HDPE, additives Antioxidants

Polyethylene and polypropylene blended with iron carboxylate complexes, for example, acetylacetonate (FeAcAc) and stearates (FeSt), and irradiated by UV light under accelerated aging conditions were shown to act as effective phtoactivators giving rise to rapid photoxidation as shown from the rapid rate of carbonyl formation without any induction period (see Fig. 16.4a for FeAcAc in HDPE) and with a reduction in molar mass (see Fig. 16.2a for FeSt in LDPE). However, these complexes have been shown to cause considerable oxidation to both PE and PP during processing reflected in a sharp increase in the polymer s melt flow index (reflecting chain scission and drop in molar mass) (Fig 16.4b) and act, therefore, as thermal prooxidants and cannot be used without the use of additional antioxidants in the system [2,3,17-19,48,49]. 

In more recent developments siloxane additives (Figure 3.22) exhibit good resistance to extraction, as shown in Figure 3.1 for Soxhlet extraction of HDPE plaques. While nonpolymeric antioxidants (Anox 20 and Anox PP18) were completely extracted after lOh, at the same time more than 40% of the initial concentration... 

Tomboulian et al. (2002) has reported that butylated hydroxytoluene (BHT) can impart a "burnt plastic" odor and is an additive in HDPE pipes. Quinone may be derived from BHT due to interactions with residual chlorine in pipes (Anselme et al., 1985). Yam et al. (1996) reported that antioxidants, such as vitamin E, Irganox 1010, and BHT, contributed to off-flavors in water. Vitamin E yielded less off-flavor, possibly due to lower aldehyde and ketone concentrations. Extrusion temperatures over 280 °C and exposure time for melt contributed to more oxidation of LDPE films and higher intensities of off-flavors in water in contact with LDPE with different antioxidants (Andersson et al., 2005). 

Heat-resistant [218] soft foams were prepared from the blends of hdPE with E-P random copolymers. The azodicarbanamide acts as a thermal antioxidant and the crosslinking of the blend was increased by electron beam radiations and foamed at 225 °C with 2320% expansion. A blend of 35 wt.% PE-PP (8 92), 15 wt.% E-P block copolymers, and 50 wt.% EPDM showed accelerated weathering resitance [219] 1000 h probably due to crosslinking between constituents of the block copolymer, polyblend and EPDM. The effect of filler and thermodynamic compatibility on kaolin-filled PE-PP blend was studied by Lipatov and coworkers [220]. The thermodynamic interaction parameter (%) decreased and thermodynamic stability increased by filler addition, the degree of crystallinity decreased with increasing thermodynamic compatibility of the components due to sharp decrease in the phase separation rate during cooling. 

Selection of the compound ingredients fractions of LDPEs and HDPEs and specific additives such as stabilizers, antioxidants, flame-retardants, and so forth. 

Starting January 2003 GeoDeck boards were made without adding antioxidant, as the HDPE supplier had assured that the plastic had an unusually high amount of antioxidants. These boards were made until March-April 2003, and after that the manufacturing continued with another HDPE source but the additions of the antioxidant was not resumed. This was a dramatic mistake. Manufacturing without the antioxidant was continued until the beginning of October 2003. The plant QC system could not detect the problem because there was no procedure in place that would have been able to detect a low amount (or a complete absence) of antioxidants in composite materials. The procedure was developed and implemented in the plant QC system later (see below). 

Mechano—chemical processes that are essential for HDPE macromolecular dispersion were defined by analyzing MWD of the transfer fragments of polyolefine—based composites doped with active additives (5 wt.%), such as antioxidant (Neozone D), aromatic compound (anthracene) and metal seilt (zinc stearate). Effect of the active additives on molecular features and certain friction characteristics of HDPE (load 0.5 MPa sliding velocity = 0.25 m/s) is shown in Table II. 

In packaging, three resins account for the majority of the market for antioxidants PP, PE, and HIPS. For PP, a combination of hindered phenol and phosphite antioxidants is commonly used, with the total concentration normally from 0.08 to 1%, depending on formulation and end use. Clba Specialty Chemicals has developed the phenolic antioxidant family of Irganox for use in PP and PE, and also the Irgafos family, which are phosphite stabilizers used in combination with phenolic antioxidants. For LDPE, BHT, a phenolic antioxidant, is normally incorporated at levels of 50 to 500 ppm however there is a tendency to employ less volatile additives to prevent their migration from the resin. For HDPE and LLDPE, antioxidants less volatile than BHT, such as polyphenols, at higher concentrations, are normally used In combination with phosphites. For HIPS, hindered phenols are used in combination with UV absorbers. Alpha-tocopherol (Vitamin E) is sometimes used as an antioxidant for polyolefins. 

Diffusion of a fat into HDPE and of an antioxidant additive from the HDPE, plotted against x/t, where x is the distance from the surface and t the time (from Figge, K, and Rudolf, F, Angewandte Macromol Chemie, 78, 179, 1979, Heuthig and Wepf, Verlag). 

Oxidative degradation and the importance of antioxidant additives have already been discussed in detail in Sect. 5.2.2. T q)ically, phosphite and a hindered phenol are used as the main components of the antioxidant package for most of the HDPE geomembranes available on the market. Normally, carbon black is added as UV stabiliser. The concentration of the antioxidant components is t3 ically in the range of a few thousand ppm (mg/kg). Depletion of these antioxidants was identified as the relevant... 

It is well known from pipe pressure tests that immersion in water enhances antioxidant migration in comparison to air, as was observed in our experiments. Smith et al. attributed this to the influence of carbon black (Smith et al. 1992). Antioxidants are adsorbed at the earbon black surface, whereby the migration process is retarded considerably. During immersion in water some moisture is also present in the HDPE bulk material and this is preferentially adsorbed by the carbon black aggregates. The adsorption of water thereby supersedes that of the antioxidants and decreases the retardation coefficient and increases the apparent diffusion coefficient of the latter. In addition, it was suggested that the antioxidant forms loosely bonded clusters within the dry PE bulk material which may disperse slowly in contact with diffusing water thus enhancing the antioxidant diffusion coefficient (Le Poidevin 1977). 

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