grunden hinzuge[8gt Allerdings kann die Zugabe yon Farbmitteln zu thermo-
Leeds, Woodhouse Lane, Leeds, West Yorkshire, LS2 9JT plastischen Systemen zu unerwarteten und manchmal unerwSnschten Anderungen der Materi
Tel: +44 (0) 113 243 1 7 5 1 Email:j.guthrie@leeds ac.uk aleigenschaften f8hren
Fax: +44 (0) 113 233 2947 Diese Arbeit beschSftigt sich mit den allgemeinen Eigenschaflenyon Polymermischungen und ihren
Copyright OCCA2006 Verarbeitungsprozessen Additive, die den Formulierungen hinzugefugt werden k~nnen, und ihre
Wechselwirkungen mit der Mischung werden beschrieben. Die Wichtigkeit dieser Prozesseswerden
dann mit Hinsicht au[ Polycarbonat-Poly(bulTlen Terephthalat) (PC-PBT) Mischungen diskutiert.
Surface Coatings International Part B: Coatings Transactions
Vol 89, B1, 1-98, March 2006
 Polymer Mend formulation and processing, with reference to the nature and the behaviour of
pigmented polycarbonate - poly(butylene tereptlthalate) (PC-PBT) blends
K E Fagelman and J T Guthrie

Introduction Table 1: Properties associated with the engineering polymers that are produced by
GE Plastics 4
Polymer blends Gf family name | Polymer base Characteristic properties
Polymer blends are physical mixtures of Lexan Polycarbonate Impact strength: good mechanical, thermal,
structurally difl'erent polymers. In such optical and thermal properties
blends/mixtures, the polymer chains are
Valox Polyesters Chemical resistance: dimensional stability: good
not held together by covalent bonds, but
mechanical, thermal and electrical properties
interact via secondary forces. These
polymer mixtures are usually based on Noryl Polyphenylene ether Dimensional stability, low mould shrinkage, low
creep behaviour, low water absorption
two or more repeat unit sequences (eg a
polyester and a polyamide). However, Cyeolac Aerylonitrile- Heat stability, chemical and ageing
they could be mixtures of two polymers butadiene styrene resistance, toughness, impact strength
from the same repeat unit family (eg Ultem P01yetherimide Heat and flame resistance, low smoke evolution,
low-density poly(ethylene) and high- high dielectric strength, transparency
density poly(ethylene). Supec Polyphenylene sulphide Heat and solvent resistance, flame retardance,
hydrolytic stability
The degree of compatibility between the Lomod Polyether-polyester Flexibility, impact resistance, ductility, chemical
polymers determines the final properties block polymer resistance
of the system, many of which have rele
vance with respect to processability. Fac
tots that influence the compatibility erties, or added to reduce the cost of the such a filler is carbon black. Carbon
include the chemical composition, the product. For any type of additive, there black has many fimctions. It is used to
molecular weight, the morphology and is a number of requirements to which improve tile hardness, modulus, tensile
the processing history. The differences in the additive must conform. For a poly strength and abrasion resistance of poly
compatibility have an impact on the mer system to be efl'ectively stabilised, meric materials as well as to impart
extent of multi-phase development the additives used must satisfy two blackness. Fibrous fillers are also used to
within the blend. This point is of impor- requirements. They must be efl'icient in reinforce polymers. These fibrous fillers
tance to those blends that are designed their action, and they must be present in take the form of single fibres of materials
to have engineering processing as a fea- the areas of the system in which they are such as cotton, nylon, glass or carbon.
ture of product development. needed. In addition, the additive must Kulkami and Mahanwar have discussed
be easily dispersed, stable under pro- the use of many types of fillers in a num-
Engineering polymers are those general cessing conditions, stable under product ber of thermoplastics.S
ly used for structural components or use conditions, non-toxic and, ideally, of
semi precision parts. In these fields they Huneault and co-workers described the
low cost. It is also important that the
are substitutes for metal parts as they use of additives to modify tile tough
additive does not adversely affect any
offer advantages such as corrosion resis ness/strength/stifl'ness property balance
other material property, or interact
tance, weight reduction and economy in of poly(propylene) systems) In general,
antagonistically with any other additives.
production. The polymer parts may be mineral fillers such as talc and calcimn
It has been stated that the phase parti
subjected to external factors such as carbonate are used to increase polymer
tioning of additives in polymer blends
mechanical stress, impact or hostile stiffness. However, this stifl'ness is
can have a large impact on the perfor
environments, and yet they are still able accompanied by a reduction in tensile
mance of the blend)
to maintain their set of properties. L2 strength, elongation and impact
The question arises as to when an addi- strength. These changes are thought to
Polymers in the category of engineering tive is really an additive and when the be due to weak interaction between the
polymers include: polyamides, polycar- 'additive' becomes a major component filler and the poly(propylene). For opti-
bonates, poly(phenylene oxide), polyac- of the system. This point has relevance mal use of such fillers, the compounding
etals and co polymers and polyesters/ to formulation processing and applica- process must allow adequate dispersion
McKechnie summarised the properties tion if the additive begins to function of the filler throughout the system. The
of a number of engineering polymers beyond its specific role and produces a authors' work 9 involved a study of
and polymer blends that are produced change in the properties of the system. poly(propylene) blends that contained
by GE Plastics. 4 Several of these are list combinations of talc and an ethylene
ed in Table 1. Examples of additives that are common
octene copolymer as an impact m o d i g
ly used in polymer blend applications
Engineering plastics are chosen for their er.
include antioxidants, heat and light sta
specific set of properties. Thus, it is very bilisers, colourants, impact modifiers, Arroyo and co workers evaluated a
important that any additives or processing aids, fire retardants, antistatic series of composites based on low den
colourants that are incorporated into the agents and antiozonants, r A number of sity poly(ethylene) and high-density
formulation do not have a negative these additive types will now be dis- poly(ethylene). 1~ The composites con-
effect on those properties/ cussed. tained unmodified sepiolite or modified
sepiolite (hydrated magnesium silicate)
A d d i t i v e s for p o l y m e r b l e n d s as a filler, with the object of improving
and general additive use the blend properties. By examining the
Fillers are additives that can be used to
fracture surfaces of different samples,
In commercial polymers, additives are modify a variety of performance proper
used in order to assist processing and/or ties, or to reduce the overall cost of the the authors observed a difference in the
to extend the range of properties exhib morphology of the modified fillers and
process and/or the product. Particulate
ited by the material. Additives may be of the unmodified fillers. Considering
inorganic fillers are used to increase the
the unmodified filler, a strong interaction
added to modify mechanical properties, modulus of polymers and improve their
physical properties and chemical prop was observed to exist between the parti
dimensional stability. An example of

Surface C o a t i n g s I n t e r n a t i o n a l Part B: C o a t i n g s T r a n s a c t i o n s
Vol 89, B1, 1-98, March 2006
 Polymer blend formulation and processing, with reference to the nature and the behaviour of
pigmented polyc~xbonate - poly(butylene terephthalate) (PC-PBT) blends
K E I:agelman and J T Guthrie

des and the polymer matrix due to the The use of rubbers for impact modifica Triaxial stress is developed in tile parti
fibrous nature of the filler. However, the tion can lead to a decrease in the stiff cles. This leads to a small volume dila
modification of the filler led to some ness of the material. This is not necessar tion in the interior of tile particles, or in
elimination of the fibrous structure. ily of benefit to the system. Yuan and the area surromlding the rigid filler par
Thus, there were fewer physical interac- co-workers modified the toughness of ticles. Void and shear band formation is
tions with the polymer matrix. From this high-density poly(ethylene) (HDPE) the second stage of deformation. Higher
observation, the authors concluded that using rigid glass beads, is Findings regard- triaxial stresses build up inside the parti-
modification of the filler had minor ing the use of rigid particles as modifiers cles and void formation occurs. As the
effects on the mechanical properties of were described. In similar studies, the voids grow, shear bands are formed in
the composites. blends were only tough if the interparti- the matrix. Once the voids have formed,
cle distance was below a critical value. stage three begins. This is induced shear
Plastk'~se~s The authors evaluated the effects of tern yielding (plastic flow), brought about by
perature and interparticle distance the stresses that are released locally in
Plasticisers are used to increase flexibili-
(based on the content of glass beads in the regions surrounding tile voids.
ty, resilience and softness to tough/hard
the sample) on the toughness of the
polymeric materials such as poly(vinyl For optimum interaction between rub
HDPE matrix. The authors concluded
chloride) (PVC).ll The plasticiser reduces bet particles and the polymer matrix,
that a transition from brittle to tough
the intermolecular attraction forces core shell impact modifiers are used. la
behaviour was achievable, either
between the polymer chains, and These modifiers have a rubbery core
through a decrease in the interparticle
increases the amount of free volume that is surrounded by a shell. The shell
distance or by an increase in tempera-
available so that the chains may undergo composition may be chosen to impart
ture.
greater amounts of rotation. compatibility to the system or to react
Kim and Michler studied the relationship chemically with the matrix.
In general, plasticiser additives must be
between the morphology and the defor-
compatible with the polymer, be of small Tseng and Lee prepared impact modi-
mation processes in a number of impact-
size to enable penetration of the poly fiers that contained functional groups for
modified poly(propylene) systems.16 The
mer chain networks, have low volatility, use in PC/PBT blend systems. 19 A core
poly(propylene) was produced in the
be stable to light and heat, be non-toxic, shell type modifier was used, with a
form of a reacted blend with ethylene
colourless and odourless, and be non- poly(butadiene) core and a shell consist
propylene block copolymers; in the
migratory. The more common commer- ing of a copolymer of methyl methacry
form of a mechanical blend with modifi
cial plasticisers are esters of orthophthal- late and a vinyl monomer that contained
er particles (ethylene propylene copoly
ic acid and, in particular, dioctyl a specific functional group. Three
mer and ethylene propylene butadiene
phthalate (DOP) and benzyl butyl monomers were used: glycidyl
terpolymer), and in the form of a blend
phthalate (BBP).12 The structures of methacrylate, acrylamide and
these two plasticisers are shown in Fig with another polymer mixed with a
methacrylic acid. The authors observed
compatibiliser. The effects of particulate
ure 1. that the better the adhesion between the
fillers were also evaluated. The authors
shell of the impact modifier and the
Ire'pact modiS, e~s described microvoid formation as the
blend, the better were the impact prop-
initiation site for plastic deformation.
Impact modifiers are rubbery materials erties of the blend. From this observa-
The microvoid formation was caused by
that are added to a polymer system to tion, it followed that the better the inter-
cavitation in the rubbery particles or by
improve the impact strength, particular- action, the less impact modifier was
debonding at the particle/matrix inter-
ly at low temperatures. Keskkula required to achieve the desired impact
face. The phase adhesion between the
reviewed the development of rubber strength. The thickness of the impact
particles and the matrix was found to be
modified thermoplastics and the modi modifier shell was also deemed to be an
a very significant factor in the type of
tiers used in specific polymer systems? 3 important property regarding the inter
deformation taking place. In a subse
When an impact modifier is added to a action and consequent impact strength.
quent paper, the authors described the
polymer, the properties of the system are mechanism for the micromechanical
Process'rag aids
dependent on a number of factors con deformation processes. 17 A simplified
cerning the rubber phase morphology. three stage mechanism was described. Any additive that has a function during
The particle size, the particle size distri The first stage involves stress concentra- the manufacturing process, but has no
bution, the rubber phase volume and tion, as the particles act as stress con- effect on the final properties of the sys
the distribution of the particles are all centrators because of their differing elas- tern, may be deemed a processing aid.
important considerations.14 tic properties from those of the matrix. However, the term is used here to
describe the use of lubricants.
Lubricants are used to change the vis-
cosity of the polymer, to assist in disper-
0 I sion processes, to release the product
| CHz O
c I I from production equipment, and to
C reduce deformation during processing.
~ ~O--CH2--CH - - (CH2)3--CH3
Internal lubricants should have good
compatibility with the polymer and
lubricate the polymer chains to reduce
I
o I' I the melt viscosity. External lubricants
CH3 O have limited compatibility with the poly
mer and migrate during processing to
form a layer between the polymer and
the interior of the processing equipment.
Figure 1: The structures or the plasticisers (a) DOP and (b) BBP12

Surface Coatings International Part B: Coatings Transactions

Vol 89, B1, 1-98, March 2006
 PolymerMend formulationand processing, with reference to the nature and the behaviourof
pigmented polycarbonate- poly(butylenetereptlthalate)(eC-eBT)blends
K E Fagelmanand J T Guthrie

This enables the polymer to be released the use of pneumatogens or chemical oxy (ROO*) radicals, and hydroperox
easily. The balance of internal lubrica blowing agents. Pneumatogens are ides (ROOH). Tile radical reactions lead
{ion and external lubrication is deter volatile liquids that volatilise at process to chain scission and cross linking, with
mined by the solubility of the lubricant ing temperatures and expand if the poly the formation of the carbonyl functional
in the polymer melt at the temperature mer is of low enough viscosity. Chemical ity and of conjugated carbonyl function-
of processing, a~ Examples of lubricants agents decompose at processing temper- alities. Compounds with such groups
include high molecular-weight fatty atures to release a high yield of gas. provide a tendency towards yellowing of
acids, waxes and orgainc salts of calci- Examples of blowing agents include: the composition.
um, zinc or sodium, inert gases (eg carbon dioxide or nitro-
Antioxidants act as kinetic chain break-
gen), azo compounds that decompose
Colouxants ers. This occurs by either an electron
to produce the gases (eg azobisdibutylni-
donor mechanism (primary antioxidants)
trile, trihydrazinotriazine) and bicarbon
Dyes and pigments are used in the col- or by an electron acceptor mechanism
ares.20
oration of polymeric materials. Factors (secondary antioxidants). Primary
influencing colourant choice/type antioxidants are generally sterically hin
Mtk~.dteg[&dtattks
include the chemical nature of the poly- dered phenols that have the general
mer to be coloured, the conditions nec- Polymer chains are susceptible to attack structure shown in Figure 2. An example
essary for the processing of that polymer, by heat, light, oxygen, high-energy radi- of such an antioxidant is h'ganox 1010
and the environment to which the fin- ation and biological agents. Anti- (Ciba Specialities), whose structure is
ished part will be exposed, el degradants are used to prevent or to shown in Figure 3. Secondary antioxi-
minimise the effects of decomposition. dants are usually thioethers and tri-esters
Dyes are able to produce intense, trans
The most undesirable reactions that take of phosphorous acid.2S In Figures 2 to 5,
parent colours but, fl'om the point of
place are main chain scission, side chain the R groups in the chemical structures
view of plastics processing, the range of
scission and cross linking. These reac are chosen in order to control the com-
dyes is very limited. Few can withstand
tions result in a reduction of molecular patibility, solubility etc with the polymer
the processing environment experi
size and loss of mechanical properties; system.
enced by the polymer and, in particulaL
altered thermal, chemical or optical
the high temperatures. However, CI Sol-
properties; and insolubility fl'om the for
vent Red 111 (an anthraquinone dye)
marion of network structures, respec- OH
and CI Solvent Orange 60 (a perinone
tively. The degradation, and stabilisation,
dye) are used in automotive brake lights R z ~ R1
of polymer systems were well described
and indicator lights respectively2 e Inor-
by White and Tumbull2 4
ganic pigments have good heat stability
and fastness properties, but produce Antidegradants are designed for three
mainly dull colours. Organic pigments purposes: to prevent decomposition R~
also have adequate colour fastness prop reactions being initiated; to interfere
erties, and a wider range of bright with the course of decomposition reac
Figure 2: General structure of primary
colours is obtainable. tions once they have been initiated; and antioxidants25
to modify the products of decomposi
N'ac\eat~ng agents tion reactions. Below is presented a lira
ited nmnber of examples of anti
It is known that nucleating agents are
degradant species, in order to give a
added to polymer systems to increase H ~ CH2CH2COOCHz~i
guide to the general types of systems.
the rate of crystallisation and the tern
perature of crystallisation23 The addi 9 Heat stabilisers
lives function by providing a large num 4
ber of stable nuclei on which Polymer decomposition by main chain
crystallisation of the polymer may take scission is the most common form of
Figure 3: The chemical structure of Irganox
place. In polymer systems, nucleating thermal breakdown. Main chain scission 101 026
agents are added to improve the is a radical chain reaction, which is usu
mechanical properties of the system or ally initiated by traces of peroxides in the Fay and co-workers described the devel-
to increase the clarity of semi-crystalline polymer. The peroxides may be catal opment of yellow chromophores in
polymers. The improvement in the clari- ysed by transition metal ions that may be polymer systems that contained pheno-
ty originates from the decrease in present in the system. Thus, there are lic antioxidants, for roto-moulding appli-
spherulite size that is obtained through three major types of heat stabilisers. cations2 7 The authors successfully
the modified crystallisation process. Radical scavengers break the chain reac undertook work to prepare a formula-
tion by transfer reactions. Peroxide tion with a 'phenol-free' antioxidant
Crystallisation is a very important feature decomposers eliminate peroxides in a package.
in the morphology development of poly non-radical manner. Metal chelators
mer blends. Thus, the nucleation deactivate transition metal ions by the 9 Light stabilisers
process and examples of nucleating formation of complexes. Photochemical damage arises as a result
agents will be discussed in more detail of the absorption of ultraviolet light by
later in this paper. 9 Antioxidants
UV light sensitive polymers. Photo
The oxidative breakdown of polymers is chemical attack is usually encountered
g \ o ~ n g agents a free radical decomposition process. as a surface phenomenon, and is
Blowing agents are used to create poly Oxidation of polymers can take place in observed via changes in colour, surface
mer foams. These cellular structures are the presence of heat or light. The reac cracking and loss of impact strength.
created by introducing a gas under pres tion is a chain radical type, and can Effects are mostly limited to surface
sure during melt processing, or through involve alkyl (R.), alkoxy (ROo) and per-

Surface Coatings International Part B: Coatings Transactions

Vol 89, B1, 1-98, March 2006
 Polymerblend formulation and processing, with reference to the nature and the behaviour of
pigmented polyc~xbonate - poly(butyleneterephthalate)(PC-PBT)blends
K E Fagelman and J T Guthrie

thermal stabiliser on the surfaces of pig

Hydroxyphenylbenzotfiazoles Hydroxyphenyls4ri#nes ments and fillers/~ Tile UV stabiliser was

N\
HO Rl

Rz
•• RI

OH
a HALS type. The thermal stabiliser was
the hindered phenol, Irganox 10 10. A
green copper phthalocyanine pigment
was among the additives that were eval-
uated. The authors observed that the
Irganox stabiliser adsorbed onto the sur-
face of the pigment, while the HALS sta-
briber did not. Thus, it was concluded
RsZ V v,.4"~ R3 that the phthalocyanine influenced the
photostability indirectly, by reduction of
the thermal stability, due to the adsorp
tion of the stabiliser on file pigment sur
face.
2 hydroxybenz0phen0nes 0xalanilides
Haake and co workers investigated tile
,0 0 0 adsorption of UV light stabilisers on pig
n II I H ment surfaces/2 The stabilisers and pig-
R2 ~ C ]. R~ N--C--C _ N Rl
ments were those used in coatings for-
mulations. The authors based their work
R4 1l2 on the reported existence of stabiliser-
pigment and filler-pigment interactions
Figure 4: Examples or UV absorber molecules2s described in the literature for plastics
formulations. In the work, a number of
properties, and there are fewer changes Four major factors can influence the pigments (organic pigments and inorgan-
in the bulk properties. photostability of pigmented polymer sys ic pigments) were evaluated. However,
terns/s These factors are the chemical in this study the organic pigments were
There are different types of additives observed to undergo no interaction with
and physical nature of the polymer itself,
and methods of stabilisation against pho- any of the stabilisers tested.
the environment in which the system is
tochemical attack. Light of all wave-
used, the chemical and physical nature
lengths may be absorbed through the Additive interactions in polymer
of the pigment, and the presence of any
incorporation of a total light screen. An blends
additional stabilisers.
example of such a screen is carbon
black. A UV screen can be used to Vaillant and co-workers studied the effi- Additives may be present in a polymer
absorb UV radiation alone, and quickly ciencies of hindered amine light stabilis- system in several forms. Generally they
transfer the radiation to heat by vibra ers in isotactic poly(propylene) (iPP) are intentionally added, as are the types
tion and rotation of the molecular con polymer matrices that contained differ discussed previously. However, they may
stituents. UV absorbers may be phenolic ent additives. 29 Phthalocyanine pigments also be formed during processing of the
or non phenolic in type. Typical exam were one such group of additives. The blend or be inherent components of the
pies are shown in Figure 4. effects of both the flocculating and the system. Examples of such additives,
non flocculating types of the ~x phthalo respectively, are the copolymer formed
The phenolic absorbers function via during an interchange reaction (a system
cyanine modification and of the [5
keto-enol tautomerism, whereas the compatibiliser) and low molecular-
phthalocyanine modification respective
non-phenolic absorbers undergo weight polymer chains (potential system
ly on the light stabilisers were evaluated
intramolecular proton transfer/s plasticisers).
in the iPP matrices. An antagonistic
A quencher dissipates the absorbed light effect was observed with each of the pig- Three types of polymer filler interaction
before decomposition reactions can take ments as a decrease in the efficiency of have been suggested .33 In the first type,
place. An example of a quencher is nick- the stabiliser was seen in each case. no interactions occur between the two
el phosphonate. Radical scavengers act From the studies of the different components and the filler has only a
by interfering with the radical chain phthalocyanines, the authors concluded physical presence in the polymer. Here,
reactions that would otherwise be taking that the more abundant and well dis- the filler is expected to act as a diluent
place. These scavengers tend to be hin persed the pigment, the greater was the and weaken the polymer system. In the
dered amine light stabilisers (HALS). Fig reduction in the efficiency of the HALS second type, the surface of the filler is
ure 5 shows the general structure of a stabiliser. This was thought to be due to wetted by the polymer either through
HALS molecule. the adsorption of the stabiliser on the inherent polymer affinity for the surface
pigment surface, thereby inhibiting the or by modification of the surface to pro-
stabilising activity by reducing the mobil vide that affinity. A physical bond takes
RI R2 ity of the active group in the polymer place between the components and the
matrix. movement of the filler is restricted. In
HIO~CH3
Maatoug and co-workers found that the the third type, a chemical bond exists
H10" "N" "CH3 between the filler and the polymer. This
incorporation of a green phthalocyanine
I results in a great strengthening of the sys
RI pigment into a stabilised high-density
poly(ethylene) film led to poor photosta- tern.
Figure 5: General structure of HALS bility of that film/~ In a subsequent FOldes investigated the factors that
moleculeszs paper, Anna and co workers examined determine the migration of small mole-
the adsorption of a UV stabiliser and a cules in a plastic system.34 Experiments

Surface Coatings International Part B: Coatings Transactions

Vol 89, B1, 1-98, March 2006
 Polymer blend formulation and processing,
with reference to the nature and the behaviour of
pigmented polycarbonate - poly(butylene terephthalate) (PC-PaX)blends
K E I:agelman and ] T Gnthrie

were carried out using atnorphous poly

mers and semi crystalline polymers, with Transportof additives in polymers
a range of additives of different size. The
author fotmd a number of relationships
that existed between the additives and
the polymers, relating to the migration of
the additive in the system. These rela-
tionships are shown in the form of a
scheme in Figure 6; the explanation of
/(dfusXi0rate,
n /01uiilit
Mobility
< Compatibility

the scheme will now be described.

The rate of migration was found to be a
Polymer Additive Specific Physical Intecadions
product of the solubility of the additive
in the polymer and the diffusion coeffi
cient, characterising the mobility of the
molecules. Diffusion depends on the co
/ X / X ~ :~a~ieti:fe/X
operative movement of the additive and Segmental Specific Specific Self With polymer
the polymer segments. Thus, important mobility free-volume volume associations mid other
factors are the size and shape of the
additive, and the amount and the distri-
additives
bution of the free volume in the poly-
Figure 6: Interactions and properties that have significance in the use of additives in
mer. Characteristics of the polymer and
polymer compositions ~4
of the additive were capable of affecting
both the solubility and the mobility of important in aliphatic hydrocarbon poly- between the molecules. From this
the components of the system. mers. An expression for the interaction expression it is clear that the magnitude
The free volume of the additive is energy between the molecules when of the interaction for polar molecules is
'added' to that of the polymer when the attractive forces are operating is given much greater than that for non-polar
two are mixed. An increase in the free by: molecules, This is the reason for the
volume of the polymer enables a higher dominance of polar interactions, such as
degree of segmental mobility. This 1~d~ C6126 +Q,8128 +Q,10~10 hydrogen bonding, in a polymer system.
increases both the solubility and the Fryer described an example of a polar
mobility of the additive in the system. Here, Udi~ is the interaction energy aris- molecule being introduced into a non
The specific volume of the additive ing from dispersion force interaction, C polar matrix, such as may be encotm
rather than the molecular weight was is a coefficient of attraction and r is the tered with tile introduction of an impu
found to be of significance, An increase shortest distance between the mole- rity into a system/6 An induced dipole
in the specific volume of the additive led cules. may be created in the matrix, Here, the
to an increase in the activation energy of expression for the interaction is modi-
When the molecules reach a certain dis
both transport phenomena, solubility fied. In this situation, the relevant rela-
tance of separation, the attractive forces
and mobility. Self interaction of the addi- tionship can be represented by:
turn to repulsive forces due to the simi
live did not affect the mobility, but did
larity of the electron clouds. When the
affect the solubility as it decreased. Inter
repulsive forces operate isotropically, rn U 4c%/,~
action of one additive with another
becomes r -12. However, anisotropic 76
additive through hydrogen bonding
forces may result in a different value of
decreased both the solubility and the Here, c~ represents the molecular polar-
n. Similar to the expressions used for the
mobility. In both cases, the interaction of isability of the non-polar molecule. This
attractive forces, the repulsive forces are
an additive with another additive mole example shows that the effect of an
represented by Ar-12, where A is a coef-
cule means that active groups are not impurity may be much greater than that
ficient of repulsion and r has its previous
available to carry out the stabilisation expected on the basis of the molecular
meaning, Combining the two expres-
roles, The thermal history of the polymer size of the impurity. This is an important
sions, an overall equation for the inter-
is also an important consideration, The point with respect to product integrity
action energy U is obtained:
solubility of an additive was found to and to the properties of the resulting
decrease reciprocally with crystallinit% polymer system (blend).
C /k
as the additive is excluded from the crys- U
tallites. In addition, any recrystallisation r6 r12 The miscibility of polymer blends is
processes can affect the amount of free related to the interactions that occur
volume in the polymer. For polar molecules, a permanent dipole between the component polymers.
is present, The interaction energy is These interactions include dipole-dipole
Interactions and reactions in dependent on the relative acidity of the interactions, ionic interactions and
composite blends groups involved and on the basicity of hydrogen bonding.
the groups involved. Thus, for two inter
London dispersion forces are those that acting polar entities, the equation for the Weber described three different cate-
are caused by the changing distribution polar interaction UpoI becomes: gories of polymer blend: miscible, par-
of electrons between two atoms or tool tially miscible and immiscible. 3r Miscible
ecules, creating an oscillating dipole/<36 2/~1/-~2 blends are those where the chain seg
The forces are dependent on the dis k]pd~- r3 ments of the polymers mix on a molecu
tance between the two interacting, non lar level. The blend exhibits a single,
polar entities involved. Hence, it is the Here, 1.t represents the dipole moment composition dependent glass transition
dispersion forces that are the most of each molecule and r is the distance temperature. An example of a miscible

Surface Coatings International Part B: Coatings Transactions

Vol 89, B1, 1-98, March 2006
 Polymer blend formulation and processing, with reference to the nature and the behaviour of
pigmented polyc~xbonate - poly(butylene tereptithalate) (eC-PBT)blends
K E Fagelman and J T Guthrie

blend is the poly(phenylene ether)/

poly(styrene) (PPE/PS) system. Partially
miscible or compatible blends have
properties that are very composition
dependent. The blends have a phase-
separated morphology and exhibit two
glass-transition temperatures that may
deviate from those of the parent
homopolymers. Examples of partially
miscible blends are given by polycar- Entanglement Covalentbond
bonates/polystyrenics. Immiscible blends
have a completely phase separated mot
phology. Two glass transitions are evi
dent, as for the parent homopolymers.
However, the lack of interracial strength
between tile two polymer phases means ;-" ,, ,..)
that mechanical properties are poor.
Sperling has discussed the interfacial
aspects of multi-component polymer Hydrogenbond Interphasechainconformation
blends. % The three major interface types
that may exist in such a blend are stated Figure 1: Common phenomena occurring in the interphase region between polymers 38
to include a symmetric polymer inter-
face, an asymmetric polymer interface compatibility/g Tile authors concluded dom of tile macromolecule, and that
and a composite interface. A symmetric that if tile pigment was compatible with fl'eedom affects adjacent macromole
interface occurs between two polymer the polymer matrix, warping would be cules, a long range interaction may
chains of the same type. This interface is observed. This was expected to be due Occur.
formed by tile contact of two melt sur to strong interactions between the pig
faces. However, tile interface may heal ment surface and the polymer chains,
over time as the polymer chains inter resulting in a composite matrix, through
Crystallisation and
mingle. which the chain movement and the nucleation of polymers
An asymmetric interface involves tile mechanical relaxations were hindered. There are four parameters that may be
presence of two different polymers. The With incompatible pigments, no warp- considered when discussing polymer
existence of such an interface depends ing was observed because there would crystallinity. 41 These parameters are tile
on the molecular weights of the poly- be no interaction between the pigment degree of custallinity, the number of
mers and on the ability of the chains to and the polymer matrix. In this case, the crystallites per unit of volume, tile aver
form entanglements. The depth of pene- pigment and the polymer chains age size of the crystallite, and tile aver
tration of the polymers at the interface behaved as separate phases, allowing age distance between crystallites. The
can range from 1 to lOOnm, depending molecular movement to take place. chemical structure of the polymer chains
upon the free energy of mixing. Tile These difl'erences were also apparent in involved in the crystallisation process
interface is commonly referred to as an the observed microstructure of the determines the morphology of the sam-
interphase where the depth of entangle HDPE. Compatible pigments resulted in ple. This is because the flexibility of the
ments at that position is broad. Tile a disrupted crystalline morphology, chains dictates the spatial arrangements
interphase may also contain physical whereas incompatible pigments did not that can take place. For example, while
bonds or chemical bonds, connecting result in any observable structure modi- a flexible chain may fold or form ran
tile two polymers. Hence, tile interphase fication. dom coils, a rigid chain may not. Tie
can have very difl'erent properties rela Kumins discussed the long-range effects molecules are parts of chains or bundles
rive to either of the constituent poly- of polymer-pigment interactions in solid of chains that extend fl'om one crystal
mers. state systems. 4~ The author demonstrat- lite, or lamellar arrangement, to another.
ed that the incorporation of small Tie molecules are very important for tile
Figure 7 illustrates the more common
amounts of pigment in a polymer could mechanical properties of the sample
phenomena occurring in the interface
produce significant changes in tile mate because these chains concentrate and
region. In the case of the interphase
rial properties. Changes were observed distribute the stresses throughout the
chain conformation, the chain ends
in terms of polymer glass transition tern material.
interpenetrate while the chain orients
itself parallel to the interphase. peratures and density values, and in the Crystallisation is the process that occurs
diffusion coefficients of gases. Tile when an ordered structure is formed in
A composite interface is that which changes were not attributed to specific the melt phase of a polymer system.
occurs between a polymer and a non surface interactions or to the pigment
Bulk crystallisation of the polymer from
polymer solid phase. Although the poly particle size, but to restricted segmental tile molten state is dependent on tern
met is not generally able to penetrate motion brought about by the adsorption perature, and may be described by
into the solid surface, it may adhere to it of active groups on the particle surface. nucleation and growth mechanisms. As
via chemical bonds or via physical The adsorption resulted in restricted tile temperature of tile melt approaches
bonds. mobility of the polymer chains, which its crystallisation temperature (TeL there
Bugnon and co-workers investigated the also restricted the mobility of neighbour- is a tendency for randomly arranged
ing chains. Thus, if an interaction molecules in the melt to become aligned
effect of organic pigments on the warp-
ing of high density poly(ethylene) between the polymer and tile surface and to form small ordered regions.
(HDPE) in terms of pigment polymer reduces tile number of degrees of free

Surface Coatings International Part B: Coatings Transactions

Vol 89, B1, 1-98, March 2006
 Polymer Mend formulation and processing, with reference to the nature and the behaviour of
pigmented polycarbonate - poly(butylene tereptlthalate) (PC-PBT) blends
K E Fagelman and J T Guthrie

These are called nuclei, and there are either of layers or rows of alternating ment in the ability of ttle poly(ethylene
two categories of nucleation. polar and non polar molecules, or they terephthalate) to crystallise.
expose a non polar surface to the melt
The first type of nucleation is primary or Mudra and Bal~s evaluated a number
while confining polar groups. This means
homogeneous nucleation. Here, small of additives as nucleating agents for
that they usually have an apolar surface
particles of the new phase, termed polyamide-6. 48 The additive range
in contact with the polymer melt. The
embryos, are formed. If a minimum acti- included: calcium stearate, poly(ethyl-
exposed faces show shallow ditches in
vation energy is met, a few molecules ene terephthalate), calcium carbonate,
which adsorbed polymer molecules can
pack side-by-side. If the energy require- talc, a phosphate compound, an alu-
be forced to assume a stretched confir-
ment is not met, the molecules return to minium salt and commercial nucleating
mation. If this occurs over some dis-
the melt state. As the embryo grows, the agents. A range of observations was
tance, crystallisation occurs much more
free energy increases. This continues made. Tile talc was the most effective
easily.
until a critical size is reached. After this nucleator of tile polyanude. Tile phos
point, tile embryo is able to grow spon Jang and co workers studied tile efl'ects phate and the PET showed minor
taneously and tile fl'ee energy decreases of sodium benzoate as a nucleating effects. Tile calcium compounds
until it is less than that of tile polymer agent in impact modified poly(propy behaved as inert fillers. However, tile
melt. Tile embryo is then considered to lene) matrices. 4s An increase in tile crys almninimn salt strongly decreased tile
be stable, and a nucleus may be formed tallisation rate and a difl'erence in the crystallisation rate. From this observa
from it. This is the rate-determining step morphological structures of the samples tion, the authors re-evaluated the origi-
of the nucleation process. were observed. However, their study nal polyamide sample together with a
was further complicated by the nature of 'pure' form that contained no additives.
The second type of nucleation is sec-
the impact modification methods that The authors found that an amide wax
ondary or heterogeneous nucleation. In
were used. These methods were reactive lubricant already present in the polymer
this case the nucleus forms on the sur-
blending and mechanical blending, and was also acting as an efficient nucleating
face of a foreign entity that is present in
this difference alone was found to be agent. The authors concluded that some
tile melt. This may be an impurity, a true
capable of changing the properties of interaction was occurring between the
component of tile system (eg pigment
the polymer system. wax lubricant and the almniniunl salt
particle) or an additive that has been
resulting in the observed decrease in tile
intentionally added for this purpose. Martin and co workers described the
crystallisation temperature.
Here, tile total interracial fl'ee energy of use of sorbitol derivatives as nucleating
tile crystalline embryo is decreased by agents for polymer systems. 46 Tile mole Okamoto and co workers investigated
tile foreign phase providing part of tile cules that were studied had tmreacted tile crystallisation behaviour of injection
interface to be formed. This decreases hydroxyl groups that enabled them to moulded specimens of poly(ethylene
the activation free energy for nucleation, form fibrous structures when the poly- terephthalate), poly(ethylene terephtha-
and also decreases the amount of super- mer system cooled from the melt. It is late) containing talc and poly(ethylene
cooling required for nucleation to take this characteristic that enhances the terephthalate) containing Surlyn
place .42 nucleating ability of these additives. The (DuPont Inc), (a poly(ethylene)
authors' work compared the crystallisa- ionomer). 49 The authors found that the
After nucleation, crystal growth takes
tion behaviour of two propylene-ethyl- blend containing the Surlyn was orien-
place. Spherulites are a morphological
ene copolymers: one that contained a tated near the surface of the specimen
feature of the melt crystallised polymer.
sorbitol based additive and one that did so that crystallisation was accelerated.
They are made up from a large number
not.
of chain folded lamellar crystallites that
radiate in all directions fl'om tile central Tankhiwale and co workers studied the Polycarbonate (PC) -
nucleus. 43 Tile size of these spherulites is efl'ect of triphenyl phosphate (TPP) on a poly(butylene
dictated by tile conditions of nucleation, poly(ethylene terephthalate)
not by the speed at which they grow. A poly(styrene) polymer blend/7 Tile glass terephthalate) (PBT)
coarse morphology results if it consists of transition temperature of each polymer blends
large spherulites. decreased as the loading of TPP was
increased. This decrease was thought to Xenoy | is a thermoplastic polymer
It is possible to use a nucleating agent to blend of an amorphous polycarbonate
be due to the interactions occurring in
shorten the induction time for nucle- (bisphenol A polycarbonate) (PC) and
the polymer matrix. At low loadings of
ation, and to enhance the overall rate of semi crystalline poly(butylene tereph
TPP, the particles were able to penetrate
transformation from the molten polymer thalate)s (PBTs). Tile PC gives the blend
into the spaces between the amorphous
to tile crystalline solid state. Tile nuclear excellent impact strength and dimen
segments. This enabled the establish-
ing agent functions by providing many sional stability over an extended temper
ment of secondary interaction forces
sites on which it is possible to initiate tile ature range. The PBT provides good
between the additive and tile polymer
crystallisation process. As spherulites chemical resistance, good flow and satis-
chain segments, while decreasing the
grow fl'om the nuclei, they impinge factory processability characteristics.
forces between the polymer chains
upon one another. This results in tile Thus, the general property profile of a
themselves. At tile higher loadings of
arrest of the spherulite growth. The Xenoy article is one that possesses high
TPP, more penetration was able to take
increased crystallisation rate leads to the impact strength and low temperature
place and the segmental mobility was
development of a fine spherulitic mor- ductility, good chemical resistance, prac-
reduced further. Considering the crys-
phology, resulting in a more uniform tical heat resistance and easy process
tallisation behaviour, the authors con-
crystalline structure. ability. This is in addition to the excellent
cluded that the TPP had a nucleation-
facilitation effect in the blend. This was aesthetic properties that can be impart
There are several major features that are
manifested by an increase in the crys- ed to articles that have been suitably
common to nucleating agents. 44 The
agents are insoluble in tile polymer melt tallinity of the blend, and as an improve- fabricated from Xenoy materials.
and are crystalline. The agents consist

Surface C o a t i n g s I n t e r n a t i o n a l Part B: C o a t i n g s T r a n s a c t i o n s
t/ol 89, B1, 1-98, March 2006
 Polymer blend formulation and processing, with reference to the nature and the behaviour of
pigmented polyc~xbonate - poly(butylene tereptlthalate) (PC-PBT)
blends
K E I:agelman and J T Guthrie

Morphology and morphology and of a variety of polyesters to examine amorphous phase. In addition, the pres
development aspects of the miscibility of the polymer ence of two crystallisation exotherms, in
blends, s2 The authors found that inter thermal studies, indicated that tile PBT
With the ratio of PC and PBT polymers pretation of the complex interactions was able to crystallise from a PBTrich
approximately equal, Xenoy displays a that occurred between the polymers was phase and a PC-rich phase. A glass-tran-
co continuous morphology with clearly difficult, but they did propose an expla- sition event that did not correspond with
separated PC and PBT phases. HoweveL nation. They concluded from their stud- either polymer was also observed. This
these phases are capable of limited ies that the interaction that led to nega- was indicative of an interchange reac-
mutual solubility. Thus, there is a partial tive heats of mixing was probably due to tion having taken place, although it was
miscibility of the two phases, to a level of n-~ complex formation between the not thought to be an extensive reaction.
2 to 5%. This solubility affects the crys electrons of the ester-carbonyl group
tallisation kinetics of the PBT compo- Delimoy and co workers observed
and the aromatic ring of the molecule
nents. At the elevated temperatures that direct evidence of tile limited miscibility
carrying the carbonate entity.
are encountered during processing, the of PC in PBT, above the crystallisation
degree of solubility between the phases Hobbs and co workers investigated the temperature of PBT.s6 The authors
increases. When the extruded material is morphology of PC PBT melt blends that observed PC in amorphous interlamellar
then injection-moulded, the more solu- also included an impact modifier. ~3 They regions, the PC having been rejected
ble state is 'frozen in'. Phase separation observed that the impact modifier was fl'om the growing PBT lamellae upon
is expected to occur as the product ages. located entirely within islands of PC. cooling. In the images observed of slow-
As slow crystallisation of the Xenoy takes TEM and SEM analyses of specimens ly cooled PC-PBT blend samples, a large
place, PBT lamellae grow from the PBT provided evidence of melt miscibility number of PBT lamellae were observed
rich phase into the PC rich phase, and of phase separation of the polymers to grow from the interface region into
depleting the PC rich phase of dissolved during the PBT crystallisation process. the PC-rich phase. This observation con-
PBT. As this happens, PC becomes The degree of crystallinity of the PBT firmed that PBT was present in the PC-
trapped between the PBT lamellae, (33?/o) was relatively constant over the rich phase and that two sets of crystalli-
residing in amorphous regions that are blend composition range that was stud- sation kinetics should exist for the PBT
then able to affect the deformation ied. HoweveL the spherulites lost defm component of the blend. Thermal treat
behaviour of the product. ition as the percentage of PBT in the ments greatly effected the observed
blend decreased. During phase separa morphology of the samples, and the
These observations can be made on the tion, the PC and the PBT polymers inter morphological changes were driven by
basis of the work that has been carried penetrated, thus creating an extremely the interracial tension of the phases and
out by many authors on PC-PBT blends strong interface. The authors believe that the PBT ccfstallisation processes. Inter
since the development of such blends the incorporation of PC into the inter change reactions were not considered in
for automotive bumper applications in lamellar regions of the PBT spherulites these studies, as the blends were sta
1978/0 The blends show complex melt could have a significant effect on the bribed against reaction.
behaviour. The major areas of research deformation behaviour of the blend.
have concerned the miscibility of the Wilkinson and co-workers described
two polymers, phase separation effects S~inchez and co-workers determined how structure development in PC-PBT
and interchange reactions that occur that the development of crystallinity was blends tends to be dominated by the
during processing. These effects are diF not an important parameter in regard to PBT crystallisation process/r This rapid
ficult to separate in terms of the phe the mechanical properties of a PC/PBT crystallisation prevents significant phase
nomena taking place. The diagram in blend/4 Instead, the free volume of the dissolution and 'locks in' the biphasic
Figure 8 illustrates the connections amorphous part of the blend was morphology. The capability of the PBT to
between each of these processes and thought to be the most significant factor. crystallise is reduced as transesterifica
the blend components, s~ tion takes place. The authors' work corn
Wahrmtmd and co workers studied
pared the behaviour of PBT alone to that
Cruz and co-workers used low molecu- blends of PC and PBT.ss They concluded
of the PC PBT blends. The PBT formed
lar-weight analogues of polycarbonates that the blends exhibited more than one
well ordered lanlella stacks that exhibit
ed reproducible melting and recrystalli-
sation behaviour. The PC-PBT blends
contained varying amounts of transester-
ification catalyst so that a series of sam-
ples with varying extents of transesteri-
Crystallisable
Blendcomposition] content fled products was obtained. The samples
with the lowest degrees of transesterifi-
CrystallisafiOnrate 1 cation showed significant disruption of
the spherulitic morphology, and the PBT
lamellae appeared to be randomly oli
(type,content)
Interfadalareabetween I
It
Residualcatalystof PBTsynthesis

.I Copolyestercontent Compatibility~
I CrystallinityI

[
entated. The lamellar structure was dis
turbed due to the PC presence within
the amorphous interlamellar regions.
The two phase morphology no longer
PCandPBTphases I "l bytransesterificati0nI 1 existed in those samples with the greater
degrees of transesterification. Instead, a
Temperature] l [Blendmorphology[ continuous semi-crystalline phase was
observed, with sheaf-like bundles of
lamellae impinging upon one another to
Figure 8: Connections between the polymer components, the potential reactions between form an entangled mass.
the components and the subsequent effects on the morphology development51

Surface Coatings International Part B: Coatings Transactions

Vol 89, B1, 1-98, March 2006
 Polymer blend formulation and processing, with reference to the nature and the behaviour of
pigmented polycarbonate - poly(butylene terephthalate) (PC-PaX) blends
K E fagelman and J T Gnthrie

Halder and co workers studied the

superstructures of a range of composi I I I I I IIII IIII IIIIIIIIII
{ions of PC/PBT blends, sa The blends
were crystallised from the melt. The I I I I I IIII II I IIIIIIIIII
presence of PC was found to effect the
crystallisation behaviour and the mor- Figure 9: Representation of the copolyrnerisation degree achieved with the progression of
phology of the PBT. As the amount of PC transesterification
in the blend was increased (up to
50%(w/w)), the rate of crystallisation the sample has a high impact strength. tion of (AB)ntype r a n d o m block
decreased and the spherulite type In semi ductile fracture, plastic defor copolymers. If the reactions continue
changed from unusual to usual patterns. marion occurs in the area that is direct- for a prolonged amount of time, even-
The usual spherulites were observed to ly around the notch tip. This plastic tually the block structure is lost and a
be more stable than the unusual deformation is followed by rapid crack statistical AB-copolymer is obtained.63
spherulites. Ludwig and Eyerer have dis propagation throughout the sample. This process is illustrated schematically
cussed the spherulitic structure of PBT, Deformation occurs only around the in Figure 9.
as observed by light microscopy, s9 notch base with little additional energy
Three mechanisms have been suggested
adsorption. During brittle fracture,
Hobbs and co workers investigated the for tile transesterification reaction:
rapid crack growth is promoted
diffusion bonding occurring between throughout the sample. No deforma 9 Alcoholysis
bisphenol-A polycarbonate (BPA-PC) tion takes place and very little energy is
and PBT.60 Laminates of the two poly- dissipated. This means that the sample Here, tile hydroxyl endgroups of the PC
mers were prepared by a spray applica- or tile PBT react in chain with another
has a low impact strength.
tion procedure. PBT fibril growth was macromolecule of either the PC or the
observed. It occurred as a result of the These fl'acture modes have been corre PBT.
crystallisation of PBT chains that had dif- lated with results obtained from tensile
testing studies. It was found that ductile 9 Acidolysis
fused into the PC upon annealing of the
sample. The fibrils were nucleated at the fracture occurs via a shearing mecha- Here, the carboxyl endgroups of the PBT
interface between the polymers, and nism, while the semi-btittle and brittle react with tile PC.
grew into the PC phase in a manner that modes occur through cavitation of the
impact modifier, followed by shearing. 9 Direct reaction
was consistent with the presence of a
concentration gradient. The number of Parker and co-workers studied the Direct carbonate ester exchange reac
chains present in the diffusion area was toughening mechanism of a core-shell lions lead to tile production of random
observed to be dependent upon, and rubber-modified polycarbonate) 2 They copolymers.
limited by, the solubility of the PBT in showed that the cavitation of the rubber
the PC. Fibril growth only occurred at particles takes place first, followed by Devaux and co-workers examined the
temperatures above the glass-transition enhanced shear yielding. The cavitation exchange reactions occurring in molten
process reduces hydrostatic stresses in PC-PBT blends. 64 The authors theorised
temperatures of both polymers.
front of the crack tip, which then influ that direct transesterification is the
Mechanical behaviour ences the ability of the polymer to shear dominant mechanism, together with
yield. This also shows that the interracial the alcoholysis and acidolysis of the PC
Because the stress transfer across the by the hydroxyl group terminated PBTs
adhesion between the rubber and the
phases is one of the critical factors that and by the carboxylic group terminat
PC is stronger than the cavitation resis-
determine the load-bearing capacity and ed PBTs respectively. The extent of the
tance of the rubber, otherwise debond-
the impact strength of the matrix, this transesterification was followed practi
ing of the rubber particles from the
strong interface should exhibit a positive cally by infrared spectroscopy and by
matrix would occur.
effect on these properties. It has been determination of the solubility of the
reported that, at low stresses, the Xenoy The transesterification reaction reaction products in methylene chlo-
blend shows PBT-like behaviour. Then, ride. In methylene chloride the PC is
b e t w e e n PC a n d PBT
at higher stresses, when the flow of the completely soluble and the PBT is
PBT component becomes significant, The potential for transreaction in poly- essentially insoluble. A small degree of
the PC phase dominates the behav mer blends is strongly dependent upon transesterification led to only a small
lout) l the compatibility of the blend compo- amount of the mixture being soluble.
nents and the processing conditions This was due to the initial formation of
Notched impact testing is a method
applied. Conditions that are particular a copolymer with a long PBT sequence.
used in the analysis of polymer blends.
ly relevant are the temperature, the As transesterification progressed, more
This is because the impact energy of
time of mixing and the presence of cat and more of the blend became soluble
the thermoplastic and the method of
alytic or inhibitive species. Transesterifi (the PBT sequences become shorter),
fracture may be directly related to the
cation reactions are known to occur until the end point of the reaction was
ability of the polymer chains to under-
between the PC and the PBT compo reached where the entire product was
go segmental motion and dissipate the
nents of the Xenoy blend under the soluble.
energy in the sample. Toughened
conditions used for extrusion and injec-
blends have been observed to fracture The titanium catalyst that remains in the
tion moulding.
by one of three mechanisms: ductile, PBT polymer after its synthesis/manufac-
semi-ductile or brittle. In ductile frac- The main chain transesterification of ture is known to be a catalyst for the
ture, stable crack growth propagation PC-PBT blends has been well docu- direct transesterification reaction. 6s
occurs throughout the sample. A slow mented in the literature. Initial transes-
teanng type mechanism with extensive teriflcation results in the formation of Kong and Ajji evaluated the effect of the
plastic deformation allows a large AB type block copolymers. Continued mixing conditions on the degree of
absorption of energy. This means that transesterification leads to the forma transesterification taking place in

10 Surface C o a t i n g s I n t e r n a t i o n a l Part B: C o a t i n g s T r a n s a c t i o n s
Vol 89, B1, 1-98, March 2006
 Polymer blend formulation and processing, with reference to the nature and the behaviour of
pigmented polyc~xbonate - poly(butylene tereptlthalate) (PC-PBT) blends
K E Fagelman and J T Guthrie

PC/PBT blends/6 Evaluations were bet of OH groups present in the PBT, 9 surface defects (eg bubbles or splay)
made by varying the particular process the greater was the amount of gas gen caused by the generation of volatile
ing conditions. The selected parameters crated. The enhanced stability of the products such as CO 2 or THF dur
were blending temperature, blending PC component in the stabilised blends ing tile processing stages;
time, mixing speed, and the absence or suggested that the breakdown was in 9 a decrease in the Vicat Softening
presence of an inhibitor in the formula- some way connected to the residual Point, as a result of the PC and the
don. The authors concluded that tem- titanium catalyst present in the system. PBT glass-transition temperatures
perature was the most significant para- This could be as a result of transesterifi- shifting towards each other',
meter, with higher temperatures cation or because the titanium catalyst 9 discoloration of the blend as the
promoting transestetification. However, directly influenced the PC breakdown. residual titanium catalyst in the
the high temperatures also contributed copolyester reacts with the free
Transesterification was observed to
to the degradation of the PC and the phenol groups in the PC;
occur in Xenoy blends studied by the
PBT components. In a similar fashion, as 9 aggregation of tile impact modifier
authors. 6a Two Xenoy blends of identical
the blending times increased, the particles due to reduced compatibil
fommlation were prepared on two
degree of transesterification increased ity with tile transesterified blend;
extrusion units and then injection
(as did the level of degradation of the 9 an increase in the viscosity as tile
moulded using the same unit. Samples
component polymers). Changing the compatibility increases with the for
of the moulded specimens were exam
speed of mixing was deemed to change mation of tile copolyesters.
ined by transmission electron
the amount of shear experienced by the
microscopy (TEM). This technique However, the transesterification reaction
blend. However, mixing speed was not
allows the evaluation of multi-phased is not always unwanted, and can in fact
found to influence the degree of trans-
polymer samples at a high resolution. be employed in polymer systems to opti-
esterification. Regarding the transesteti-
For each image, the lighter areas corre- mise particular properties of polymer
fication inhibitor, the authors observed
spond to the PBT phase of the blend and blends) ~
that an optimum amount of inhibitor
the darker grey areas to the PC phase of
was necessary for stabilisation of the sys- Several chemical additives have been
the blend. The very dark spherical inclu-
tem. Above that amount, no further used as transestedfication inhibitors in
sions are caused by the presence of the
improvement in stabilisation took place. Xenoy blends. The catalytic nature of the
impact modifier particles. The scale of
It was also concluded that the transes titanimn residue is partly due to the
the micrographs is shown in the bottom
terification process could not be open co ordination sites present at the
left hand corner of each micrograph (see
stopped entirely, and that a small metal centre. Inhibitors act by quench
Figure 10).
amount of copolymer was always pre ing, or complexing, with the titanimn
sent in the blend system. catalyst via the formation of bidentate
9S , ~ l # ' , " , ~ l ~ 0 % ligands. Organophosphites and phos-
Pellow ]armen and Hetem carried out
phate salts are Wvo of the chemical types
gas decomposition experiments involv-
that are used as inhibitors.
ing stabilised PC-PBT blends and an
unstabilised PC-PBT blendY Carbon ~--~.'.-r,e~ , ~ ~ - ~
Initially the rate of transesterification is
dioxide was produced by both groups Ir,.'i j'y faster than the rate of complexation of
of samples. However, the stabilised the inhibitor with the titanium catalyst.
..~,-..~~_~,, _~d]
blends did not generate the gas until a This means that a small amount of
considerably higher temperature had Figure 10: TEM images of the Xenoy blends copolymer is always present in the PC
been reached (300~ compared with PBT blend. Being such a small amount,
220~ and even then, they generated Figure 10 shows the TEM images that it is very difficult to identify and to quan
only 20% of the amount produced by were obtained for the Xenoy samples.
tify using standard analytical tech
the unstabilised blends. Apart from car The sample that was compounded on niques/0
bon dioxide, the decomposition prod Extruder 1 shows the typical morpholo-
gy for the Xenoy blend. The phases of The observation has been made that
ucts generated by the two groups of
samples were markedly different. The PC and PBT are easily distinguished and PBT with a high carboxylic content
the impact modifier particles are well transesterifies less than PBT with a low
unstabilised blends produced mainly
bisphenol A, phenol, possibly the poly- dispersed and located entirely within the carboxylic content. This is due to the
carbonate and poly(butyl terephtha- PC phase. The sample that was corn quenching ability of the carboxylic
late) oligomers and methane. The sta- pounded on Extruder 2 shows a very diF group (COOH), which is similar to the
bilised blends produced mainly ferent morphology. It is difficult to distin POOH group of the phosphates. How-
guish the different PC and PBT phases ever, the complex formed would not be
tetrahydrofuran (THE) and poly(buty-
and there are large clusters of rubber as stable as the complex with the phos
lene terephthalate) oligomers. Thus, it
modifier particles. This morphology is phate and, thus, the PBT would still have
appeared that the unstabilised blends
typical of a transesterified sample. the ability to transesterify.
and the stabilised blends produced
polycarbonate and poly(butylene Transestetification has a negative effect
terephthalate) breakdown products on the properties of the Xenoy blend. Conclusion
respectively. These differences were The major consequences of the This review has shown that there are
concluded to be due to the different exchange reactions are: many factors which must be considered
degrees of transesterification taking
place in the two groups. Further exper 9 a decrease in the crystallinity of the when manufactuting polymer cornposite
blend; articles. The components included in tile
iments indicated that carbon dioxide
9 a decrease in the chemical resis fommlation may have effects beyond
release originated from the PC compo-
tance, as a result of the decreased those expected. Control of tile process
nent, and was linked to a reaction
crystallinity; ing conditions is very important and
beWveen the PC and the PBT. It was
deviations from standard practice may
also observed that the greater the num-

Surface C o a t i n g s I n t e r n a t i o n a l Part B: C o a t i n g s T r a n s a c t i o n s 11
Vol 89, B1, 1-98, March 2006
 Polymer blend formulation and processing, with reference to the nature and the behaviour of
pigmented polycarbonate - poly(butylene terephthalate) (vc-P~) blends
K E Fagelman and J T Gnthrie

result in samples with difl'ering mor 11. Wypych G, (ed), iCandbook o[ Polymer Chemistry, University of
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1 895198 29 1 and W R Murphy, "The influence of
Acknowledgement 12. Dubault A, L Bokobza, E Candin nucleating agents on the extrusion
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(financial and experimental) provided to interactions on the viscoelastic and lene', Pol,jme~ Engineering and
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12 Surface Coatings International Part B: Coatings Transactions

Vol 89, B1, 1-98, March 2006
 Polymer blend formulation and processing, with reference to the nature and the behaviour of
pigmented polyc~xbonate - poly(butylene terephthalate) (PC-PBT) blends
K I~Fagelman and J T Guthrie

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Surface Coatings International Part B: Coatings Transactions 13

Vol 89, B1, 1-98, March 2006
 Polymerblend formulationand processing,withreference to the nature and the behaviourof
pigmentedpolycarbonate- poly(butylenetereptlthalate) (PC-PBT)blends
K E I:agelmanand J T Gnthrie

70. Pompe G and L H~ul31er,

'Investigations of transesterification
in PC/PBT melt blends and the
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1997

14 Surface Coatings International Part B: Coatings Transactions

Vol 89, B1, 1-98, March 2006