Characterization of Monopolymer Blend of Virgin and Recycled Polyamide 6

R.SCAFFARO and F.P.LA MANTIA

Dipartimento di Ingegneria Chimica dei Prmessi e dei Materiali Universita di P a l e m Vide delle Scienze, 90128 P a l e m , Italy
It is a common industrial practice to blend virgin polymer with the same recycled polymer coming from plastic scraps that, in general, has not undergone relevant degradation. In this work, the characteristics of blends of virgin and recycled polyamide have been considered by changing the amount of recycled polymer and the presence of humidity and a stabilizer. Neither dry nor wet stabilized recycled polyamide samples show significant variations of the molecular weight, but the melt Newtonian viscosity of the blends are slightly different from that predicted by an additive rule, despite the same chemical nature of the two components. This holds true even more for the humid unstabilized sample, as its noticeably lower molecular weight implies values lower than those expected on a linearity basis. The situation is different for the mechanical properties: here the morphology reached in the solid state determines a more rigid and brittle material, compared to the pure components, with relevant deviations from linearity for a l l the recycled samples used to prepare the blends. A different crystallinity as a function of the composition can be invoked to explain this phenomenon. The blends containing dry and wet stabilized recycled polyamide show almost the same behavior, confirming the reduced degradation of these samples.
INTRODUCTION

t is a common industrial practice to reuse plastic scraps by blending them with the same fresh polymer. This operation is, in general, carried out by using the plastic scraps produced in the same industry, i.e., with materials that did not undergo any relevant degradation and then showing properties and characteristics very close to those of the virgin polymer (1-10). In previous works (1-2, 4 6 , 10)we investigated the characteristics of these blends-monopolymer or homopolymer blends-marking the relationships between the properties (mechanical, rheological) with the amount, the structure and the properties of the recycled component. The characteristics of these blends are never easily predictable on the basis of the properties of the components, even if they show very similar chemical natures, because of differences in the molecular weight, in the crystallinity and crystallization kinetic, and in the chemical structure because of the presence of new functional groups in the recycled component resulting from its processing. This feature, of course, can give rise even to incompatible blends with properties that

cannot be predicted on the basis of the properties of the two components and, moreover, are in general lower than those expected on the basis of a linear composition rule ( 1 3 ) . In these cases the properties are generally determined by those of the recycled component. Of course, practical industrial application would prefer, at least, a qualitative prediction of the final properties as a function of the concentration just to determine the optimum amount of the recycled polymer to use in the blend (1-3, 7, 10). Even though homopolymer blends containing recycled polyamides (WA) are widely used for the production of automotive components (1-3). few works have been devoted to this subject. The aim of this work is to evaluate the rheological and the mechanical properties of monopolymer blends of polyamide 6. The influence of humidity and of a stabilizing system will be taken into account.
EXPERIMENTAL

The material used in this work is a sample of polyamide 6 (Rhodia)with an intrinsic viscosity of 3.8 dl/g measured in sulfuric acid. The operation of recycling and the preparation of the blends have been carried

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Monopolymer Blends o f Virgin and Recycled PA6 out by using a single-screw extruder (Brabender, L/D = 25, D = 19 mm) with a flat temperature profile of 240C and a n extrusion speed of 100 rpm. The recycling operations were carried out both on humid [H) and dried (D) materials. In the latter case, the material was kept in a vacuum oven for about three hours at a temperature of 120C. In all cases the humid material was processed together with 500 ppm of a n antioxidant (P-EPQ, Clariant) (HS). This antioxidant has been found by L a Mantia and Scdlaro (11) to be very effective in preventing the hydrolytic degradation of the wet polyamide during processing, as the properties of the humid recycled PA6 were very close to those of the dry recycled sample. Further details on the action of this antioxidant on the properties of the recycled PA6 can be found elsewhere [ 11). The recycled material was obtained by two different passages in the extruder: the first passage simulates the processing while the second one simulates the recycling step. In the preparation of the blend, the recycled material was milled in a knife mill, premixed with fresh polyamide at the solid state, and then fed into the extruder. The sample codes of the materials of this work are reported in Table 1. The specimens used for the rheological and for the mechanical characterization were prepared by compression molding by using a Carver laboratory press at the temperature of 240C. In this case the materials were dried before following the same procedure employed before processing. The rheological properties were measured using a parallel plate rheometer (Rheometrics RDAII) at the temperature of 240C; the radius of the plates was 25 mm and the gap 1.7 mm. The main tensile properties, elastic modulus, tensile stress, elongation at break, were measured by using an Instron 1122 apparatus: the crosshead speed was 50 mm/min and the sample used for testing were rectangular shaped (10 mm width, about 1 mm thick, grip distance 50 mm). To ensure that the equilibrium humidity was reached, the samples were left at room temperature for at least three days. Separated analysis demonstrated that the moisture amount in Ny samples can reach 2.3-2.7% by weight. Thermal measurements were carried out by using a dserential scanning calorimeter (Perkin Elmer DSC7). The scans were effectuated in the range 20"C-240C at a heating/cooling rate of 20"C/min.
RESULTS AND DISCUSSION

The Newtonian viscosity of the monopolymer PA6 blends is reported in Fig. 1 as a function of the recycled polyamide (RNy) content. The values of the Newtonian viscosity are intermediate between those of the two components and are only slightly different from the additive rule:
pb

= puqu

+ pr(l

qu)

(1)

Table 1. Compositions and Sample Codes o f the Materials Used in This Work. Sample code PA6 D H HS Composition

Virgin PA6 Dried recycled PA6 Humid recycled PA6 Humid stabilized recycled PA6

where P,, P, and Pb are the generic property of the virgin polymer, the recycled polymer and of the blend, respectively, and the volume fraction of the virgin component. In our case, as the components display almost the same density, the weight fraction and the volume fraction can be considered the same. Slightly deviations from the additive rule can be evidenced for the dry and for the wet stabilized sample. This result can be reasonably interpreted with the very similar chemical nature of the two polymers of the blend and with the very similar molecular weight of the components. Nevertheless, on increasing the differences in the molecular weight between the two components, i.e., for the H containing blends, the values of the viscosity are si@cantly lower than those calculated by using the additive rule displayed in Eq 1. This behavior can be easily understood considering that the compatibility between polymers of the same type decreases with an increase in the difference between the molecular weights of the two components of the blend. This explanation hold also for the HS containing blends. As reported in Fig. 1 , the highest values of the Newtonian viscosity are displayed only by the HS containing samples. This result, apparently surprising, is related to the strong inhibition of the polyamide hydrolysis, and then of the low reduction of the molecular weight, due to the presence of the P-EPQ as stabilizer (11).The small difference between the molecular weight of the two components leads to a higher compatibility, and this is why the HS containing blends display the highest values of viscosity in the whole composition range. This is confirmed by the very good agreement between the experimental data and the lines relative to the additive rule calculated by Eq 1. The mechanical properties-composition curves, reported in Figs. 2 4 , are certainly much more complex than those of the viscosity. In particular, maxima in the curves of the elastic modulus and minima in the curves of the elongation at break can be observed. This means that some blends, in particular the high RNy containing ones, are more rigid and less ductile of the component of the blend taken separately. While a positive deviation from the additive rule is, in general, evidence of some compatibility between the phases, the negative deviations suggest j u s t the opposite with weak phase interaction and bad morphology. The two features are apparently in contrast and then are very diacult to explain by invoking only compatibility/incompatibility effects. Moreover, the rheological results

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R. Scafiwo and F. P. La Mantia

--ti>

-B-H -6-HS
Prediction b\ eqn 1

1400 1200

I
- - __. . 1 -

,
0

--

---

7-

rn\ I +
00

25

50

75

100

Fg. 1 . Newtonian uiscosity-composition ames for different monopolymer blends o f polyamide 6.

clearly indicate that these blends present only a very limited incompatible behavior, due only to some differences in the molecular weight. Therefore, the morphology in the blend at the solid state can be invoked to explain the shape of the mechanical propertiescomposition curves. During cooling, the polyamide is able to crystallize, and therefore it is only the crystalline fraction that determines the mechanical properties and also the different behaviors in the solid state and in the melt. In Table 2 the heats of fusion of virgin and humid recycled polyamide and of two monopolymer blends

are reported. The heat of fusion of H is noticeably higher than that of virgin PA6. This can be explained as the crystalline fraction is increasing with the severity of the melt processing and particularly with the presence of water as on decreasing the molecular weight the crystalhation kinetic increases. Thus, the heat of fusion reported in Table 2 can be considered proportional to the degree of crystallinity. As for the blends, the results indicate that the blends present values of crystallinity that increase with the amount of the recycled component, becoming even higher than that of the two components of the blend. This behavior,

850

I:, hIPa

+D
ROO

750

700

650

25

50

75

100

Fg. 2. Elastic modulus-composition curvesfor dflerent monopolymer blends o f polyamide 6.

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Monopolymer Blends o f Virgin and Recycled PA6

-e-D -8--H
+HS

38

, RV!
O o

- -~

_______
50

____--____

25

75

100

Fig. 3. Tensile stress-composition curues f o r di3erent monopolymer blends o f polyarnide 6.

apparently surprising. has been already observed for other monopolymer blends and can be reasonably i n terpreted considering that the lower molecular weight chains of recycling component act as nucleating agent for the higher molecular weight fraction. This feature also explains why these effects are amplified on increasing the degradation level: in these cases the molecular weight is lower and the crystallization kinetic is even higher. Moreover, the crystal morphology is also affected by the recycling operations. In Fig. 5 the DSC curves of D, H and the D/H 50/50 blend are reported. It is worth noting that all the curves are related to the first heating on samples cut off from the same ones used to measure the mechanical properties, to

put i n evidence the relationships between the crystall i n i t y ,the crystal morphology and the results obtained by mechanical measurements. The heat of fusion is larger in the H sample with respect to the D sample, and a slight increase of the onset temperature can be also observed. The onset temperature of a DSC thermogram is strictly related to the dimension of the crystals, and in particular, a higher onset temperature indicated larger crystals. Apart from these features, the main difference between the two curves is that in the H sample a low melting phase is present (with some kind of a secondary peak not present in the D sample), and the main melting peak is broader in the H sample. As for the D/H blend,

50 4
~

RN\. __
25 50

00

0-

I
100

75

Flg. 4. Elongation at break-composition c m s for different monopolymer blends o f polyamide 6.

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R. Scaffmo and F. P. La Mantia

Table 2. Heats of Fusion of Virgin and Humid Recycled Polvamide and of Two Monopolymer Blends. Sample
PA6 H PA6IH 75/25 PA6IH 25/75

Heat of fusion, Jig

67.1 69.5 69.6 71.8

and the increase of crystallinity tend to depress this property. Finally, it must be evidenced again that the blends prepared with the wet stabilized recycled polyamide show almost the same properties of the dry polyamide containing samples and the relative property composition curves can be superimposed, confirming the behavior already discussed concerning the rheological properties.
CONCLUSIONS

the situation is intermediate between the two pure components but a low melting phase is still present. These features of the curves indicate that there is not only a n increase of crystallinity but also a variation of the crystal morphology. In particular, a low melting phase with a limited crystalline order seems to appear in the monopolymer blend. This change of crystallinity a n d of the crystal morphology of the monopolymer blends influences, of course, their mechanical properties, a s already reported for other systems (1-3, 6, 9-10). In particular, comparing with the properties of the pure components, an increase of the elastic modulus, 3. 2, and of the tensile stress, 3. 3, together with a decrease of the elongation at break, Fig. 4 , are observed and a noticeable deviation from the additive rule is to be evidenced. Of course, also to be considered is the concurrent effect of the decrease of the molecular weight as a result of the thermomechanical degradation that occurred during processing. The elastic modulus and the tensile stress would, in fact, decrease with decreasing molecular weight, and their increase can be reasonably attributed to the increase of crystallinity that is prevalent. shows a very marked The elongation at break, 3 . 4 , variation as both the decrease of the molecular weight

This work deals with the rheological and mechanical properties of monopolymer blends of virgin and recycled polyamide 6. The results indicate that as the dry polyamide does not undergo relevant degradation phenomena, the molecular weights are very similar to those of the fresh polymer and the Newtonian viscosity-composition curve is near to a linear additive rule. This occurs also for the wet sample but only if a stabilizer is added. Wet unstabilized sample containing blends show noticeable deviations from the additive rule owing to the deep difference in the molecular weights caused by hydrolytic degradation of the recycled component. The mechanical properties-composition curves display a more complex behavior with noticeable deviation from linearity. This can be explained by invoking a different morphology in the solid state for the different crystallinity, as a function of the composition, due to some nucleating effect of the lower molecular weight degraded polyamide chains. The final result is a more rigid and brittle material, if compared with the pure components, in the whole composition range.
ACKNOWLEDGMENTS

This work has been financially supported by the University of Palermo RS 60%.

Fig. 5. DSC curves o f D, H a n d D / H 50/50 w / w blends.

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Monopolymer Blends of Virgin and Recycled PA6

REFERENCES
1. R. Scaffaro and F.P.La Mantia, in Handbook ofPoZymer a Mantia, ed.. W R A , in press. Recycling, Ch. 6, F.P. L 2. F. P. La Mantia, Frontiers i n the Science and Technology o f Polymer Recycling, p. 385, G. Akovali, C . A. Bemarrdo, J. Leidner, L. A. Utracki, and M. Xanthos, eds., Kluwer Academic Publishers, Amsterdam (1998). 3. J . Scheirs, Polymer Recycling, J o h n Wiley & Sons, United States (1998). 4. F. P. La Mantia and M. Wenguang, Polym. Network Blends, 5 , 173 (1995). 5. M. Marrone and F. P. La Mantia, PoZym. Recycling, 2, 17 (1996).

6. A. Valenza and F. P. L a Mantia, Polym. Degr. Stab., 20, 63 (1988). 7. C. Albano, G. Sanchez, and A. Ismayel, J. Macr. Sci. Pure Appl. Chern, ASS, 1349 (1998). 8. N. Hannig and E. Raddatz, Recycling and Recovery o f Plastics, p. 571, J. Brandrup, M. Bittner, W. Michaeli. and G . Menges, eds., Carl Hanser Verlag, Vienna ( 1996). 9. C. Pattanakul, S. Selke, C. Lai, and J. Miltz, J. Appl. Polym Sci., 43, 2147 (1991). 10. F. P. L a Mantia and R. S d a r o , P o Z g y m e r Recycling, 3,1 (1997). n 11. F. P. La Mantia and R. S d a r o , PoZym. Degr. Stab., i press (2001).

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