THE EFFECT OF NITROGEN PURGING ON DEGRADATION DURING REPROCESSING IN INJECTION MOLDING

J. S. Archer and S. H. Dillman, Western Washington University Bellingham WA, 98225 Abstract
This study investigated the effect of nitrogen purging in the material hopper on the melt flow index (MFI), residual oxidative induction time (OIT), color and impact strength of impact modified polypropylene copolymer and polycarbonate during repeated reprocessing through an injection molder. Heat history had the expected effect of increasing MFI, changing color and decreasing impact strength for both resins and decreasing OIT in polypropylene. In polypropylene nitrogen purging significantly reduced the changes in MFI and OIT resulting from repeated reprocessing. However, nitrogen purging did not have a significant effect on the properties of polycarbonate, probably due to its inherent resistance to oxidative degradation. number of times material can be reprocessed. The general response to this situation by industry is to establish a ratio of regrind to virgin material which yields acceptable processing and end product properties for a given part. This procedure poses a problem since it limits the possible benefits associated with the use of regrind. One of the principle modes of degradation is oxidation where oxygen degrades the material through a free radical process [1]. Oxidation can be reduced by the addition of antioxidants (AOs). A large percentage of AO is used up during melt processing where the material is exposed to high temperatures. In addition to temperature, the amount of oxygen present plays a role in the rate and extent to which oxidation occurs. A common test used to determine the effectiveness of AO in polyolefins is OIT by differential scanning calorimetry. The test exposes the sample to an oxygen rich environment while held at constant temperature. OIT is the time at the onset of oxidation less the time required to reach the isothermal temperature. Larger values of OIT suggest greater resistance to oxidation. In an oxygen free environment, oxidation is retarded. One common way to eliminate oxygen from a given environment is through displacement with another gas. Nitrogen is widely used as a purge gas because of its inert properties, availability, low cost and non-toxicity. The hypothesis for this study is that the introduction of nitrogen into the injection molding machines material hopper during processing will limit the amount of oxidative degradation and increase the ability of the material to be reprocessed while retaining critical properties.

Introduction
One of the key advantages of the injection molding process is the ability to limit the amount of waste by reprocessing granulated scrap parts, runner systems and sprues. As the world continues to learn more about the impact humans have on the planet, the need to reduce waste will only increase. The use of regrind not only has environmental benefits but also has economic benefits. With some part designs the sprue and runner system comprises more material than is used for the parts. Reusing this material, which would otherwise be waste, significantly reduces the part cost. However, the use of regrind is not without drawbacks. Non-uniform pellet sizes can lead to inconsistencies in the polymer melt which can cause processing variation and subsequent end product property variations. As virgin material melts from the heater bands and the shear forces applied by the plasticizing screw, some amount of thermooxidative degradation is likely to occur. This degradation has an effect on one of the most important processing properties of the polymer, viscosity. As the molecules degrade, the molecular weight distribution broadens to some degree, which in turn affects the viscosity of the material. Changes in viscosity become most problematic in processing but degradation can also have adverse affects on end product properties. Common problems associated with changes in molecular weight include; changes in color, decreased tensile strength and decreased impact strength. Essentially, any property that is enhanced as the degree of polymerization increases is affected negatively. As a result of decreasing properties there are feasible limits to the

Experimental Procedure
Two resins were used in the experiment; an impact modified polypropylene copolymer of natural color (Dow 7C50H) and polycarbonate with white color (Lexan 141) [2] [3]. The experimental design used was a two factor 3k full factorial with three center points. The experiment in standard run order can be found in Table 1. The two factors were heat history and nitrogen purge rate. Heat history refers to the number of times the material was processed through an 80 ton injection molding machine with an ASTM test sample mold. Samples with one heat history are made from 100% virgin material processed

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once, samples with two heat histories are made by granulating samples with one heat history then 100% of this regrind is reprocessed to make samples (i.e. no virgin/regrind mixtures were used). Nitrogen purge rate refers to the flow in liters per minute at 0.10 MPa (15 psi) of nitrogen into the material hopper. The flow rate was regulated by a flow meter capable of measuring 0 20 LPM. The gas was introduced near the top of the hopper via a small hose fitting. The purging of oxygen was facilitated by the use of a dehumidifying hopper dryer. The intake of the dryer was at the top of the hopper and the output was near the feed throat. The factor levels for heat history were determined by reprocessing material and monitoring the change in properties after each pass. It was found that 5 heat histories would produce sufficient changes in properties to qualify for the high level for both materials. The low and mid factor levels for heat history were subsequently set at 1 and 3 respectively. Table 2 shows the un-coded and corresponding coded values used for each factor in the experiment. The low, mid and high factor levels for nitrogen purge rate were set at 0, 10 and 20 (LPM) respectively. The order of the test runs was randomized to evenly distribute variation among the factors and to prevent any time dependent variation from being inaccurately attributed to a factor. The processing parameters were obtained by resin suppliers recommendations and by following ASTM D 3641. Heater band temperatures were purposefully chosen from the high end of the suppliers recommendation to promote degradation. Polycarbonate was dried at 121C for 3 hours or at 79C overnight. Polypropylene was not pre-dried but the dryer was set at 35C during processing to eliminate surface moisture and to facilitate the circulation of nitrogen. Processing variations were expected to occur with increasing heat histories since changes in molecular weight were expected. These processing variations were monitored by weighing parts throughout processing. If significant changes in part weight were observed the hold pressure was manipulated to retain consistent part weight [4]. Hold pressure was used since it has minimal effect on degradation. Once all the runs were completed samples were grouped into randomized blocks and tested. The tests performed were MFI (ASTM D 1238), OIT (ASTM D 3895), notched Izod impact strength (ASTM D 256) and yellowness index (YI ASTM D 1925). Samples for OIT testing were prepared by using a cylindrical punch on molded falling dart impact discs. The weight of each sample was approximately 6 mg. YI testing was performed on molded tensile bars with a BYK-Gardner handheld spectrophotometer. The illumination/observer used was C/2. Readings were taken at the center of the tensile bar approximately 3 cm from the end opposite the gate. For polypropylene a white background was used.

Background was irrelevant for polycarbonate since the samples were opaque.

Results and Discussion

For polycarbonate heat history had the expected effect of decreasing impact strength, increasing MFI and changing color. The P-values and regression coefficients can be found in Table 3. An alpha of 0.1 was used to determine significance. Since no distinct exothermic peak was observed during OIT testing no values were obtained. This lack of an exotherm is likely due to the oxidative stability of aromatic rings. The oxidative stability of polycarbonate is also evidenced by the fact that nitrogen purging did not have a significant effect on the properties under investigation. For polypropylene heat history had the expected effect of decreasing impact strength, increasing MFI, changing color, and decreasing OIT. Refer to Table 4 for the regression statistics. Contrary to the results for polycarbonate, nitrogen purge rate had a significant effect on the MFI, OIT, and impact strength of polypropylene. Figures 1-3 show the response surface for each of these tests. The abundance of tertiary hydrogen atoms in polypropylene plays a major roll in the results of oxidation. The thermodynamics of the reaction favor the abstraction of a tertiary hydrogen to that of a primary or secondary hydrogen. When a tertiary hydrogen is abstracted from the chain, a sterically hindered carbon radical is formed. The steric hindrance of this radical decreases the likelihood of cross-linking, therefore, chain scission is preferred [5]. The effect of chain scission is a broadening of the molecular weight distribution and a bulk decrease in the molecular weight. Chain scission is responsible for the relatively large positive main effect of heat history on MFI. The negative main effect of nitrogen purge rate on MFI suggests that the presence of nitrogen is in fact reducing the changes in molecular weight caused by oxidation. It is desirable that before oxidation causes chain scission it would be suppressed by the AO present and therefore preserve the molecular weight of the material. As material is reprocessed AOs are depleted as is evidenced by the negative main effect of heat history on OIT. The positive main effect of nitrogen purge rate on OIT provides reason to believe that nitrogen purging increases the life of AO in the material. Higher concentrations of residual AO provide for the possibility of further reprocessing and extended post process life. Changes in molecular weight not only affect rheological properties but also physical properties. In the case of polypropylene, the number of chains completely integrated into a crystal significantly affects the impact strength [5]. The reduction of molecular weight causes an increase in the number of chain ends present in the crystalline phase and effectively decreases the impact

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strength. The negative main effect of heat history on impact strength combined with the MFI data show that the decrease in molecular weight does in fact result in a decrease in impact strength. The interaction between heat history and purge rate shows a kind of stabilization of impact strength at high levels of purge rate. The values are essentially the same at high purge rate regardless of heat history. At a single heat history purge rate appears to have a negative effect on impact strength. It is unclear why this behavior was observed.

References
1. Robertson, Jennifer E., Thermal Degradation Studies of Polycarbonate, PhD thesis dissertation, Virginia Polytechnic Institute (2001). Liang, R and Gupta, R. K., Rheological and Mechanical Properties of Recycled Polycarbonate, SPE ANTEC Proceedings, 3, 2903-2907, (2000). Case, R. M., Korzen, A. P., and MacLean, S. B., The Effects of Regrind Loading Levels and Heat History on the Properties of Selected Engineering Polymers, SPE ANTEC Proceedings, 9125-3128, (2001). Shriver, M. E., Beiter, K. A., and Ishii, K., Performance Characterization of Recycled Thermoplastics for Material Life-Cycle Analysis, SPE ANTEC Proceedings, 40, 2910-2915 (1994). Moore, Edward P. Jr., Polypropylene Handbook. Hanser/Gardner, Cincinnati, 180 (1996).

2.

Conclusion
The effect of nitrogen purging on the reduction of degradation during reprocessing was determined for polypropylene and polycarbonate. Nitrogen purging did not have a significant effect on the properties of polycarbonate. Nitrogen purging significantly reduced the increase in MFI resulting from degradation, increased residual OIT, and stabilized the impact strength of polypropylene.

3.

4.

Acknowledgements
The authors would like to thank Warner Weisbach at GE Plastics for the donation of material and Professor Nicole Hoekstra at WWU for technical support.

5.

Table 1. Experimental Design standard run order.

Heat History -1 1 -1 1 -1 1 0 0 0 0 0 Nitrogen Purge Rate -1 -1 1 1 0 0 -1 1 0 0 0

Table 2. Un-coded and (Coded) Factor Levels.

Low 1 (-1 ) 0 (-1 ) Mid 3 (0 ) 10 (0 ) High 5 (1 ) 20 (1 )

Heat History Purge Rate

Table 3. Regression Statistics Polycarbonate.

MFI (g/10 min) Coefficients P-value Intercept 13.179 0.000 Heat History 2.127 0.000 Purge Rate 0.078 0.655 Interaction -0.120 0.574 HH^2 0.909 0.002 N2^2 0.509 0.065 Impact Strength (J/m) Yellowness Index Coefficients P-value Coefficients P-value 858.127 0.000 14.019 0.000 -45.247 0.000 -1.167 0.000 2.491 0.760 0.027 0.905 2.802 0.779 0.021 0.940 1.947 0.877 0.400 0.259 -20.419 0.108 0.173 0.621

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Table 4. Regression Statistics Polypropylene.

MFI (g/10 min) Coefficients P-value Intercept 10.163 0.000 Heat History 2.549 0.000 Purge Rate -0.938 0.000 Interaction -0.926 0.000 HH^2 0.846 0.000 N2^2 0.193 0.130 OIT (min) Coefficients P-value 6.471 0.000 -1.360 0.000 0.717 0.012 -0.020 0.953 -0.206 0.629 0.444 0.301 Impact Strength (J/m) Yellowness Index Coefficients P-value Coefficients P-value 104.43 0.000 -10.765 0.000 -7.79 0.000 1.179 0.000 -1.90 0.362 -0.041 0.508 7.18 0.007 -0.107 0.161 -1.59 0.620 0.407 0.000 4.12 0.201 0.042 0.659

16 15 14

9 8.5 8

MFI (g/10 min)

13 12 11 10 9 8 -1 0
Heat H istory

OIT (min)

7.5 7 6.5 6

5.5 5 -1 0 Heat H is to -1
ry

1 0

Ra te

rg e

Pu

-1 1

Figure 1. Surface plot of MFI Polypropylene.

Figure 2. Surface plot of OIT Polypropylene.

120

Impact Strength (J/m)

115 110 105 100 95 90 85 -1

Heat 0 H ist ory

1 0

-1 1

Figure 3. Surface plot of Impact Strength Polypropylene.

Key Words: Nitrogen Purge, Oxidation, Recycling

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