Journal of Cleaner Production 229 (2019) 1397e1411

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Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

Green-PVC with full recycled industrial waste and renewably sourced

content
Carlos Alberto Correa a, *, Cristiano Ribeiro de Santi b, Andre

Leclerc c
a
Universidade Federal Do ABC, Núcleo Estrat
~o de Resíduos - REVALORES, Campus Santo Andr

egico de Revalorizaça e, SP, Brazil
b ~o Carlos, Programa de Po
Universidade Federal de Sa
s-Graduaça ~o Em Ci^
encia e Engenharia de Materiais, Campus Sa~o Carlos, SP, Brazil
c
ADM e Archer, Daniels Midland Company, Amidons Industrielles, Industrial Starches, NE, Canada

a r t i c l e i n f o a b s t r a c t

Article history: Polyvinyl Chloride (PVC) resins and their compounds are very versatile materials with applications
Received 27 December 2018 ranging from flexible packaging to rigid building products, such as extruded pipes, profiles and injection
Received in revised form moulded electrical/plumbing fittings. Nowadays, large amounts of industrial waste resulting from PVC
25 March 2019
processing must be handled in order to comply with enacted environmental and health hazards legis-
Accepted 28 April 2019
Available online 7 May 2019
lations concerning plastic waste disposal. Nonetheless, provided the waste contamination is controlled at
its source, PVC waste is potentially recyclable and can be compounded with thermoplastic starches
leading to reprocessed formulations with renewable content. These formulations can be reengineered
Keywords:
PVC waste
onto injection moulded appliances within a closed-loop manufacturing framework. Starches can be
Thermoplastic starch gelatinized by heat, pressure and shearing with glycerol, and in the present work, a by-product of the
Closed-loop manufacturing biodiesel manufacturing was used for this purpose. The main aspects related to cascaded recycling of PVC
Eco-innovation waste from pipe processors are discussed, in regard to challenges for developing alternative green
Waste reduction markets for plastic products in terms of recycling technology and properties compliance for using
reprocessed plastic plumbing waste on electrical fittings. Coping with hygroscopic nature of glycerol
plasticized starch was the main challenge and many bioderived plasticizers have been tested to over-
come this drawback. The research on Green PVC implied that eco-innovation in the conventional plastic
industry requires “drop-in” solution regardless of their renewably or fossil sourced feedstock. Further-
more, the green value is not clearly perceived as marketing advantage by plastic processors and con-
sumers and a green-premium associated with production costs tend to hinder a pervading market.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction
Owing to a well-balanced combination of lightness, low cost and
versatility the global production of plastics has grown exponen-
tially in the last decades, reaching about 300 million metric tonnes
in 2013 (Plastics Europe, 2015). The well-known plastic commod-
ities, polyolefins (polyethylene and polypropylene, styrenic plastics
Abbreviations: DJSIE, Dow Jones Sustainability Index Europe; EDC, Ethylene
DiChloride (EDC); ECHA, European Chemicals Agency; DOP, Di-Octyl-Phthalate;
MVC, Monomer Vinyl Chloride; PVC, Poly (Vinyl Chloride); REACH, Registration,
Evaluation, Authorization, and Restriction of Chemicals; TPS, Thermoplastic Starch.
* Corresponding author.
E-mail addresses: carlos.correa@ufabc.edu.br (C.A. Correa), crsanti@uol.com.br
(C.R. de Santi), Andre.leclerc@adm.com (A. Leclerc).
URL: http://www.ufabc.edu.br, http://www.ppgcem.ufscar.br, http://www.adm.
com
(PS, EPS and HIPS), vinyl plastics such as Polyvinyl Chloride (PVC)
and Polyethylene Terephthalate (PET) represent the major part in
the market, with more than 70% destined to packaging applications
(Ellen MacArthur, 2016, 2017). In regard to PVC resins, the use of
plasticizers and mineral fillers yield an even broader range of ap-
plications in products such as laminated films, blow moulded
bottles, flexible and rigid pipes, connectors, profiles and extruded
sheets for thermoforming and building products application.
Owing to its extreme versatility the global production of PVC
resins is currently within the top three commodities, bellow poly-
olefins only. PVC market is expected to reach installed capacity of
about 60 million tonnes by 2020 with almost ¾ of the production
destined to applications in building products such as plastic pipes,
electrical and plumbing fittings. The PVC value chain itself is very
complex, encompassing petrochemical feedstock producers, addi-
tives and filler suppliers, processors (equipment and tools), re-
tailers, consumers (Fig. 1).

https://doi.org/10.1016/j.jclepro.2019.04.383
0959-6526/© 2019 Elsevier Ltd. All rights reserved.
1398 C.A. Correa et al. / Journal of Cleaner Production 229 (2019) 1397e1411
Fig. 1. The PVC value chain from cradle-to-grave.
On the other hand, this huge volume of plastic products along
with the littering of post-consumer waste is causing widespread
environmental problems to the point that waste managing policies
have been pointed out by United Nations as a top priority to be
addressed by governments around the world. In Brazil, the solid
waste management bill enacted in 2010, is mostly concerned with
reduction, reuse, and recycling of solid waste. Data from ABRELPE, a
Brazilian Institute pro-municipal waste management, recorded 71.6
million tonnes collected in 2017 considering a covered area of
91.2%. Over this amount, 6.9 million tonnes was presumed leaked
into the environment without formal collection.
Reducing environmental impact of plastics has also been
considered through some technological routes aimed to reduce
greenhouse gas emissions, by decoupling its sourcing from fossil
fuel feedstocks (Petroleum). For instance, the bioethanol from
sugarcane has been used successfully in the manufacturing of green
polyethylene by Braskem (Pinto et al., 2012), while polysaccharides
alternative routes (starches), such as thermoplastic starches (TPS)
and Poly Lactic Acid (PLA) obtained from corn crops are mostly used
in North America and Europe (Shen et al., 2009).
1.1. The PVC market
Braskem the largest manufacturer of thermoplastic resins in
South America argues that PVC is not 100% originated from pe-
troleum, once its 57% weight is comprised of chlorine molecules
sourced from marine salt. Furthermore, besides this unique feature
of PVC based resins, as a thermoplastic, PVC can be primarily
recycled by means of conventional processing equipment (Rodolfo
et al., 2006). On the other hand, PVC is a high energy demanding
material for manufacturing of its basic products, makes use of
hazardous heat stabilizers containing cadmium and lead, as well as
phthalic plasticizers which are being banned around the world for
many applications. Today, there is not a sustainable alternative
route for recycling PVC waste and its inadequate dumping in
landfills may contaminate the ground water with leaking chem-
icals, and its incineration may release chlorine and dioxins on the
atmosphere.
PVC waste are 100% recyclable depending only upon an effective
collection to prevent contamination. However, in the case of post-
consumer municipal waste in large urban areas, recycling repre-
sents only 15e20% of the collected waste, and the major volume is
dumped into public landfills or leaked direct into the environment.
The present manuscript is focused on industrial waste from PVC
pipe manufacturing, which the most relevant types for the present
work are described according to their physical characteristics as
follows.
1.2. PVC industrial waste from pipe manufacturing
In the pipe and fittings manufacturing, a PVC powder resin
(50e200 mm) is dry blended with additives and fillers in intensive
mixers and further compounded by melt processing either through
injection moulding or extrusion. Typically, these PVC dryblend
formulations for pipe and fittings application contain high levels of
mineral fillers to account for the end-product strength and stiffness
(usually up to 50phr of calcium carbonate, CaCO3).
However during the melt compounding to the end-product,
there are undesirable waste generation in several steps of the
processing. For instance, at the intensive mixers there are micro
particles leaking resulting from suspension and powder degassing
under 30 mm. During the extrusion process, waste is also generated
in the form of “molten lumps” when exchanging formulations and
extruder purging. Disposal of non-complied fittings is also a source
of waste. As though as in many other industrial processes, in the
pipe and fittings manufacturing, waste generation must be reduced
and handled properly to avoid environmental problems, particu-
larly those related to micro plastics leaking.
In regard to occupation health, PVC processors pursue compli-
ance to ISO 14.001 and OHSAS 18.001 standards concerning clean
 C.A. Correa et al. / Journal of Cleaner Production 229 (2019) 1397e1411
manufacturing, aiming international recognition in terms of envi-
ronmental compliance. Accordingly, waste management is one of
the issues which is currently rising to the top of the agenda of many
plastic processors, as they have become more mindful of the
environmental impact of their industrial activities, and their need
to reduce, reuse or cascaded recycling products and manufacturing
waste.
Besides the degassing powder waste and non-complied pipe
fittings, there are two other relevant waste types, the extrusion
purge and chips from pipe sawing operations. The extrusion purge
has a very heterogeneous chemical composition and high levels of
contaminants while the chips are very light and fluffy. Both are
hard to be reprocessed and are refused by recyclers as having low or
almost no market value. The total amount of PVC pipe and fittings
waste from the company Amanco Inc. in Brazil was estimated at
approximately 500 tonnes/month (Danella, 2009).
The most relevant PVC pipe waste characteristics are described
as follows and depicted in Fig. 2:
1.2.1. Chips from pipe sawing
Chips waste comes out from sawing standard 6 m length pipes.
The chemical composition of this waste is a standard PVC pipe
formulation.
1.2.2. Extrusion purged waste
The purged waste is generated when different formulations in
terms of color and chemical composition are exchanged and the
extruder is cleaned with purging resins. When a new formulation is
loaded the extruder must be purged and cleaned. The cleansing
agents are usually high stabilized PVC masterbatches which are
discharged by the extruder as lump shapes. Once cooled, these
lumps can be stored as such or ground to be stored as a powder.
1.2.3. PVC degassing powder waste
Along with the extrusion purge waste, the degassing powder is
the largest volume waste generated during the compound prepa-
ration at the intensive mixers or from the powder exhaustion
system at the extruder hopper. During batch preparation, an
Fig. 2. Types of PVC pipe waste. (a) Chips from pipe sawing; (b) Extrusion purged waste; (c) PVC degassing powder waste.
1399
exhaustion system filters and removes the finer portions. These
fines are drifted away through a pipe system and stored tempo-
rarily before storage in big bags for commercialization. The
degassing powder poses a great challenge for reprocessing once
they are extremely fine (lower than 30 mm), and is very heteroge-
neous, particularly in regard to the proportion of PVC resin to cal-
cium carbonate. Moreover, many recycling companies are not
interested in PVC degassing powders, once it cannot be recycled
efficiently and economically (as opposed to non-complied recycling
plumbing fittings which find their way very easily into the recycling
market. As though, degassing powders are prone to end up in
public landfills if companies cannot find their way for a proper
waste disposal. These days, degassing powder waste represents
approximately 1e2% of the overall output waste of PVC pipe pro-
cessors operating in Brazil, which is about 200 tonnes per month.
Commercial PVC formulations are required to be thermally
stabilized and plasticizers are used for processing and provide
controlled rheology for target product applications. Low thermal
stability and extensive use of additives in the formulation may also
hinder PVC reprocessing. Among the additives which are consid-
ered as “health and environmental hazards” there are lead base
stabilizers and some phthalic plasticizers. Nonetheless, although
many countries are imposing severe environmental legislations to
vinyl plastics disposal, in many parts of the world such chemicals
remain in use without restrictions owing to increasing global de-
mand for such resins. Nonetheless, a general trend towards phasing
out hazardous chemicals is taking place worldwide, in the last two
decades (Eliason et al., 2007; Lithner et al., 2011).
Recycling of PVC waste may attract growing interest if their
formulations pose low hazard and renewables are employed as
chemical additives. Some examples already in use by industries are
epoxidized soya oil (ESO) and glycerol, as PVC and starch plasti-
cizers, respectively. In this regard, recycled PVC formulations con-
taining renewable feedstock additives may help to reduce
environmental impact related to PVC disposal, and for this reason
they are being referred to as more sustainable solutions. They
encompass not only reprocessed PVC compounds with renewable
content but also the base polymer resins obtained from sugar cane
1400 C.A. Correa et al. / Journal of Cleaner Production 229 (2019) 1397e1411
ethanol (Madaleno, 2007).
1.3. Biobased plastics e thermoplastic starches (TPS)
Biobased plastics are materials obtained from renewable feed-
stock, mostly biomass of vegetal or animal sources. Owing to
environmental concern on non-renewable fossil feedstock, biomass
has become a major source of chemical building block for plastics.
Recent data released by Nova Institute (Ellen MacArthur, 2017) has
shown that bioplastics global production has reached about 2.05
million tonnes in 2017; with a market share of 57.1% bio-based/
non-biodegradable and 42.9% biodegradable. Accordingly, the
most relevant bioplastics in terms of market share are Bio-PET
(26.3%), thermoplastic starch blends (18.8%), Polyamides (11.9%),
PLA Poly Lactic Acid (10.3%) and Green Polyethylene (9.7%).
Nonetheless, these figures correspond to less than 1% of the
global installed capacity of commercial plastics which includes not
only bioplastics from renewable sources but also biodegradable
plastics from fossil feedstock (mostly petrochemical polyesters).
Notwithstanding their still small production capacities worldwide,
the emerging biobased plastic market has gained momentum over
the last two decades, has made impressive strides towards
improved performance and has pervaded consumer awareness
over green products.
Starch, cellulose and glycogen are polysaccharides which are
comprised of two glucose (sugar) molecules; a linear structure
named amylose and a branched one, amylopectin. In the most
typical starches, the weigh fractions of amylose range between 72
and 82% and 18e28% of amylopectin, although in genetically
modified species these proportions may vary substantially.
In technological terms, the conversion of native in thermoplastic
starches requires desestructuring1 or partial fragmentation of the
characteristic crystalline structure of the polysaccharides. During
the conversion, native starches are transformed in amorphous
thermoplastics, which can be processed like any other thermo-
plastic by means of applied heat, shear and pressure. Consequently,
native starches can be destructured in co-rotating twin-screw ex-
truders by controlled addition of plasticizers such as water or
glycerin and well defined operational parameters, (Hongsheng
et al., 2009; Liu et al., 2001; Willet et al., 1995).
In twin screw extruders the shear level is controlled by the
screw profile. The presence of kneading blocks generates high
levels of pressure, shear gradient and adiabatic heat required for
occurrence of physical-chemical transformation of starches. In the
twin screw extruder, the destructuring of the starch is based on the
penetration of the plasticizers in its structure producing an irre-
versible swelling under mechanical loading and heat. As though,
destructuring and fragmentation of starch particles takes place by
intensive shearing and high levels of heat dissipation as a result of
the destructuring of spherulitic structures through fragmentation
of primary and secondary chemical bonds, as well as the hydrogen
bonds responsible for stabilization of amylose helices (Wiedmann
and Strobel, 1991; Aichholzer and Fritz, 1998; Gonzalez et al., 2006).
Starches cannot be destructured or gelatinized without a plas-
ticizer or gelatinization agent once its decomposition temperature
is lower than its melt temperature before gelatinization. For this
reason, many plasticizers have been tested to evaluate the effi-
ciency of the gelatinizing process during melt processing, including
water, polyols derivatives, glycerol, glycol and sorbitol (Da Roz et al.,
2006; Hulleman et al., 1998).
1
In the literature destructuring is used interchangeably with gelatinization or
plasticizing.
Fig. 3. Biodiesel production by transesterification reaction (Sourced from www.
biodieselbr.com.br).
1.4. Biodiesel glycerol waste
Biodiesel is a mixture of fatty esters resulting from the trans-
esterification reaction of any source of triglycerides with an alcohol
as methanol. The global production of biodiesel was estimated at 12
million metric tonnes in 2007, (Osaki and Batalha, 2008). European
countries were the first to start producing and trading biodiesel
globally; Germany is the main producer, followed by France and
Italy (Fig. 3).
Glycerol or glycerin are typical names for the 1,2,3-propanotriol.
Glycerin is mostly used to refer to the end-product at the retailer
consisting of a 50e90% aqueous solution of 1,2,3 propanotriol while
the name glycerol is used for the pure 1,2,3-propanotriol. Besides
its petrochemical route, glycerol is also the main by-product of the
biodiesel manufacturing and for every 100 tonnes of biodiesel
produced 10 tonnes of crude glycerol are generated as waste.
Crude glycerol may present varying glycerol content, with levels
below 30% are very common. The “blond glycerol” from biodiesel
presents levels of glycerol within a range of 80% and is regarded as a
low value waste in the marketplace due to its abundance and low
quality. It is also used as a source of energy by producers in the
mills. Glycerol reprocessing has great importance for many indus-
trial sectors and market prices may vary broadly depending on the
glycerol content.
According to local market surveys, biodiesel industry in Brazil
produces 330 million liters of crude glycerol which correspond to
approximately 10% of the whole biodiesel processed in the country.
Crude glycerol contains large amounts of impurities (water, salts,
catalyst traces, methanol and even biodiesel), and consequently it
has limited use for the main consumer market, pharmaceutical
industry, cosmetics and food. As though, reprocessing of crude
glycerol may add value to the biodiesel process and is considered as
a challenge to improve biodiesel competitiveness in respect to
petroleum diesel (Rivaldi et al., 2003).
Another important and exclusive market is the use of glycerol in
the synthesis of high value feedstocks. For instance, the PDO
(propanediol) from fermentation of glycerol, can be used as
building blocks for plastics, and is being considered as a biobased
route for production of 1,3 propanediol and di-hydroxy ketone. The
potential use of blonde glycerol as plasticizer for thermoplastic
starches and its further melt compounding with reprocessed PVC
was the base for development of the concept of sustainable Green-
PVC, as described further.
1.5. The green PVC approach within the circular economy
proposition
The idea of a circular economy has its theoretical foundations in
the field of industrial ecology developed in the early 1990s and was
based on the concept of industrial metabolism as a whole
 C.A. Correa et al. / Journal of Cleaner Production 229 (2019) 1397e1411
integrated collection of physical processes that convert raw mate-
rials; energy and labour into finish products and wastes in a (more
or less) steady-state condition (Bocken et al., 2016).
The concept of circular economy still lacks of a commonly
accepted terminology and its definition may sometimes be subject
of disputes by different authors, depending on their research field.
As though, terms such as closed-loop economy or zero-waste
economy are often used as synonymous of circular economy,
which could also be related to other derived concepts such as green
supply chain management, performance economy, cradle-to-cradle
and industrial symbiosis. The following definitions of circular
economy were compiled in the literature reviewed by Kalmykova
et al. (2018):
- An industrial economy in which material flows keep circulating
at high rate without entering the biosphere unless they are
biological nutrients;
- An industrial economy that's restorative by intention, aims to
rely on renewable energy; minimizes tracks and eliminate the
use of toxic chemicals, and eradicates waste through careful
design;
- An economy that provides multiple value creation mechanisms
which are decoupled from the consumption of finite resources;
in a circular economy, growth comes from “within” by
increasing the value derived from existing economic structures,
products and materials
The importance of closed-loop systems in a cradle-to-cradle
(circular) rather than cradle-to-grave (linear) economy was recog-
nized by McDonough and Braungart (2002) and is well represented
by a closed-loop diagram of resource flows through a value chain in
a circular economy represented by materials sourcing, design,
Fig. 4. The Green-PVC concept. (For interpretation of the references to color in this
figure legend, the reader is referred to the Web version of this article.)
Table 1
Raw-materials and suppliers.
Material Code
PVC recycled r-PVC
Regular starch RS
Glycerol CG
Thermal stabilizer CZ1820
Epoxidized soybean oils ESO
Lubrificant TR251/TR016
Plasticizer DOP
1401
manufacturing, distribution and sales, consumption and use,
collection and disposal, recycling and recovery, remanufacturing
and circular inputs (Kalmykova et al. (2018). These are the basic
elements taken into account on the design of the Green-PVC, which
besides its biobased content is within the scope of drastically
reduce the disposal of plastic waste by recovery, recycling and reuse
plastic waste within a closed-loop manufacturing system.
Furthermore, the relevance of using renewable feedstock as ma-
terials sourcing for development of biobased plastic within the
circular economy proposition is highlighted in recent reports by
Ellen MacArthur (2013, 2017).
Starches, as a renewably sourced feedstock for plastics, have
been used as inert fillers in PVC, and blended with polyolefins,
styrenics and some biodegradable plastics for biodegradable
packaging. Three major techniques involve starch co-precipitation
in a PVC latex followed by film calendering. It can also be dry-
blended with PVC resin and additives followed by melt com-
pounding or calendering before moulding. In all cases mechanical
strength remains high for starch content up to 50% wt. despite of
loss in ductility. Calendered films tested for biodegradability were
considered 60e100% biodegradable according to ASTM D-1924-70
(Whistler et al., 1984).
Alternatively, the proposed Green PVC approach (Fig. 4) is based
upon 100% PVC waste from pipe industry containing about 21% wt.
of a glycerol plasticized starch. The reprocessed PVC dryblend is
melt compounded with the thermoplastic starch in a two-step
process for a fine dispersion of the starch into the vinyl matrix.
The Green PVC approach is also in line with circular economy
principles as proposed by United Nations SDGs 15 (Sustainable
Development Goals), and current literature on practices and stra-
tegies for its implementation (Kalmykova et al., 2018; Oliveira et al.,
2018; Ellen MacArthur Foundation, 2013). It was initially designed
for applications in injection moulded electrical appliances whose
certified materials may find their way into a thriving green building
market. Consequently, green-PVC was designed as a market-push
technology which requires incremental strides to percolate and
prevail as a full sustainable eco-business proposition.
In a nutshell, the Green-PVC concept was focused on develop-
ment of new technological strategies to improve recovery and reuse
of bioenergy and industrial plastic waste, and at the same time
minimize dependence on fossil resources by its gradual replace-
ment with renewable feedstock.
2. Materials and methods
The Green PVC formulations were developed using PVC pipe
waste supplied by the company Amanco do Brasil, the natural
starch was supplied by CASCO e Canadian Starch Company and its
Brazilian subsidiary Corn Products do Brazil. The “blond glycerol”
used on starch gelatinization was collected at the Brazilian bio-
diesel mill Granol. The basic ingredients used in Green-PVC
Characteristics Supplier
Waste (pipe) Amanco/Brazil
AMIDEX 3001 Corn Products do Brazil
Blonde glycerol (max 85%, 11%water) Granol Mills, Brazil
Ca/Zn Baerlocher
Drapex 6.8 Inbra Inds. Químicas Ltda/Brazil
Scandiflex SP22
Nexoleum
Fatty acids and stearic acid Struktol/USA
Di-Octyl-Phthalate Replas do Brazil
1402 C.A. Correa et al. / Journal of Cleaner Production 229 (2019) 1397e1411

Table 2 2.3. Preparation of the recycled PVC dryblend

Green PVC basic formulations.

Ingredient Phr wt. % The formulation of the recycled PVC dryblend is prepared by
Recycled PVC 100 70.67
sieving and homogenizing the pipe waste powder, for further
Regular Starch 21 14.84 mixing with additives such as heat stabilizer, plasticizer and
Glycerol 9 6.36 lubricant in a High Speed Blender (HSB). A HSB with batch capacity
Plasticizer e DOP and ESOs 10 7.07 of 100 kg, was used for the preparation of the recycled PVC dry-
Lubricant 0.5 0.35
blend. The ingredients were loaded in sequence with time spans of
Heat stabilizer 1.0 0.71
15 s at maximum rotation for each ingredient. The resulting
formulation is regarded as the PVC dry-blend which is ready for
melt processing.
formulations are listed in Table 1.
Best formulations for testing as injection moulded appliances
consisted of 70.67% wt. of recycled PVC, 21% wt. glycerol plasticized 2.4. Green PVC processing - PVC/TPS melt compounding
starch (starch þ glycerol) and 17% wt. of the plasticizers plus ad-
ditives, according to Table 2. The preparation of the Green PVC was carried out using a two-
step process consisted of glycerol starch gelatinization followed by
thermoplastic starch melt compounding with the reprocessed PVC
2.1. Compounding PVC/Starch formulations dryblend as sketched in Fig. 6.
The thermoplastic starch was melt compounded with the PVC
Definition of a processing protocol was the bottle neck to ach- dryblend in a twin-screw extruder Coperion STS35-44D using the
ieve a fine dispersion of the thermoplastic starch on the reproc- screw profile and temperature range as shown below:
essed PVC matrix, once a good performance of the resulting Screw profile depicting conveying (green) and kneading blocks
compound in terms of rheology and mechanical strength depends (blue) zones. Feeding and degassing zones indicated by red and
on a combination of efficiency of melt compounding and a good blue arrows, respectively.
interaction between polar groups in the vinyl and starch phases.
The G-PVC compounding was carried out in two-steps, as follows:

A. Melt compounding of the thermoplastic starch by means of Barrel zones temperatures

gelatinization of the natural starch with glycerol in a twin-screw Zones Z1 Z2 Z3 Z4 Z5 Z6 Z7 Z8 Z9 Z10
extruder. Temp. 170 170 170 170 170 175 175 175 175 180
o
B. Blend compounding of the thermoplastic starch with PVC waste C
by twin screw extruder

2.5. Specimen preparation and testing protocols

2.2. Gelatinization of the natural starch with glycerol Dumbell specimens were injection moulded for tensile testing
according to ASTM D638 and rectangular bars were moulded for
The processing trials started off using 80%wt. glycerol content in testing of structural stability and Heat Distortion Temperature un-
the blonde glycerol but difficulties in pellet granulation was caused der Load (ASTM D648/ISO 75e1). The samples were also tested for
by an excess in moisture. Therefore, the moisture content in the other relevant properties for electrical applications, such as
blonde glycerol was adjusted to approximately 11% for a continuous dielectric strength at 60% and 93% relative humidity; mass loss in
smooth granulation. The starch/glycerol/calcium stearate weight air forced oven (ASTM D2288-97); water absorption at varying
ratio was set according to values depicted in Table 3. moisture levels, and UL flammability testing, as further described in
The thermoplastic starch was processed in a co-rotational twin- more details.
screw extruder (72 mm e L/D ¼ 40) equipped with a side feeder for
glycerol uploading and details of the TPS compounding is shown in
Fig. 5. 2.5.1. HDT/DTUL e heat distortion temperature or deflection
To avoid starch degradation, the maximum temperature on the temperature under load)
heating zones was set to 120  C according to the following tem- Testing protocols followed standard ISO 75e1 e ASTM D648. As
perature profile along the extruder barrel: shown in Fig. 7 specimens are tested in three point bending in order
to produce flexural nominal stresses (Method A: s ¼ 1,90 MPa;
Method B: s ¼ 0,45 MPa and Method C: s ¼ 8 MPa. Specimens are
tested immersed in silicone oil and temperature is raised at a
Zones 01 02 03 04 05 06 07 08 09 Die
controlled heating rate of 120  C ± 10  C/h. The temperature at
o
which 0.2% deflection occurs (0.25 mm for ASTM, 0.32 mm for ISO
Temp. C 50 110 115 120 120 120 120 120 120 120
flatwise, and 0.34 mm for ISO edgewise) is assigned the material

Table 3
Thermoplastic starch formulations.

Material % Glycerol feeding rate (125 kg/h) after moisture correction

Regular starch 69 98,31 kg/h

Blond Glycerol* 30 41,67 kg/h
Calcium stearate 1 1,25 kg/h

*Moisture content: 11% and ** Glycerol content: 90%.

 C.A. Correa et al. / Journal of Cleaner Production 229 (2019) 1397e1411
Fig. 5. (aeb) Details of the starch glycerol plasticizing process on the twin screw extruder. (c) Classified TPS pellets e (d) TPS pellets out of specification.
Fig. 6. Schematic diagram showing preparation of Green-PVC by two-step process.
Heat Distortion Temperature (HDT), an important reference for
temperature limitations of the material structural stability.
The tests were carried out in a Tinus Olsen equipment with
three platforms for simultaneous testing. Recycled PVC specimens
without glycerol and Green-PVC were tested in flatwise ISO using
80 mm  10 mm x 4 mm bars. The HDT tests were performed to
evaluate the effect of the plasticizers DOP (Di-octyl phthalate) and
ESO (Epoxidized Soya Oil) in samples with and without glycerol. A
standard PVC formulation used in the injection moulded of elec-
trical parts by the market was also tested as reference.
2.5.2. Water absorption
Any starch based plastics product should be tested for its hy-
groscopic nature, particularly when vegetal plasticizers are used on
the formulation. As though, the water absorption tests were carried
out comparatively for recycled PVC with and without glycerol and
for Green PVC plasticized with DOP and ESO at controlled levels of
humidity.
1403
The test consists of placing 20  10mm specimens inside tight
closed flasks containing saturated solutions of different salts which
allow simulation of varying humidity ranges between 11 and 90%
(Table 4). Flasks containing immersed samples were stored for a
period of 4 weeks and samples weighted after equilibrium was
attained.
2.5.3. Mass loss in oven at 110  C
The test method is based on ASTM D2288-97 and is recom-
mended for evaluating plasticizers volatility in PVC samples under
heat. Testing specimens were taken from injection moulded sam-
ples which were weighted after 48 h under air circulating oven to
compare the initial and final weight after conditioned.
2.5.4. Dielectric strength
Electrical appliances must comply with ABNT - Brazilian Stan-
dards with dielectric strength one of the most important properties
for safety and prevention of electrical shock. As though, injection
moulded parts of commercial PVC, recycled PVC and Green PVC
were tested for dielectric strength according to the standard ASTM
D-149a - Dielectric Breakdown Voltage and Dielectric Strength of Solid
Electrical Insulating Materials at Commercial Power Frequencies. The
tests were carried out at 60% and 93%RU, whereas test voltages
varied within the range of 100e5000 V.
A. Test Pre-Set
A. 1 Test run at 60 Hz (commercial frequency)
A. 2 Voltage gradual increase for 10 s until test voltage is
achieved
A. 3 Electrodes fixing on both sides of the specimen
B. Specimen Conditioning
The specimens were conditioned at 25  C/60%RH for 24 h and at
25  C/93%RH for 48 h.
2.5.5. Flammability test
UL testing standards (Underwriters Laboratories, USA) are
worldwide accepted for by the electrical and electronics industry
1404 C.A. Correa et al. / Journal of Cleaner Production 229 (2019) 1397e1411
Fig. 7. Illustration of the Tinus Olsen equipment assembling for HDT testing according to ISO 75e1 (flatwise).
Table 4
Relative humidity of saturated salt solutions at 23  C.
Saturated salt solution Relative humidity (%)
LiCl 11
MgCl2 33
NaBr 58
NaCl 75
BaCl2 90
for evaluation of materials self-extinguish capacity and resistance
to fire propagation. Accordingly, there are many classifications
which are based upon velocity of combustion, time for flame
extinction, dripping resistance capacity and if dripping in flame will
propagate to the cotton positioned under the sample.
The tested formulation will be classified according to its color
and/or thickness. Usually the material specification for a given
application, the UL classification should be related to a thinner
specimen wall thickness than the plastic part it is aimed for. Thus
the UL classification will be meaningless without a thickness
reference.
The specimen dimensions used for the UL94 testing were
127 mm  12.7 mm x 3.0 mm which complies with the proposed
application on electrical parts and are suitable for comparison of
formulations performance. The Green PVC flammability test was
carried out according to the UL 94 V e “Test for Flammability of
Plastic Materials for Parts in Devices and Appliances e 20 mm Vertical
Burning Test”. In this test, the specimen is positioned vertically in
relation to the test flame. The flame is applied for 10 s and the
specimen response is recorded in terms of the time (t1) for self-
extinction of the flame on the specimen. In case of self-extinction
the flame is applied for another 10 s and the time for self-
extinction of the flame on the specimen after flame removal is
recorded as t2. The time which the sample remained in flame after
the second flame contact is also recorded as t3. Testing evaluation
related to UL94 Vertical and corresponding categories are classified
according to the criteria:
V0 ¼ Combustion is ended in less than 10 s in a vertical spec-
imen. Dripping is not allowed.
V1 ¼ Combustion is ended in less than 30 s in a vertical spec-
imen. Dripping is not allowed.
V2 ¼ Combustion is ended in less than 30 s in a vertical spec-
imen. Incandescent dripping is allowed.
3. Results and discussion
3.1. Starch characterization
Samples of the regular starch (Amidex 3100) were observed on
the optical microscopy at 400 magnification using straight and
polarized light. After reaction with iodine solution, the deep dark
blue indicates the reaction with amylopectin, as shown in Fig. 8.
The suppression of crystalline structure caused by glycerol
gelatinization was confirmed by Wide Angle X-Rays Scattering
(WAXS) shown on Fig. 9. Regular starch curve depicts sharp peaks
at diffraction angles 2q ¼ 15.2 ; 17,1 ; 18 and 23 , which corre-
sponds to the amylose type A crystal structure, whereas the glyc-
erol plasticized starch curve the absence of such peaks indicates the
extent of the gelatinization process by swelling and increase of the
helical interspacing.
3.2. Mechanical strength
The results from mechanical testing of recycled PVC and Green
PVC with 21% renewable content carried out at 23  C/65% UR ac-
cording to ASTM D-638 showed are showed on Table 5. The Green
PVC compounded by the double-step process presented a good
performance in terms of balance of flow properties, stiffness and
strength in tensile loading as compared to recycled PVC without
thermoplastic starch.
According to the results, the major impact of glycerol plasticized
starch on recycled PVC was an average 30% reduction in Young's
modulus. Strain at failure was the most sensitive property with an
average drop of about 70%. It was also noticeable a slightly better
 C.A. Correa et al. / Journal of Cleaner Production 229 (2019) 1397e1411
Fig. 8. Starch sample observed by optical microscopy. a) Regular light; b) Polarized light and c) After reaction with iodine (Magnification 400x).
Fig. 9. Starch x-rays spectra before and after the gelatinization process with glycerol.
performance of the samples containing Blonde glycerol (CG) than
the pure glycerol (PG) used on the starch plasticizing process. So, in
terms of mechanical strength, the Green PVC could be used on
electrical fittings without compromising on structural performance
for formulations with up to 21%wt renewable content.
3.3. Mass loss at 110  C
DOP is the most widespread used plasticizer for PVC owing to its
effectiveness and low exudation. However, there is a trend toward
its replacement by renewable sourced counterparts due to envi-
ronmental and health concerns over phthalates. As though, some
alternative bioderived plasticizers, including oxidized soya oil
(ESO) were tested on PVC dryblend formulations.
The plasticizer effect was evaluated by comparing loss mass data
of recycled PVC samples without starch as depicted on Fig. 10. The
plots show small variation between samples containing DOP and
the other three vegetal plasticizers. However, the values are mostly
under 1% for the whole batch evaluated, which indicates a good
chemical interaction polymer-plasticizer and consequently a high
resistance to exudation.
3.4. Moisture absorption test
The plasticizer effect on water uptake of recycled PVC (with and
Table 5
Tensile properties for recycled PVC and Green PVC samples ASTM D638 (23  C).
Sample Young's Modulus (MPa) Yield Stress (MPa) Tensile Stress (MPa) Tensile Stress at Failure (MPa) Strain at Failure (MPa)
Recycled PVC (without thermoplastic starch) 2,363.06 ± 311.14 34.48 ± 0.41
Green PVC (PG)a 1,689.98 ± 361.34 17.11 ± 1.07
Green PVC (CG)a 1,705.69 ± 201.94 23.22 ± 1.02
a
PG¼ Pure glycerol; CG¼ Blonde glycerol from biodiesel. Green PVC with 21%wt. of renewable content (Starchþglycerol).
1405
without starch) was compared for the plasticizers DOP and ESO in a
broad range of moisture environment. The results are shown on
Table 6.
In terms of water uptake, there are even more revealing obser-
vations. The recycled PVC is rather more stable than Green PVC
independently of the type of plasticizer used. However, Green PVC
formulations showed water uptake nearly doubled, in relation to
DOP, reaching 4.4% for samples with ESO plasticizer. Data also show
that Green PVC samples were very sensitive to environmental
moisture and tend to lose moisture to the environment below 60%
RH, and absorb moisture above it. Water uptake in Green PVC
samples might be related to residual glycerol which is highly hy-
groscopic itself or even due to starch recrystallization over time
leading to embrittlement and plasticizer migration as discussed by
Soroudi and Jakubowikz (2013). In practice, this could pose a severe
problem for applications on electrical fittings direct in contact with
current either in dry or humid areas, once after moisture uptake it
should be a compromising factor for safety. The OSE plasticizer also
increased the water uptake by Green PVC and was disregarded in
favour of DOP. Any residual content of glycerol in the thermoplastic
starch should be minimized to control moisture uptake which
could be done by encapsulating the starch phase or reducing its
content.
3.5. Heat deflection temperature under load - HDT
The heat deflection temperature under load was also measured
for recycled PVC samples with different plasticizers. The results
were compared to a commercial grade of PVC used in electrical
appliances and the standard Green PVC with 21%wt. renewable
content plasticized with DOP. The tests were carried out in flatwise
bars according to the ISO 75e1 for two levels of stress: 0.45 MPa
and 1.8 MPa, and results are shown on Table 7.
The results for heat deflection temperatures of recycled PVC and
Green-PVC compared very well with the commercial grade Ferpl
as
for the two levels of stress tested. Bioderived plasticizers Scandiflex
and Nexoleum did not show any performance advantage over DOP
and ESO and were also disregarded.
For all samples HDT values just above 50  C may be considered a
low value for plastics. This fact is explained by the molecular
structure of PVC with its long sequence of carbons linked by single
covalent bonds which makes the chain backbone very flexible.
34.48 ± 0.41 22.01 ± 6.38 8.86 ± 4.79
17.11 ± 1.07 16.13 ± 1.33 1.86 ± 0.26
23.22 ± 1.02 21.67 ± 1.13 2.97 ± 0.29
1406 C.A. Correa et al. / Journal of Cleaner Production 229 (2019) 1397e1411

Fig. 10. Effect of the type of plasticizer on mass loss of recycled PVC after 48 h inside air circulating oven at 110  C.

Table 6
Moisture absorption test results for recycled PVC and Green PVC with DOP and ESO plasticizers.
a
Relative humidity (%) RePVC/DOP RePVC/ESO Green PVC/DOP Green PVC/ESO

11 0.10 ± 0.11 0.25 ± 0.02 2.69 ± 0,19 3.64 ± 0,14

33 0.18 ± 0.38 0.12 ± 0.02 1.97 ± 0.35 2.59 ± 0.16
58 0.01 ± 0.04 0.12 ± 0.17 0.40 ± 0.07 0.15 ± 0.21
75 0.05 ± 0.04 0.05 ± 0.11 2.06 ± 0.24 2.51 ± 0.20
90% 0.12 ± 0,12 0.24 ± 0,23 2.59 ± 2.05 4.45 ± 1.37
a
RePVC ¼ Recycled PVC.

Consequently, PVC compounds in general present a lower HDT than
other rigid thermoplastics such as styrenics. In building products
which demand high stiffness and structural bearing, this disad-
vantage may be compensated by adjusting the amount of mineral
fillers, such as calcium carbonate in the formulation until the
desired level of stiffness is achieved.
3.6. Dielectric strength
Electrical appliances must comply with ABNT - Brazilian Stan-
dards with dielectric strength one of the most important properties
for safety and prevention of electrical shock. As though, injection
moulded parts of commercial PVC, recycled PVC and Green PVC
were tested for dielectric strength at 60% and 93%RU and results
presented on Table 8.
The dielectric strength results indicate that the presence of
thermoplastic starch in the formulation of Green PVC reduces
drastically the electrical isolation capacity of the material as
compared to commercial and recycled PVC formulations. At 93%RH,
Table 7
Heat deflection temperature under load for recycled and Green PVC with varying
plasticizers.
Material Stress: 0.45 MPa (oC) Stress 1.8 MPa (oC)
the dielectric strength is reduced even further which makes Green
PVC unsuitable for electrical devices even at home voltage ranges of
(110e220 V).
As the test was carried out above 60%RH it is hard to imply
whether the low dielectric strength of Green PVC is related to
moisture uptake above this humidity level, as shown by water
absorption results. While the recycled PVC presented electrical
performance equivalent to the commercial grades, these are issues
that must be looked after if Green PVC should be intended for
electrical applications.
3.7. Flammability tests
The results for UL 94 Vertical tests presented on Table 9 show
that all samples received a V0 classification. The VO grade indicates
that all samples are self-extinguished, and as though they do not
propagate fire and are in full compliance for application in electrical
fittings. A V0 classification for PVC compounds is a strong advan-
tage over other plastic materials used in electrical fittings since they
will not require the use of flame retardants which are usually
expensive, and in the case of halogen based, they may pose envi-
ronmental and health concerns.
3.8. Injection moulding of electrical fittings prototypes

Commercial grade (Ferpl

as) 56.6 51.8 On the design of injection moulded products the tooling plays a
Recycled PVC (DOP) 50.1 46.7
determinant role and is strongly dependent on the flow properties
Green PVC (DOP) 53.9 50.2
Recycled PVC (ESO - Drapex) 53.1 e of the formulation, especially when they are multicomponent
Recycled PVC (ESO - Scandiflex) 49.3 e blends or compounds. Compounded resins should fill out the
Recycled PVC (ESO - Nexoleum) 45.7 e mould cavities in reasonable short times and without part failures,
ISO e 75e1 e Flatwise testing specimens 80  10  4mm; span 64 mm; maximum as the high productivity in the plastic industry is considered a
deflection 0.32 mm. major advantage over other materials conformation processes.
 C.A. Correa et al. / Journal of Cleaner Production 229 (2019) 1397e1411 1407

Table 8
Comparative test results for dielectric strength of PVC electrical parts.

Test run at 60%RH Test Voltage (V) Current (mA)

Commercial PVC Recycled PVC Green PVC

1 100 0.02 0.02 1.14

2 200 0.02 0.02 2.15
3 300 0.04 0.04 9.50
4 400 0.04 0.04 20.30
5 500 0.04 0.06 10.70
6 600 0.06 0.06 12.09
7 700 0.06 0.06 >40
8 800 0.06 0.06 >40
9 900 0.06 0.06 >40
10 1000 0.06 0.06 >40
11 1500 0.08 0.08 >40
12 2000 0.08 0.10 >40
13 2500 0.10 0.11 >40
14 3000 0.13 0.15 >40
15 3500 0.15 0.16 >40
16 4000 0.15 0.18 >40
17 4500 0.18 0.20 >40
18 5000 0.21 0.23 >40

Test run at 93%RH Test Voltage (V) Current (mA)

Commercial PVC Recycled PVC Green PVC

1 100 0.02 0.02 6.96

2 200 0.02 0.02 18.41
3 300 0.04 0.03 7.51
4 400 0.06 0.07 >40
5 500 0.08 0.10 >40
6 600 0.09 0.11 >40
7 700 0.11 0.13 >40
8 1000 0.16 0.19 >40
9 1500 0.24 0.28 >40
10 2000 0.32 0.37 >40
11 2500 0.40 0.47 >40
12 3000 0.49 0.56 >40
13 3500 0.58 0.68 >40
14 4000 0.70 0.80 >40
15 4500 0.81 0.93 >40
18 5000 0.94 1.07 >40

Moreover, the injection moulded prototypes for the electrical parts
must comply with ABNT e Brazilian Technical Standards and are
consisted of three basic components: the external plate, the plate
support and the plug core.
The mould cavities were prepared by the electrical erosion of
stainless steel plates and parts were injection moulded with the
recycled dry blend PVC and Green-PVC for evaluation of in-situ
performance. Fig. 11 illustrates the three moulds designed for in-
jection moulding of electrical fittings prototypes with recycled and
Green PVC.
Design of injection moulding tooling is a mix of art and technical
which requires high expertise. It also depends on a deep under-
standing of rheological principles of the injection moulding process
combined with a good knowledge of the flow properties of the
resin. In this regard, multicomponent polymer systems usually
pose an extra challenge, particularly for too much detailed mould
cavities with variations in thickness and multiple gates. For this
reason the melt compounding step was decisive to achieve a fine
dispersion and good chemical interaction between components in
Table 9
UL94 vertical classification for PVC samples.
Commercial PVC V-0
Recycled PVC V-0
Green PVC V-0
the Green-PVC, as to assure a good balance in terms of flow,
mouldability and structural strength.
PVC compound technology has also some particularities which
tend to make its injection moulding more complex if compared to
polyolefins and styrenic resins. In this regard, recycled PVC without
starch presented a reasonable easy flow and had no major problems
during injection moulding of all prototypes. On the other hand, the
Green PVC required some minor adjustment in the type, size and
number of moulding gates to compensate pressure drop within the
cavity with flow length and strength of welding lines. These hurdles
usually compromise the productivity of the moulding process by
reducing its cycle time and consequently increasing end-product
costs. That's the reason because processors demand “drop-in” so-
lutions and a green-premium is always associated with longer
processing times for reprocessed green products.
3.9. Implications of the Green-PVC approach
Measures to reduce GHG emissions and cope with climate
change have been implemented by the industrial sector in the last
decade following regulations laid by the Kyoto's Protocol in 2005
(Quesada-Rubio et al., 2011). However, since the expiring of the
Protocol's commitments in 2012, carbon trade for waste manage-
ment projects seems to have greatly waned and carbon financing
for solid waste management are currently strong dependent on
regulatory frameworks on emissions and air quality, to re-establish
1408 C.A. Correa et al. / Journal of Cleaner Production 229 (2019) 1397e1411
Fig. 11. Injection moulding cavities of electrical fittings prototypes.
an active marketplace with high prices (Silpa et al., 2018). Apart
from several landfill gas capture projects in Brazil, which were
partially financed by selling emissions reductions through the
World Bank's carbon partnership facility, no reference to reductions
on emissions related to projects of recycling plastic waste, although
some bioplastic producers such as the Brazilian Petrochemical
Braskem often claims carbon sequestration by biomass feedstock or
its carbon neutrality.
Indeed, the implications and limitations of the Green-PVC
approach could be tentatively assessed in terms of sustainability
performance of biobased plastics in comparison to fossil-based,
through the study of lifecycle impacts as proposed by Weiss et al.
(2012). A recent review by Spierling et al. (2018) about environ-
mental, social and economic impact assessments of biobased
plastics aimed to propose a comprehensive approach to calculate
the sustainability performance of bio-based plastics, as compared
to fossil-based plastics using literature data from LCA (Life Cycle
Assessment); S-LCA (Social Life Cycle Assessment) and LCC (Life
Cycle Costing). However, owing to scarce reliable and comparable
data from S-LCA and LCC, the results were summarized in terms of
the environmental impact category of global warming potential
(GWP100), which is currently the most covered impact category
within the environmental assessment of bioplastics. Nonetheless,
despite the study had inventory limitations, for a hypothetical
substitution potential of 2/3 of the global demand for fossil-based
plastics by bioplastics, the authors have shown that fossil-based
plastics replacement by biobased could potentially save 241 to
316 million tonnes of CO2eq annually.
The Global Warming Potential (GWP) published by
PlasticEurope (2015) ranges from 1.6 to 6.4 kg CO2-eq/kg for fossil-
based plastics while for bio-based plastics the GWP ranges
from 0.3 to 11.9 CO2-eq/kg. The Non-Renewable Energy Use
(NREU) for bio-based materials ranged 1.1e92 MJ/kg and
55.5e155.9 MJ/kg for most fossil-based plastics. For the subjects of
interest to the present study, the following figures were found in
the literature (Table 10):
 C.A. Correa et al. / Journal of Cleaner Production 229 (2019) 1397e1411
It's important to note that most literature LCA data available for
bioplastics are calculated on a cradle-to-gate basis, which is linear
(make, use and dispose), and not cradle-to-cradle (circular), with
estimate effects of indirect land use, water, biodiversity for bio-
based not accounted or just assumed as carbon-neutral. The uptake
of short cycle atmospheric carbon through the feedstock is regar-
ded as a special feature of biobased products, which is usually
accounted as negative flow in the GHG emissions profile. In this
case, the final balance on CO2 emission strongly depends upon the
final destination of the waste at its end-of-life, as negative GHG
emissions can be neutralized by incineration, or in case of land-
filling, the carbon could be released as methane on the atmosphere
if energy recovery is not deployed. Even in the case of the so called
certified compostable bioplastics, many environmental impact is-
sues have been related to their end-of-life disposal in North
America, due to the lack of industrial composting infrastructure to
handle bioplastic waste properly, Meeks et al. (2015).
A Progress Report by VinyPlus (2018) showed some direct im-
plications of PVC recycling on reduction of CO2 emissions and non-
renewable energy use in Europe. According to the report, for a total
amount of 2.5 million tonnes of PVC waste generated in 2017,
639,648 tonnes were recycled, which corresponds to 25% of the
total waste available. Considering for each kg of PVC produced a
corresponding 1.9kgCO2-eq is emitted, the PVC market recycling in
Europe may have represented a reduction of about 1.2 million
tonnes in CO2 emissions and at the same time generated approx-
imately 1,000 direct jobs. In terms of non-renewable resources, the
production of PVC requires 55.5 MJ per kg, or 35.5 GJ in NREU
savings for the whole PVC recycled in Europe. However, this figure
may vary from country to country depending on the technology
used in the electrolysis of chlorine production, which tends to be
more environmental friendly and less NREU demanding (Narita
et al., 2002).
As global demand for PVC reached about 31.1 million tonnes
(Plastics Europe, 2015), and resin grades employed by the building
industry representing about 20% of the total amount, environ-
mental concerns regarding GWP and NREU should continue to
make PVC recycling more attractive economically, socially and
environmentally, particularly when associated with renewable
feedstock. Moreover, petrochemicals all over the world are
currently very much concerned about the future image of their
products, as they continue to be scrutinized and related to many
environmental issues, such as the persistent and ubiquitous spread
of plastic littering over lands and oceans.
Relationships among environmental, economic and financial
performance of companies were investigated by Perez-Caldero
n
et al. (2011) by testing the hypothesis that organizations with
better environmental performance are those which achieve better
financial and economic performance, and also greater generation of
external value, according to the DJSEI (Dow Jones Sustainability
Index Europe). To apply these assumptions to PVC manufacturing,
one must consider that PVC represents an industrial sector of high
environmental impact sensitivity due to high toxicity, flammability
and carcinogen potential of its main building blocks, Ethylene
DiChloride (EDC) and Monomer Vinyl Chloride (MVC) (Lithner
et al., 2011). These chemicals have been scrutinized by ECHA e
Table 10
Environmental impact data for bio-based PVC and Thermoplastic Starch in comparison to fossil-based PVC (Spierling et al., 2018).
Material 1 kg Global Warming Potential (GWP100) [kgCO2-eq]
PVC Biobased Alvarenga et al., 2013 9.3E-0.2
PVC fossil-based Plastics Europe, 2015 1.9
Thermoplastic Starch (TPS) Narita et al., 2002 1.9
1409
European Chemicals Agency/REACH e Registration, Evaluation,
Authorization, and Restriction of Chemicals), and as a result of
growing environmental concerns, there were some advances in
technologies for PVC manufacturing, including the use of less
hazardous electrolysis processes for chlorine production, new
research in non-phthalic plasticizers, lead-free additives, and most
importantly by attempts to decoupling production from fossil
feedstock. The Biobased PVC or simply Bio-PVC is obtained from
renewable sources through the use of sugarcane to make bio-
ethanol based ethylene is identical to its fossil-based counterpart,
a drop-in solution with 80% of potential substitution replacement
of fossil by biobased (Alvarenga et al., 2013; Shen et al., 2009).
The real cost of biobased feedstock for plastics production, such
as corn starch currently relies on subsidies to become more
competitive with fossil feedstock, and owing to many crossroads,
biobased product developers and producers still face many market
diffusion challenges. These are hurdles that could impose market
limitations to fossil-plastic replacement by biobased, Brockhaus
et al. (2016). On the other hand, considering the low average
plastic recycling rates, having a relative simple technology, that in
principle can be performed by small companies in their own fa-
cilities, or even used in closed-loop manufacturing processes by
PVC processors, large amounts of PVC industrial waste could be
diverted from landfills, open air dumping and incineration.
Conversely, market prices for recycled PVC are usually lower than
virgin PVC and its blending with thermoplastic starch may repre-
sent an extra value to the recycled waste into the products made
out of Green-PVC. In regard to end-of-life disposal practices, the
industrial activities which are environmental sensitivity may have a
clear influence on economic, finance and value generation, as
suggested by analysis of Pe
rez-Caldero
n et al. (2011). However, lack
of detailed information about the economics of specific business
sectors (including PVC, bioplastics and recycled plastics), in market
databases such as the DJSIE, may hamper further conclusions about
the economic benefits of the Green-PVC approach.
An important part of this equation may lie on considerations of
risk assessment and the economic impacts of plastic pollution.
Cost-benefit analysis of recycling PVC waste carried out by Arche e
Consulting in Belgium concluded that recycling PVC waste was
preferable and more economically efficient than incineration or
landfilling and it also creates more jobs than any other end-of-life
option. Risk assessment by FABES e German Institute also has
shown that potential lead leaching (named as legacy additives)
from recycled PVC applications is small compared to the environ-
mental, economic and job creation benefits (VinylPlus, 2018).
The Green-PVC concept also fulfills many other aspects outlined
by the circular economy as laid out in a recent report of the
European Commission (2018). The European Commission has also
associated the move towards a circular economy with strategies
such as: boosting recycling, and preventing the loss of valuable
materials; creating jobs and economic growth, showing how new
business models, eco-design and industrial symbiosis can move
Europe towards zero-waste and reducing GHG emissions and
environmental impacts.
The eco-efficiency principle could be regarded as the sole pur-
pose of circular economy or one of its several consequences, along
Non-Renewable Energy Use (NREU) [MJ]
13.8
55.5
39.8
1410 C.A. Correa et al. / Journal of Cleaner Production 229 (2019) 1397e1411
with economic value and job creation, reduction on emissions and
waste, improved resource security and reduced price volatility for
resources (Kalmykova et al. (2018). As though, whether the Green-
PVC approach benefits complies with Porter's hypothesis for eco-
innovation and other circular economy principles such as eco-
efficiency or eco-effectiveness, shall require further investigation.
Literature data on LCC e Life Cost Cycling is rather scarce, and so far
there is no market evidence to conclude that an improved envi-
ronmental performance of Green PVC would be translated in an
improved economic performance for PVC producers and recyclers.
Furthermore, the Brazilian PVC market is concentrated on a few
companies without too many competitors, and public perception of
the value of reduced environmental impact products is not yet
perceived in this market segment due to the lack of environmental
regulatory factors and consumer awareness. Additionally, in many
sectors, companies are often reluctant to release confidential in-
formation about their products under development, which make it
difficult to establish any correlation between economic perfor-
mance and drivers for eco-innovation such as in the research car-
ried out in China by Wugan and Guangpei (2018).
Another aspect to achieve sustainable development in plastic
waste management is the potential of substitution of fossil based
PVC by Biobased PVC, claimed as 80% in the literature, while no
reference about substitution of PVC by thermoplastic starch has
been found (Shen et al., 2009). Thus, for the time being, adding
renewable content to PVC industrial waste by mechanical blending,
rather than a more costly investment shift to a bio-ethylene feed-
stock, should make the Green-PVC approach an eco-innovation
within the circular economy concept, even without a market
evaluation performance. Moreover, the approach is in full compli-
ance with eco-effectiveness, as the real purpose of the circular
economy, whose main goals are generate cyclical cradle-to-cradle
metabolisms and extend material usage rather than sole mini-
mize the cradle-to-grave flow of materials, Kalmykova et al. (2018).
Finally, blending fossil-based polyolefins (polyethylene, poly-
propylene) with biobased thermoplastic starch has already been
used as a strategy for gradual replacement of fossil-based feedstock
by renewable in many single-use, throw-away packaging applica-
tions, Soroudi and Jakubowikz (2013). Nonetheless, in the mean-
time, a full paradigm shift from fossil to biobased might be
hindered by the small global installed capacity for bioplastics
production, which has been steadfast growing in the last two de-
cades but remain less than 1% of the global capacity of the fossil-
based commodity plastics. It is also important to ensure that this
paradigm shift will measure up to environmental benefits in terms
of well-defined sustainability indexes, and to that effect, the Eu-
ropean Commission has already started work on understanding the
lifecycle impacts of alternative feedstock used in plastic production,
including different sources of biomass and GHG effluents, such as
carbon dioxide or methane. In the case of carbon dioxide feedstock
for plastics production, it seems to have a strong potential for
capturing carbon emissions, but conversely, it has some drawbacks
as high demand for NREU and new catalytic systems to break down
the very stable CO2 covalent linkages. (European Commission,
2018; Ellen MacArthur, 2017).
4. Conclusions
The green concept for PVC compounds is a current market trend
which makes use of not only bioderived plasticizers in replacement
of phthalates but also biotech routes accounting for biobased
polymers sourced from biomass. This is the case of bioethanol
feedstock used on the biosynthesis of bioplastic commodities such
as polyethylene, polypropylene and PVC which has been used by
many companies in their sustainability campaigns. Nonetheless,
many plastics currently produced by biotech routes are chemically
identical to their petroleum counterparts differing only by their
renewably sourced feedstock. The main environmental claims on
such bioplastics are reduction of GHG emissions and carbon foot-
prints with no difference at the end-of-life, which remain a source
of major concerns related to plastic waste disposal. While the
recycling rates of plastics remain rather low, most of its waste are
still buried or incinerated, which require solutions based on reuse,
revaluation or reprocessing, within a circular manufacturing
framework.
The presented Green PVC is a twofold approach which takes into
account the reuse and recycle of post-industrial waste which was
melt compounded with renewable starch thermoplastic plasticized
with glycerol waste from biodiesel. The resulting material can be
either closed-loop recycled (same or similar-quality applications)
or cascade recycled (in lower quality applications), once the ratio of
the ingredients in the formulations can be fine-tuned, as a “cake
recipe” for any target application. The case study presented for
injection moulding of electrical fittings has shown reasonable
performance considering the shape complexities of the compo-
nents. In this case, the major concern was related to hygroscopic
behavior of the Green PVC as the product will tend to take up
moisture from air above 60%RH, as shown by water absorption
tests. The hygroscopic nature of the formulations seemed to
interfere with electrical properties, with dielectric strength drop-
ping drastically in the presence of thermoplastic starch. Besides
residual glycerol on the formulations, hygroscopic behavior of
Green PVC may be related to heterogeneities and/or uncontrolled
porosities resulting from moulding process, considering Green PVC
is a multicomponent material.
Moreover, the presented Green PVC approach may be consid-
ered as an alternative to avoid illegal dumping of post-industrial
waste, particularly PVC degassing powder which can be very
harmful to the environment as microplastics and if either buried or
incinerated. This approach may also contribute to raise interest of
PVC manufacturers and transformers on initiatives such as the
extended product responsibility (EPR), as a means to have their
waste back into closed-loop supply chains in full compliance with
waste disposal regulations.
And last but not least, the present Green PVC approach should
be regarded as a type of market push eco-innovation which de-
mands a paradigm shift in terms of green marketing strategies. The
green approach may also require effective business models for
commercialization, mitigation of eventual green-premiums, and
above all enacting public policies in terms of eco-labelling and end-
consumer awareness in regard to sustainability of products and
processes.
Acknowledgements
The authors acknowledge FAPESP (State of Sao Paulo Funding
Agency e Grant Number 2009/54664-1), University of Toronto,
Canada and Corn Products of Brazil for their processing laboratories
and testing facilities.
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