Polymer Additive

There are four main polymer AM material classes: StereoLithography Apparatus

(SLA) in which a laser solidifies liquid layers of photo-sensitive monomer in a vat;

From: 3D Bioprinting for Reconstructive Surgery, 2018

Related terms:

Nanoparticle, Fiber-Reinforced Composite, Polyethylene Glycol, Three Dimensional

Printing, Perovskites, Extrusion, Antioxidant, Plasticizer

View all Topics

Polymers for Advanced Functional Ma-

terials
C. Kröhnke, in Polymer Science: A Comprehensive Reference, 2012

8.14.9.1 Introduction
Besides already established technical polymers, the plastics industry is continuously
developing new polymeric materials. Most of these products have to fulfill strict
requirements during their service life depending on the individual applications.
However, indispensable properties of plastic materials can only be achieved by
optimal adjustment of the additives package to the specific requirements. Therefore,
the development of tailor-made recipes and also the introduction of novel polymer
additives and additive combinations contribute to strengthened and continuously
improved plastic articles.

As a consequence, it becomes mandatory to assess quickly the efficiency of

additives with respect to technical and environmental conditions to which they
are likely to be subjected. Since examination of changes of polymer materials at
ambient conditions often requires long time periods, several methods have been
developed which allow an accelerated degradation. Nevertheless, it has to be ensured
that accelerated aging processes correlate with degradation steps observed under
normal service conditions. Regarding thermal and UV light-induced degradation,
various accelerated test methods are established studying the influence of additives
on polymer performance.58

TGA coupled to FTIR, TGA/FTIR, has been investigated to study the degradation of
several polymeric systems containing additives such as poly(methyl methacrylate),
graft copolymers of acrylonitrile–butadiene–styrene and styrene–butadiene with
sodium methacrylate and styrene with acrylonitrile, blends of styrene–butadiene
block copolymers with poly(vinylphosphonic acid) and poly(vinylsulfonic acid), and
crosslinked polystyrenes. It must be pointed out that additives may interact with
poly(methyl methacrylate) by coordination to the carbonyl oxygen to a Lewis acid and
the subsequent transfer of an electron from the polymer chain to the metal atom
or by the formation of a radical that can trap the degrading radicals before they can
undergo further degradation.

> Read full chapter

UV STABILIZERS AND OTHER COM-

PONENTS OF FORMULATIONS
In Handbook of UV Degradation and Stabilization (Third Edition), 2020

Polymer processing additives are used to reduce melt fracture, increase the pro-
cessing window, and eliminate die-lip build-up and gels in polyolefins.15 Some
additives may interfere with the performance of the polymer processing additive
by four main mechanisms – adsorption, abrasion, site competition, and chemical
reaction.15 Strong bases such as hindered amine light stabilizers can cause the
polymer processing additive to lose effectiveness, due to both site competition and
chemical reaction.15 In the presence of HAS, chemical reactivity is possible with
typical polymer processing additives composed of reactive fluoropolymers, which are
most frequently used in these applications. While such an interaction occurs, it has
been demonstrated that the HAS interaction does not change its stabilizing ability,
but only affects the performance of the processing additive.15 Nonreactive polymer
processing additives have been found.15 It allows for broader selection of other
additives, processing at higher temperatures, and reduces the required amount of
polymer processing additive necessary to eliminate melt fracture and lower extrusion
pressure.15

> Read full chapter

Fluorinated Additives
In Introduction to Fluoropolymers, 2013

8.1.3 Vinylidene Fluoride Polymer Additives

A polymer processing additive (PPA) has been developed from copolymers of vinyli-
dene fluoride (polyvinylidene fluoride, PVDF) by Arkema Corporation. The applica-
tion is as a process aid for the extrusion of polyolefins (linear low-density polyethyl-
ene, high-density polyethylene, polypropylene), in particular in the form of film [3].

Kynar Flex® PVDF PPA is added in low concentrations, of the order of 0.02% to 0.08%
by weight, to help increase processing speed while reducing energy consumption,
processing temperatures, and pressure. It also helps prevent blockages in equipment
and, in particular, the formation of drops and knots on converting lines. With respect
to the finished product, this PVDF additive enhances the film’s transparency and
mechanical properties, eliminates “sharkskin” surface defects, and melt fracture.

> Read full chapter

Understanding the durability of ad-

vanced fibre-reinforced polymer (FRP)
composites for structural applications
BenzartiK. , ColinX. , in Advanced Fibre-Reinforced Polymer (FRP) Composites for
Structural Applications, 2013

12.4.3 Loss of additives

Most technical polymers contain additives like antioxidants, plasticizers or process-
ing agents that do not form chemical bonds with macromolecules. These molecules
can migrate within the host polymer with a rate depending on their size, their
solubility and diffusivity among other parameters. The following discussion reviews
the limiting steps in additive migration.

A polymer–additive mixture is out of thermodynamic equilibrium. Since the additive

concentration in the environment is equal to zero, there is no equality between its
chemical potentials in the environment and in the polymer. Additive molecules tend
to migrate outside the polymer in order to reach an equilibrium. This migration is
composed of two elementary steps (see Fig. 12.7):
12.7. Schematization of a two-step migration of molecular species outside the
polymer. L is the sample thickness.

1. The first step corresponds to the passing of some additive molecules into a
medium of molecules close to the polymer surface, that is to say the crossing
of the polymer–external medium interface. It is an additive evaporation in
the case of an external gaseous medium (e.g. atmosphere), or an additive
dissolution in the case of an external liquid medium (e.g. water),
2. The additive molecule exchange between the polymer and the external medi-
um leads to a gradient of concentration in a region adjacent to the material
surface. This latter is the ‘driving force’ for the diffusion of additive molecules
from the core towards the sample surface. If diffusion obeys the second
Fick’s law, the diffusion distance (ℓ) is proportional to the square root of time
(td):[12.1]

where D is the coefficient of additive diffusion into the polymer.

For the sake of simplicity, we only consider here the Fickian diffusion process which
may occur in the glassy state far from Tg. But there are exceptions to this process
and we invite the reader to refer to extensive literature reviews for the treatment
of other transport modes of small molecules into polymers (Müller-Plathe, 1994;
Masaro and Zhu, 1999; George and Thomas, 2001).

One can see from [Equation 12.1] that td is an increasing function of the sample
thickness L. As a result, one can distinguish two distinct kinetic regimes, depending
on the relative predominance of the previous steps:

1. Regime 1: Evaporation (or dissolution)-controlled kinetics. In the case of thin sam-

ples (fibres, films, coatings) and high additive diffusivity, additive evaporation
(step 1 in Fig. 12.7) is the slowest step and thus controls the global migration
kinetics. Its concentration C (into the polymer) decreases proportionally with
time (see Fig. 12.8(a)):[12.2] The evaporation rate H is a decreasing function
of the additive molar mass and the cohesive energy density.Fig12.8 Additive
migration governed by (a) evaporation and (b) diffusion. Top: shape of weight
changes as a function of time. Sample weight (m) corresponds to polymer
weight (mp) plus additive weight (ma). Bottom: distribution, in the sample
thickness, of additive concentration (C) for different times of exposure: t0 <
t1 < t2 < t3. The initial concentration is C = C0 (at t = t0).
2. Regime 2: Diffusion-controlled kinetics. In the case of relatively thick samples
(typically a few millimetres) and low additive diffusivity, diffusion in the bulk
(step 2 in Fig. 12.7) controls the global migration kinetics. in the simplest case,
the second Fick’s law can be successfully applied. It is found that, in the early
period of exposure, the sample weight m decreases proportionally with the
square root of time (see Fig. 12.8(b)):[12.3]

where z is the spatial coordinate in the sample thickness.

Thus, a gradient of the additive concentration appears in the sample thickness.

Figure 12.8 shows the shape of the time variation of sample mass and concentration
profile in the cases of evaporation- and diffusion-controlled additive migration.

If the additive molar mass is relatively high, its evaporation (or, more generally
speaking, its crossing of the polymer-medium interface) is slow. Then, its concentra-
tion at the sample surface takes an intermediate value between C0 and zero. It is thus
necessary to take into account this variation in the boundary conditions for solving
[Equation 12.3]. If the additive concentration is high (in the case of plasticizers),
it modifies the polymer properties. Then, its diffusivity becomes concentration
dependent (an increasing function of the plasticizer concentration). Complications
appear when a phase transition takes place during the additive migration. As an
example, in case of diffusion of plasticizers in PVC, a dramatic increase in Tg occurs in
regions of low plasticizer concentration. The resulting Tg profile can have the shape
illustrated in Fig. 12.9.

12.9. Shape of distribution, in the sample thickness, of plasticizer concentration (C

expressed in weight fraction) and resulting local glass transition temperature (Tg) for
a plasticized PVC aged at room temperature (Wypych, 2004).

One can see that, in the sample bulk, the polymer remains in a rubbery state. On
the contrary, in the superficial layer of thickness ℓa, the polymer vitrifies and thus
becomes brittle. Since the coefficient of plasticizer diffusion varies by at least one
order of magnitude on both sides of the glass transition, the real gradient will display
rather the shape of Fig. 12.10. In such cases, the diffusion ‘front’ is very abrupt and
the sample weight decreases proportionally with time.
12.10. Correction of the hypothetical curve (right) presented in Fig. 12.8. Real shape
of the distribution, in the sample thickness, of plasticizer concentration (C) for
different times of exposure: t0 < t1 < t2 < t3 < t4.

From the mechanical point of view, the loss in additives leads to a loss in the specific
properties targeted by the introduction of these additives: long-term durability in
the case of antioxidants, flexibility in the case of plasticizers, etc. If the additive
concentration is high (in the case of plasticizers), their loss induces a volume
shrinkage (of the same order of magnitude than the weight loss, but slightly lower).
This shrinkage can generate local stresses and thus lead to crack initiation in the
brittle superficial layer.

> Read full chapter

3D printing
Christopher J. Hansen, ... Jay H. Park, in Handbook of Thermoset Plastics (Fourth
Edition), 2022

Future directions
As polymer AM continues to grow and mature, sustained innovation in AM of
thermosetting polymers is likely, driven by these materials’ high-performance capa-
bility and the high resolution achievable by many thermoset AM methods. The new
knowledge and techniques detailed in this chapter are concentrated in the previous
decade, and only recently are being heavily transitioned into commercial applica-
tions. In this section the likely trends in growth that drive future efforts in research,
opportunities for new processing routes, and commercialization possibilities are
summarized. These estimates are extrapolated based on existing trends in research
and production, as well as gaps in the literature that are likely to be exploited by
researchers, designers, and manufacturers.

Large-scale printing. Many thermoset AM methods have evolved at the desktop scale;
however, many applications of thermosets require much larger prints. As the field
grows, new approaches to achieve larger structures are needed. ARE is an example
thermoset AM method where larger scale has been demonstrated [21], but much
more investigation is necessary to achieve a wide range of end-use structures.
Massivit 3D is an example of a large dimension [1.45 m (w) × 1.1 m (d) × 1.8 m (h)]
AM that dispense UV-cured polymeric gel, though this is only possible for hollow
structures [137]. Mammoth is a large-scale SLA with a resin bath dimension of
2.1 m (w) × 0.7 m (d) × 0.8 m (h) [138]. Future directions of research that would
enable large-scale thermoset AM include research in processing methods, design of
printed structures, and materials that are capable of being printed on larger scales
(e.g., self-supporting polymer networks for ARE). For parts in which the thermoset
polymer is only partially reacted, thermal management will become increasingly
important to avoid thermal runaway reactions in thick cross-sections, potential
thermal degradation of the polymer, and nonuniform thermal stresses.

Composites and multimaterial prints. Structural thermosets are primarily used as

the resin phase of composites; however, AM of composites remains a challenge
due to rheology, light diffraction, and thermal management issues, among other
considerations. Overcoming these challenges is likely to be a major future direction
in thermoset AM. MatEx processes are better suited to processing of high viscosity
liquids/pastes than vat photopolymerization, so one option may be re-formulation of
vat photopolymerization resins, including addition of secondary reinforcing phases,
for use in UV-DIW.

Multimaterial printing is available in only a few commercial printers, but is a frequent

request of industry researchers. Large challenges exist in adhesion between different
materials, different processing conditions, material delivery systems, and maintain-
ing throughput. However, thermosets are likely to play a substantial role in the
multimaterial AM revolution due to their chemical versatility, low initial viscosities,
and proven adhesion to materials from all other material families (e.g., metals,
ceramics, polymers, foams, and natural materials).

Hybrid printing. Increasingly, the drive to maximize conflicting manufacturing de-

mands, such as high throughput, larger areas, greater precision and accuracy, finer
feature sizes, and smoother surfaces, are resulting in hybrid AM techniques. Though
there is additional complexity required to manage multiple techniques in a single
print, this complexity is counteracted by the ability to offset disadvantages of one
technique with the advantages of a second technique. An existing example of this
hybrid AM is the use of SLS to create a metal component, onto which a thermoset
polymer is bonded and printed using stereolithography [127]. A number of machines
fusing traditional subtractive manufacturing with newer AM techniques are also
hitting the commercial market, further driving innovations in hybrid manufacturing.

Circular economy and safety. A circular economy is one where flows of materials,
products, and wastes form circular streams, in which material and products are
regenerated at their end of life to feed into new products. This circularity reduces the
intensity of resource usage, creation of waste, and impact on global natural systems.
AM has been touted for its potential to further circularity, with AM proponents
claiming only the material necessary for the printed part are used, and avoidance
of mold creation and other material and energy intensive processes. A recent study
showed that a significant progress has been done for compounding, feedstock,
and printing. A concept known as Distributed Recycling via AM (DRAM) has been
examined from six stages of chain such as recovery, preparation, compounding,
feedstock, printing, and quality [139]. A comprehensive literature study from 2009 to
2019 showed that significant progress has been made in compounding, feedstock,
printing, and quality stages, while only a few have addressed recovery and prepara-
tion.

However, many studies have produced equivocal results in achieving material and
energy savings by the use of AM. Moreover, thermosetting polymers add an addi-
tional layer of difficulty in supporting circularity goals. Whereas thermoplastic ma-
terials can be re-pelletized and melted as an addition to material streams, thermoset
materials typically form permanent cross-links that increase the difficulty in their
recycling. Traditionally thermosets have been incinerated for thermal (i.e., energy)
recovery; however, the primary value of the thermoset chemistry is destroyed and
results in low circularity. Issues with accelerated aging and excessive brittleness of
older photoinitiated resins used in PolyJet and in stereolithography AM techniques
also resulted in short product lifespans that produce waste and require new manu-
facture, both corresponding more to a traditional “linear economy” approach. New
technologies supporting the recycling, remanufacture, or regeneration of thermoset
resins, and which are already being investigated for thermoset applications in the
automotive, aerospace, and wind energy industries, may be adapted and ported
to the AM community. High-profile efforts in printing of thermoplastics waste in
military Forward Operating Bases or on naval vessels is an example of upcycling
food packaging or other waste streams for product creation. Recently thermoset
rubbers have been recycled as a latex material for inkjet printing [140]. Dynamic
“healable” PU compositions which can re-form at a later date are an approach
to maintain product lifespan and re-form the material into new products [132].
Another study has demonstrated reprogrammable epoxy for DLP by enabling a
two-step photopolymerization method [141]. Bio-sourced chemistries will increase
in importance as circularity principles drive a greater proportion of future business
decisions. For instance, a recent study has demonstrated recycling of a bio-based
epoxy composite as a thermoplastic filament for FFF [142].

AM is prized for its ability to bring manufacturing closer to the worker and, in the
most advanced situations, employees now have a desktop machine colocated in
their office space. However, the human health hazards and safety issues that have
traditionally been addressed in factories and other manufacturing environments
sometimes are not considered in this transition. Some of the thermoset chemistries
discussed in this chapter present substantial dermal contact, inhalation, and other
health hazards. Some studies on thermoset chemistries have demonstrated aquatic
toxicity when postcure is not properly performed. The principles of toxics use
reduction and hazard reduction advocates for developing formulations that are
inherently benign, or as benign as possible, rather than relying on engineering
controls (e.g., fume hoods, gloves and masks, waste disposal procedures). The best
practice approach requires researchers to consider from the initial stages of their
materials development and manufacturers in the establishment of their product
cycle how to minimize these hazards while meeting their engineering constraints.

Data, machine learning, and computational approaches. The combination of high-per-

formance materials and high resolution achievable in thermoset AM represents an
exciting opportunity. Combined with advancements in modeling and data science,
there is huge potential for hierarchical topology optimization and other types of
structural design to achieve systems with new combinations of properties. The
drive to multimaterial AM will require substantial modeling of the expected physics
during processing and in the final parts, and how the physical results relate to part
performance.

> Read full chapter

Trends in Polyolefin and Additive Use

Michael Tolinski, in Additives for Polyolefins, 2009

2.2 Overall Trends in Additives Production and Use

Because many polymer additives are likewise based on petrochemicals, additive use
and production is tied to oil prices as well. Additives are often more expensive than
the resins they are used in; yet these additives can provide synergistic value-added
functions to raw resin that offset their own costs. With the goal of increasing value
when loaded in polymers, recent overall trends indicate both lower loadings of
more-effective high-priced additives and higher loadings of low-cost additives, such
as fillers and reinforcements [2-13].

The use of polymer additives, of course, follows the growth of the polymers they are
used in. As with POs, the global growth rate of polymer additives varies by region,
with about 4% global growth, but 10% in China and 12% in India. Thus, additive
suppliers are consolidating and shifting operations to these regions. Also like POs
themselves, the consumption of PO additives, such as stabilizers, is growing faster
than with PVC additives. However, PVC still consumes by far the majority of all
polymer additives produced, since roughly 40% or more of most PVC grades are
plasticizers or other additives. In contrast, POs use about 10% of all plastics additives
produced [2-5, 2-11, 2-13]2-52-112-13.

Additives used at high volumes in POs and other polymers include inorganic fillers,
which make up over half the market share of polymer additives. The most-used fillers
are calcium carbonate (CaCO3), titanium dioxide, talc, and aluminum trihydrate
(ATH flame retardant). CaCO3 dominates as a plastics filler; in the United States, the
volume of CaCO3 for plastics in 2007 (1.7 million metric tons) reportedly outweighed
the volume of all other fillers combined, while ATH is the fastest-growing filler, with a
5.5%–7% annual growth rate (compared with other fillers growing at about 2%–5%).
Meanwhile, organic fillers and fibers, such as wood, given that their cost per pound
is about one-third that of PO resin, have been used in highly filled PO composites
for durable construction material applications [2-5, 2-12]2-52-12.

Inorganic fillers and reinforcements have relatively more stable prices that them-
selves are only indirectly connected to fossil-fuel prices. This allows them to act as
reliable hedges against raw resin price changes. Thus, PP compounds filled with talc
or glass fiber, for instance, only tend to track the price of propylene monomer (which
itself tracks with oil prices), rather than some wildly fluctuating filler price index
as well. Moreover, filler/fiber price relationships tend to be stable, with 30% glass
fiber-reinforced PP compounds tracking consistently at about $0.20/pound higher
than 20% talc-filled PP [2-3].

Performance additives such as antioxidants (AOs), heat and light stabilizers, antista-
tic agents, and other functional additives used at relatively low concentrations are
likewise growing, though at different rates. Given their high volumes and suscep-
tibility to oxidation, POs consume over half of all AOs used for plastics, with about
two-thirds of AOs used at primary resin producers and one-third by compounders.
For light stabilizers, over 60% are used by POs, 40% by PP alone, and over half are
added to resin by compounders. Light stabilizers, in particular, are growing faster
than fillers and other additives at over 7% per year [2-12, 2-13]2-122-13.

Additives are often integrated with resin by compounders and converters using
masterbatch concentrates. The masterbatch market for delivering colorants or other
additives is composed of color, additive, white and black masterbatches, roughly in
order of global market value. As with polymer additives, the highest growth rates
for masterbatch use are in Asia and Eastern Europe (10%–12%), with only slow 3%
growth in mature markets in North America and Western Europe, which already rely
heavily on masterbatches [2-12].

> Read full chapter

POLYMER ADDITIVES: SUPERCRITI-

CAL FLUID CHROMATOGRAPHY
T.P. Hunt, in Encyclopedia of Separation Science, 2000
Polymer Additives
The most common polymer additives are stabilizers, plasticizers, lubricants and
flame retardants. Stabilizers are added to prolong the useful life of a polymer
formulation by protecting it from thermal and light-assisted oxidation. This process
is caused by the formation in the polymer chain of free radical sites which can
react with oxygen to form unstable peroxy radicals and ultimately cause polymer
chain scission. Stabilizers are divided into four main classes: UV absorbers, primary
antioxidants, secondary antioxidants and quenchers.

UV absorbers such as benzophenones and triazoles screen the polymer from harmful
photons by absorbing them and then dissipating the excitation energy as heat so
there is no radical formation. Primary antioxidants are typically hindered phenols.
They react with free radicals to prevent further propagation. Secondary antioxidants
destroy the hydroperoxide sites on the polymer chain which could otherwise be
converted to peroxy radicals. They tend to be sulfur- or phosphorus-containing
compounds. Quenchers are usually organonickel compounds and their function is
to take over the energy absorbed by the chromophores in the polymer and dissipate
it as heat.

Lubricants are added to make the polymer easier to process by controlling the
melt rheology during thermoplastic moulding. They optimize the properties of the
finished article to create smooth and unblemished surfaces and minimize stress
fractures. External lubricants are compounds that are added to a polymer blend
to control the degree of adhesion and friction between the polymer melt and hot
processing equipment. Internal lubricants are added to polymer blends to reduce
the melt viscosity to facilitate lower processing temperatures and to improve heat
dissipation. Many lubricants posses a combination of internal and external char-
acteristics. Lubricants are typically fatty alcohols, acids and esters and hydrocarbon
waxes.

Plasticizers are high-boiling, organic chemicals which are often present at high
concentrations, solvating the polymer chains to form stable gels. As a result, in-
termolecular forces are reduced and this leads to a lower polymer glass transition
temperature. The polymer is consequently less brittle and more easily worked. Typ-
ical plasticizers are phthalates, adipates and polychlorinated hydrocarbons. Flame
retardants are typically chlorinated organophosphates.

It is evident then that a vast number of chemical species are used as polymer
additives. They have widely varying volatilities with molecular weights potentially
varying from 200 to 1000 Da. They tend to be of low to medium polarity and many
do not have UV chromophores. Polymer formulations contain unique combinations
of additives (called additive packages) which often contain 10 or more compounds.
Thus the identification and quantitation of these additive packages is a challenging
chromatographic problem.

> Read full chapter

Biopolymers for superhydrophobic

photocatalytic coatings
A.Z.M. Rus, in Biopolymers and Biotech Admixtures for Eco-Efficient Construction
Materials, 2016

18.5.1 Benefit of fillers for biopolymers

The global demand for fillers or reinforcing fillers, including calcium carbonate,
aluminium trihydrate, talc, kaolin, mica, wollastonite, glass fibre, aramid fibre,
carbon fibre and carbon black for the plastics industry is estimated about 15 million
tonnes (Xanthos, 2005). The primary end-use markets are construction, furniture,
packaging and automotive industrial. Automotive interior and underhood parts and
electrical connectors and microwaveable containers are examples of applications
requiring high-temperature resistance (Mahajan, 2003).

The term ‘functional filler’ is often used to describe materials that do more than
provide cost reduction. Examples of functional fillers include carbon black and
precipitated silica reinforcements in tyre treads, the role of stabilizers to reduce
in-process degradative effects, and many more miscellaneous additives for polymers
such as blowing agents, impact modifiers, lubricants or antimicrobials. Increased
polymer consumption over the past 20 years has not only stimulated developments
in manufacturing plants, but has also led to a parallel growth in the usage of a large
variety of liquid and solid modifiers, including fillers and reinforcements.

Fillers may be classified broadly as organic or inorganic substances, and further

subdivided according to chemical family as tabulated in Table 18.1. In a recent
review, more than 70 types of particulates or flakes and more than 15 types of fibres
of natural or synthetic origin have been used or evaluated as fillers in thermoplastics
and thermosets (Bierman, 1983).

Table 18.1. Chemical families of fillers for plastics (Mahajan, 2003)

Chemical family Examples

Inorganic
Oxides Glass (fibres, spheres, hollow spheres, flakes),
MgO, SiO2, Al2O3
Hydroxides Al(OH)3, Mg(OH)2
Salts CaCO3, BaSO4, CaSO4, phosphates
Silicates Talc, mica, kaolin, wollastonite, montmorillonite,
nanoclays, feldspar, asbestos
Metals Steel
Chemical elements Boron
Organic
Carbon, graphite Carbon fibres, graphite fibres and flakes, carbon
nanotubes, carbon black
Natural polymers Cellulose fibres, wood flour and fibres, flax, cot-
ton, sisal, starch
Synthetic polymers Polyamides, polyesters, aramid, polyvinyl alcohol
fibres

The classification of polymer additives is according to their primary function and a

plethora of additional functions. The scheme adopted by Xanthos involves classif-
ication of fillers according to five primary functions as shown in Table 18.4. From
the point of view of this research, TiO2 should be added as an optical agent. TiO2
has an important role as a (white) colourant in synthetic polymers such as poly(vinyl
chloride) which is used as a building material (windows, doors, fascia boards) and
polyethylene film (the familiar supermarket shopping bag material) (Kemp and
McIntyre, 2006).

• Fibrous fillersA search has been made for plant fibres with optimal material
properties for structural purposes in composite materials (Dahlke et al., 1998),
and the most well-known example of the use of a fibrous filler is in glass
fibre-reinforced plastic (GFRP) in which the synthetic polymer is most often
a polyester or a poly(vinyl ester), but other plastics, like epoxy (glass-reinforced
epoxy (GRE)), are also sometimes used. The use of natural fibres, such as
flax, hemp, sisal or yucca, is of increasing interest for various applications,
amongst them the automotive industries, in which the composites can be
used in door pockets, covers, instrument panels and sound insulation.In
addition, those fibres obtained from plants such as hemp, kenaf, sisal or
flax, when combined with suitable resins, can give cost-effective materials for
many applications. Physical methods include stretching, calendering, thermal
treatment and electronic discharge. Meanwhile, chemical methods include
alkali treatment, treatment with compatibilizers and other coupling agents.
Plant fibres are known to have very high strength and can be effectively utilized
for many load-bearing applications. A comparative study between different
types of natural fibre–polyester resin composites on the basis of strength and
cost has been reported (Bledzki and Gassan, 1999) and the addition of such
fillers to composites is made for technical and economic reasons.
• Particulate fillersThe most widely used mineral particulate fillers in polymer
composites are calcium carbonate CaCO3 (as chalk or limestone), china clay,
mica, microspheres, silica and talc. New organic fillers have also entered
commercial markets, including corn cobs, flour fillers etc. Similarly, newly
developed ceramic microspheres and their metal-coated forms have recently •
found application in aerospace and conductive plastics (Ray et al., 2002).-
Inorganic materials are very attractive because they have the advantages of
high mechanical strength, good chemical resistance, thermal stability or en-
hanced optical properties. As inorganic fillers, a range of different metal-oxide
particles can be dispersed into the polymeric matrix (Schmidt et al., 2000).
Examples of inorganic pigments include titanium dioxide, iron oxides and zinc
chromate. As a practical matter, the particle size of the particulate materials
should not be greater than 1 mm, and preferably from 0.1 to 500 μm (Cho
et al., 2005).
Nanocomposite fillersA growing interest in polymer material has been in
polymer nanocomposites. Polymer nanocomposites are a mixture of organic
polymer matrix and nanoscale fillers. The advantages in the application of
these polymer nanocomposites in automotive parts are their greater stiffness,
saving of weight, improved surface quality, less brittleness at low temperatures
and being easily recyclable (Harris, 2003).For structural applications, compos-
ites have become very popular and are sold in billion pound quantities because
these composites, compared to neat resins, show improved properties includ-
ing tensile strength, heat distortion temperature and modulus. Clearly, the
idea of adding fillers to thermoplastics and thermosets to improve properties,
and in some cases to decrease costs, has been very successful for many years.

> Read full chapter

Electrical Conductivity Behavior of

Biopolymer Composites
H.S. Abdo, ... K.A. Khalil, in Biopolymer Composites in Electronics, 2017

3.1 Pure PPy Polymer

The preparation process and polymer additives affect strongly the electronic con-
ductivity of PPy, which is prepared chemically in aquatic solution. In addition, some
of recent researches illustrate that the use of polymers could control the electrical
conductivity by sterical stabilization of PPy chains [25]. To achieve this target, water
soluble polymers which have molecular mass more than 22,000 g/mol such as PVAc,
methyl cellulose, PEO, poly(2vinylpyridine), PVP, poly(vinylmethylether), and others
were studied by Rodriguez et al. [26]. They found that, by using those additives,
electrical conductivity of a wide range 10−9 : 10−12 S/cm can be achieved [26]. Spe-
cially, for polyethylene-oxide (PEO) with a molar mass of 131,000 g/mol an electrical
conductivity of 2.1 × 10−3 S/cm was achieved [27–31].

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Applications of Processing Aid Addi-

tives
Sina Ebnesajjad PhD, President, Richard A. Morgan PhD, President, in Fluoropoly-
mer Additives, 2012

11.2.3 Advantages of PPAs

1. Melt Fracture ReductionPPAs enable polymers to be processed (e.g., extruded)
at higher shear rates without the melt fracture (surface roughness/shark skin
effect) that may occur with untreated polymer melts. The addition of process
aids results in good-quality products that are produced at higher output rates.
2. Reduced Die Buildup, Die Drool, and Gel FormationDuring processing, de-
posits of low-MW polymer, additives, and degradation products can build
up on the die and extruder surfaces. Such deposits can create die lines and,
when/if they are released, defects on the extrudate. A process aid is able to re-
duce die buildup because, as the coating layer develops, any degraded material
clinging to the die is displaced and also stagnation in the extrusion process is
minimized, reducing the production of thermal degradation products.A more
recently discovered benefit of PPAs is the prevention of gel formation, for
which various mechanisms have been proposed [1,2]. The low-energy surface
provided by the coating reduces internal buildup and subsequent degradation,
leading to crosslinked and oxidized gels. Reducing unmelted/unmixed gels
is believed to be related to the prevention of solid bed breakup and the
process aid may prevent premature melting in the feed section, thus helping
to maintain a coherent solid bed [3].
3. Process Efficiency ImprovementsThe use of a PPA reduces resistance be-
tween the polymer melt and the die, resulting in die pressure and motor torque
falling. If process temperature and outputs are kept constant, process aids
can reduce motor energy consumption, whereas if process temperature and
extrusion pressures are kept constant, higher outputs can be achieved. As a
result of process aids reducing die buildup, the extruder does not need to be
stopped frequently during production to clean such deposits, thus limiting the
downtime. Industrial trials have also found reductions in the time for color or
resin changes to be completed.
 4. Recycling PlasticsPPAs can help reduce extruder pressure when processing
blends of polymers, such as LLDPE with LDPE and LDPE with HDPE. While
this does not solve incompatibility issues, it can increase processing flexibili-
ty/options.

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