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PhD FPS - NCSU

RECYCLED POLYAMIDES, A LITERATURE REVIEW AND

RESEARCH OPPORTUNITIES.
Edmir Silva.
With the strength of the green movement increasing daily, fiber
manufacturers had to adapt and become more creative, developing ways
to save and improve the environment. This article will review the current
state of the art of recycling polyamide, its implications and opportunities
that exist covering more ground of scientific exploration in this field. Brief
discussion on testing is made and focus is given for the mechanical
properties where multiples researchers results are compared. Finally
recommendations are made for future works in the field.

Keywords: Recycled materials; Polyamide; re-used materials; Nylon recycling;

Contact information: College of Textiles, NCSU, email: easilva@ncsu.edu.

1. INTRODUCTION

Worldwide Textile Mill consumption of Nylon is averaging 3.5 million tons

yearly since the 90s and new investments in China announced recently, will drive the
number even higher. With such consumption levels, the industry is forced to develop
ways to re-use, re-cycle or just using the market language, become green at some extent.
This data comes from yearly strategic research done by Unifi Inc.. The research also
shows that polyester has 10 times more annual consumption worldwide than Nylon, on
average.
The Figure one is a break down by staple and filament fiber. The filament is
separated further into carpet, industrial and textile. It is clear that over the years Nylon
staple demand has been low in quantity, where the filament side has a good balance
between carpet, industrial and textile. Some growth is being seen on the industrial side
for high value end-uses. The industry believes that raw material prices and availability

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are the biggest factors influencing the Nylon business; the competitive market against
polyester and vice-versa is a constant battle.
In this context the re-use of the polyamide is clearly a way to get an extra source
of raw material, and enable claims for carbon footprint reduction what aligns both
industry and market needs.

Textile Mill Consumption

5000
4000
'000 tons

Nylon Other Fil.

3000

Nylon Carpet Fil.

2000

Nylon Industrial Fil.

Nylon Textile Fil.

1000

Nylon Staple

0
1990 2000
2005 2006
2007 2008
2009

2010

Years (estimation 2010 on)

2011

2012

2015

Figure 1. Graph on demand by type.

Was observed by (3) that the majority of Nylon (Polyamide 6 and 66) is used on
carpet, the recycling of carpet was thought and patented first by DuPont in 1944, even
though the recycling of a dirty carpet represents a challenge still today.
The collection and sorting of materials are the biggest challenges for the supply
chain on recycling for that various methods on sorting are used, being the most common
the checking the melting point of the polymer and infrared or near infra-red technologies
(IR). The IR being a fast, accurate and non-destructive test are by far the most used.
There many ways to re-use the polymer and few studies are available in the
literature. The work from (1) at USC (University of South Carolina) did list four classes,
(2) and (3) agrees with it:
1. Chemical recycling or De-polymerization method to break down the long chain
of polymer into monomers than can be re-polymerized, which possibly converts

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the waste into products having a quality equivalent to that of the virgin
polymer. Polyamide 6 can be depolymerized to its monomer caprolactam, by
acidolysis, hydrolysis, aminolysis or catalyzed-de-polymerization in vaccum.
Whilst aminolysis is now the preferred route being used by DuPont, catalyzed
depolymerization in vacuum has recently been developing into promising process.
Companies recycling polyamide 6 and 6.6 by depolymerization includes: DuPont,
AlliedSignal, BASF and Novalis Fibers. This classic system for the closed-loop
recycling of carpets, which in theory can proceed forever.
a. Acidolysis Nylon 6 depolymerized using an acid catalyst, the cut nylon
6 waste is melted in a continuous reactor and treated with steam, the
monomer is formed by hydrolysis. After distillation and filtration the
caprolactam is recovered read for further usage.
b. Hydrolysis Depolymerization of PA6 in high-pressure steam reactor
(AlliedSignal), PA6 hidrolytically depolymerized in an aqueous system
under pressure give yields around 70% of caprolactam, see figure 2, the
expensive part on this process is the distillation to remove water.
c. Aminolysis DuPont identified ammonolysis as the best depolymerization
option for scrap carpet, yields on this process can reach 80% in theory. All
the preparation work is also required (backing separation, removal of dirt
and contaminants), followed by shredding, chipping, going through a
hammer mill, screening and then grounded to particles of 1.5mm. Water is
added to the material to form a slurry and then further separation by
density is performed, reaching ratios of 98.5% purity, this material is
transferred to the de-polymerization reactor. In the ammonolysis reactor,
the nylon is mixed with ammonia gas and phosphate catalyst, what is
separated later by distillation. This process is versatile and can even
process copolymers.
2. Extracting recycling or Recovery of polymer components method to recover
individual components of the polymeric mixture without reaching the monomer
level. Includes multiples extraction and separation steps.

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3. Mechanical recycling or Re-melting this method is the melt-blending of the

entire structure. Used on carpets, for example, where a thermoplastic mixture is
prepared from the melt-blending of the entire carpet waste, which produces a
product with lower quality.
4. Thermal recycling or Energy generator which involves only energy recovery
during incineration of the polymer waste.

Figure 2. Diagram of Carpet Recycling (extracted from AlliedSignal Catalog).

An example of the chemical recycling is illustrated in Figure two. This recycle

program, in use by AlliedSignal, defines that a new carpet is sold to a commercial
building owner, when in need to be replaced a carpet installer removes the old worn
carpeting and returns it to the carpet collector. The carpet collector uses a hand-held
infrared scanner to sort and bale all the returned carpeting. A recycler picks up all the
nylon 6 carpeting and takes it to the re-polymerization plant, where the worn carpeting is
fed into the front end of the de-polymerization plant. Molded nylon 6 parts (even those
with paint) can also be used. Super-heated steam is used to de-polymerize (chemically
separate) the nylon 6 from the other components of the carpet, including the rubber
backing. Finally the depolymerized nylon 6 is further processed to return it to its

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caprolactam feedstock, which is then filtered for high purity and shipped to AlliedSignal
polymerization plants to make their product branded INFINITYTM nylon 6 resin.
Some considerations about the cited classes is that de-polymerization is the
preferred route because it breaks the product into monomers which can then be repolymerized into new high quality nylon. It can be argued that this process does cut some
steps from the original monomer generation. When there is a blend and the nylon needs
to be separated by a solvent, for example, it can be difficult to re-use the solvent since it
will probably facilitate the dissolution of impurities that were on the outside of the
polymer and hence limit the polymer usage or require filtering. In case of melting blends,
where a different polymeric material is resultant, every time can restrict the future
number of applications in which the product can be used. Blends result in batches and
therefore quality levels can vary from time to time; still the possibility of avoiding
separation makes this method attractive for some applications.
In order to characterize what normally happens in the industrial processing of
nylon, one has to understand how virgin and recycled material, blended with different
ratios, behaves as raw material characterization, thermal and mechanical properties of the
fiber. The work of (2) was the one that most approximate to a fiber production reality.
The product variability is intrinsic to the amount of impurities present in the
polymer since recycled products have more impurities than virgin materials which
becomes an important point of control during the processing of such polymers. The work
of (4) demonstrates this point and discusses that the durability and reliability of products
using recyclate might be significantly reduced by the presence of impurities acting as
stress concentrators. The absence of impurities is the key for reliable mechanical
properties, therefore characterizing the size and concentration of impurities that the
product can allow could be critical to the success of the processing of the recyclates.
Degradation is another point that will occur in the process. The paper (5)
recommended color readings to access the degree of degradation noting substantial
differences after re-use of the polymer. In (6) the researcher observed the degradation
phenomenon not only results in brittleness and deterioration of the mechanical properties
of polymers, but also decreases stability and restricts the applications of the final

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products. In the textile apparel for example, this would limit the shades that the fiber can
be used in, normally light shades can be challenging.

2. TYPICAL PROPERTIES MEASURED

2.1.

Moisture Content
Increase confidence of the drying process is normally checked before and after
drying. The existence of moisture in melt spinning provokes hydrolytic scission
of chains with consequent reduction on molecular weight and therefore,
catastrophic reaction on fiber properties.

2.2.

Color Readings
Degradation can have big impact on color and a way to perceive such changes is
measuring the color of the chips or the as-spun fibers. The color readings of
waste streams or raw material, as well as cutting edge inline color measurements
(normally at the extruder, melted fiber), can enhance process control and allow
containment in case of off-quality events.

2.3.

Intrinsic Viscosity
Property checked in chips and as-spun samples using a capillary diameter
viscometer. This measurement will enable the calculation of molecular weight. In
order to determine material consistency, its recommended to combine rheology
measurements with filtration measurements over time.

2.4.

Density
Property measured on a density gradient column of carbon tethacloride with
toluene, suggested three readings after 6h equilibrium. With the density the
crystallinity fraction can be calculated. This measurement can indicate thermal

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history in case there is significant variation in the readings between material to

material.

2.5.

DSC (Differential Scanning Calorimeter)

The curve provided in this test will allow crystallinity to be measured indirectly,
glass transition region and melt point region on the samples analyzed, normally
as-spun or drawn yarns. This test requires a considerable amount of time and
precision to be able to use the results, one should not depend only on it, but use
as a reference since it will detect significant molecular structural changes.

2.6.

Birefringence
Provide clear information of the amorphous and crystalline regions hence
orientation of the polymer. Normally defined by reflectance of light over the
lamellas which will have 0 if they are perfectly oriented; normally fibers will
vary around the 20 to 40.

2.7.

Melt Flow Index

Measurements that can indicate melt viscosity changes and molecular weight
changes working as a check against other measurements.

2.8.

Linear Density
Property measured in yarns, normally Denier (g/9000m) or Dtex (g/10000m).

2.9.

Mechanical Properties
For all the samples the tensile strength, modulus, and breaking elongation can be
measured using ASTM 3822. This measurement will be used for comparison of

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the many researchers reported in the literature. The well-known Instron machines
or Statimat from Textechno are widely used in the industry and research
laboratories today.

2.10.

Shrinkage and Crimp properties

In case of yarns the shrinkage is an important factor and in case of textured yarns
crimp is also good information. This paper will not discuss much of the thermal
properties such as shrinkage and crimp, but since thermal history is rich in
recycled materials, it is wise for the researcher to verify its effects mainly on
properties that will require further thermal treatment. This paper discusses
shrinkage and crimp of the yarn, but this should be carried out as far as the fabric
dyeing and its thermal setting finishing processes before garment preparation.

3. DISCUSSION ON MECHANICAL PROPERTIES

For this paper the results of many authors experimental work will be presented in
an indexed form. The initial property (the virgin material) value is set as an index one and
the following values are the percent variation in relation to its virgin value. This
eliminates the need to state the units and allows an overall qualitative comparison.
References are provided for further understanding of individual experiments performed.
The properties that will be discussed are first, tensile strength, which is a measure
of the steady force necessary to break a fiber and is given experimentally by the
maximum load developed in a tensile test performed using ASTM 3822. The second is
the elongation necessary to break a fiber, normally expressed as a percentage increase in
length, also termed as elongation at break, using the same ASTM standard.
The intention is to combine the available literature values into graphics that
explain or indicate the to be expected behavior of the re-processing of polymer. By the
end of the discussion an inclusion of waste will be presented, but the following graphs are
re-processing of same polymer, which should demonstrate the thermal history behavior

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existent on each polymer after re-processing. As in the well-known Boltzmanns

superposition principle, where his first conclusion was that the effect of load applied
anytime continues forever, the thermal history suffered somewhat cannot be erased from
the polymer.

Tensile Stress

Indexed Tensile Stress

1.30
1.25
1.20
1.15
1.10
1.05
1.00
0.95
0.90
0.85
0.80

(6)
(4)
(5)

9 10 11 12 13 14 15 16

Number of cycles
Figure 3. Results on Tensile Stress versus number of cycles

As observed on Figure 2 obtained from (4), (5), and (6):

From (4), while testing strength, the diameter was verified for aged and un-aged
samples showing limited influence on it. Since the exploratory work was
considering influence of impurities diameter as well as cycles were verified that
samples containing impurities above 100 micrometer, their tensile strength
slightly decreases as the impurity diameter increases, which is expected as results
of localized stress on the chains. Its also concluded that impurity sizes have a
critical point for tensile properties and one should consider studying the impurity
impact by its type. This material characterization can be visualized by a plot of
Tensile strength versus (Diameter)(-1/2), suggested the author.

From (5), the tensile strength as a function of a number of processes, a small

increment in the tensile strength property of PA6 is observed when the number of
processes increases. The increase is considered significant by the author.

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From (6), the load at the yield point and draw point increases with increased
cycles of injection molding. The overall increment in the yield stress from the 1st
to the 16th cycle is approximately 25%, and a higher load at the cold drawing
region is observed for the 8th and the 16th processed PA6 samples.

Indexed Elongation at Break

1.10
Elongation at Break

1.00
0.90
(6)
0.80

(7)

0.70

(8)

0.60

(4)

0.50

(5)

0.40
1

9 10 11 12 13 14 15 16

Number of cycles
Figure 4. Results on Elongation at Break versus number of cycles

Figure 3 illustrates the elongation behavior from the work of (4), (5), (6), (7) and
(8).

From (4), the elongation is similar or lower compared with re-extruded reference
samples. Again, the existence of impurity explains the reduction on elongation
and was also noted in a relationship of the elongation with the diameter of
impurities, suggesting that there is a critical diameter after what cause
catastrophic failure.

From (5), the re-processing has an obvious reduction on elongation, making it the
most abrupt decrement.

From (6), the elongation at break is somewhat stable up to the 12th cycle and then
has an abrupt reduction in contrast with all the other works. The author also noted
the increase of the standard deviation after the 13th cycle on top of its value
decrement, which can be the characterization of a non-stable polymer chain.

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From (7), relates its tensile properties decrease to be directly related to molecular
weight reduction.

From (8), just note that this work was performed on nano-composites; the
elongation decrease follows the other tests trends.

The mechanical properties are affected to a different extent as a result of

reprocessing operations. The results show that there is an increment in tensile yield stress,
flexural strength and consequently modulus, therefore it is possible to observe that the
mechanical properties of PA6 were gradually modified from soft and tough to hard and
brittle after each processing cycle. The modification in mechanical properties should be
thus attributed to the macromolecular chain scission and broad chain length distribution,
propose (6).
During the recycling of the injection molding (5), a darkness patterning was
observed from the 4th re-processing time increasing to the 10th time, therefore it
concludes that the cause of decrement on physical-mechanical properties of PA6 was
polymer degradation, and added further PA6 can be processed up to seven times without
effecting its physical-mechanical properties and morphology; the only change registered
was the color, but can be used if the end-use is directed only to highly pigmented items.
Furthermore, the author does not recommend exceeding 10 cycles of re-processing,
which is not in agreement with the practical world since this cannot necessarily can be
measured.
The observation made by (7) was that the degradation is due to the thermomechanical stress acting on the molten polymer. Re-processing of wet material provokes
a drastic reduction of molecular weight by hydrolytic chain scission, thus the usage of
additives is recommended to remove water, making it possible to recycle PA (and other
poly-condensation polymer) in wet conditions.
The discussion proposed by (8) is interesting for its detailed measures taken of
ductility of the material at break, as well as viscosity, molecular weight, reprocessing at
different temperatures, and dispersion versus shear stress.
The only pure textile driven work was presented by (2) where the approach differs
from all the others by use of a % of waste combined with the virgin material, or namely a
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blend, was observed that by the increasing the fraction of recycle PA6 in the samples,
glass transition temperature decreases which suggested that amorphous regions were
extended with increase in waste material. The analyses was made in two phases, as-spun
and drawn fibers, the tensile properties of as-spun yarns such as tensile strength, breaking
elongation, and modulus were made and statistical studies on the samples indicate that
there is no significant difference between tensile properties of different samples at 95%
confidence level. Therefore, they were consider to have similar behavior as can be seen in
Figure 5.

Indexed Property

Tensile Properties of As-spun Fiber

1.10
1.08
1.06
1.04
1.02
1.00
0.98
0.96
0.94
0.92
0.90

Tensile Stress
Elongation

20

40

60

80

100

% of Waste
Figure 5. Tensile Properties of As-spun Fiber versus blend

The second part of the study was performed on drawn yarns where statistical
analyses of tensile properties of drawn samples show that strength and modulus of 0%
(virgin material) samples is different from those of other samples at a 95% confidence
level, but elongation at break of drawn samples are the same. As seen in Figure 6, tensile
strength and elongation of virgin material are somewhat higher than yarns containing reused PA6-drawn yarns, of course drawing as-spun yarns results in the increase of tensile
strength and modulus with consequent decrease of breaking elongation, which can be
explained by the orientation and crystallinity increase of as-spun yarn subjected to the
drawing process.

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Tensile Properties of Drawn Fiber

1.02
Indexed Property

1.00
0.98
0.96
0.94

Tensile Stress

0.92

Elongation

0.90
0.88
0.86
0

20

40

60

80

100

% of Waste
Figure 6. Tensile Properties of Drawn Fiber versus Blend

Further work was performed on textured yarns by (2), but potential miss conceptions
about the texturing process could have misled the researcher. This paper will not discuss
the results, in order to be fair to the author a series of questions were forwarded to him
with no answers so far.

4. OPPORTUNITIES FOR FUTURE RESEARCH

The academic research carried up to now focused on the re-use of the same
material over and over; just one or two groups explored the blends. In the industrial
reality waste stream is not readily available and definitely not constant or homogenous. It
is necessary to study and characterize waste streams and discuss methods to validate its
quality over time in an online and non-destructive way. An example is to receive a
material from a certified source and overtime verify its filtration levels and consistency as
well as intrinsic viscosity variation; in case of Nylon, watch batch to batch moisture
levels. Further than that can be the discussion of formulation of recipes where one can
take multiple batches and combine them (blend) in ratios that can assure a reasonable
consistency for the fiber producer. If the blend is considered, the number of cycles may
not be a measurable factor since the material does not seem to carry an aging

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characteristic in regards to number of cycles suffered besides the degradation of its

properties.
Little research consideration was noted in regards to the uniformity of the
measurements or lack of sound statistical analyses on uniformity over re-processing
which could have shown signs of degradation of polymer, which was confirmed when the
color was considered. The only exception was work done by (2). A more robust statistical
approach is therefore recommended in order to establish definite root causes and factors
that truly need to be controlled, examples include: impurity levels, coloration, machine
and process parameters, waste stream usage and its fraction on the entire blend, the
nature of the blend itself and its uniformity.
An important factor for a recycled product is its enriched thermal history which
can be studied in the form of the polymer, yarn as-spun, drawn yarn or drawn-textured,
dyeing and fabric framing or finishing. Its believed that the recycled products will
generate a lot of challenges for all those involved in these processes. Studies need to
verify ways to better treat those materials that have somewhat suffered some thermal
stress in their past.

5. CONCLUSION

The paper discussed briefly the current state on polyamide recycling and its
relevance in volume and technology. Emphasis was made on the various tests and
procedures employed by different researchers on this field, citing and comparing the
mechanical properties analyzed by them, overall was observed that there is no obstacle in
recycling fibers. This work did not discuss the thermal properties but do recommend to
not be forgotten by users of recycled fibers. Furthermore thoughts for further research are
shared on the last part of the paper.

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6. REFERENCES

(1) Mihut C, Captain DK, Gadala-Maria F, Amiridis MD. Review: Recycling of nylon
from carpet waste. Polym.Eng.Sci. 2001;41(9):1457-1470.
(2) Meyabadi TF, Mohaddes Mojtahedi MR, Mousavi Shoushtari SA. Melt spinning of
reused nylon 6: structure and physical properties of as-spun, drawn, and textured
filaments. Journal of the Textile Institute 2010;101(6):527-537.
(3) Scheirs J. Polymer recycling : science, technology, and applications. New York:
Wiley; 1998.
(4) Eriksson PA, Albertsson AC, Boydell P, Mnson JAE. Influence of impurities on
mechanical properties of recycled glass fiber reinforced polyamide 66. Polym.Eng.Sci.
1998;38(5):749-756.
(5) LozanoGonzlez M. Physicalmechanical properties and morphological study on
nylon6 recycling by injection molding. J Appl Polym Sci 2000;76(6):851-858.
(6) Su KH, Lin JH, Lin CC. Influence of reprocessing on the mechanical properties and
structure of polyamide 6. J.Mater.Process.Technol. 2007;192:532-538.
(7) La Mantia FP, Curto D, Scaffaro R. Recycling of dry and wet polyamide 6. J Appl
Polym Sci 2002;86(8):1899-1903.
(8) Goitisolo I, Eguiazbal JI, Nazbal J. Effects of reprocessing on the structure and
properties of polyamide 6 nanocomposites. Polym.Degrad.Stab. 2008;93(10):1747-1752.

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