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High Density Polyethylene

Mohamad Shoaib,20511595,m3shoaib@uwaterloo.ca Introduction and Applications: High Density Polyethylene (HDPE) is a thermoplastic polymer with density range of 0.94-0.98 g/cm3. The only type of polyethylene used until 1950s was LDPE. This was produced at high pressure which results in branching and therefore its use was limited. The processes using coordination catalysts for its production were first discovered in early 1950s.Then Karl Ziegler, a German Scientist, made a great contribution by introducing a coordination catalyst which allowed the low pressure production of polyethylene with higher density and thus enhanced mechanical properties. This polyethylene had no branching and was more crystalline, compactly packed and named as HDPE. He along with Natta got Nobel Prize for this contribution. The introduction of coordination catalyst revolutionized the polyethylene industry by providing a better control over the structure of polymer. (Cornelia Vasile, 2005) It has a characteristic high strength to density ratio. Its low degree of branching leads to stronger intermolecular forces and high tensile strength four times that of LDPE. FDA approves it for direct food contact applications because of its non-toxicity. Its high molecular weight and low coefficient of friction gives products which are resistant to gouging, scuffing, and scraping. Moisture and water have no effect on it so it can be used in saltwater and freshwater immersion applications. This reason along with its excellent mechanical properties and mirror smooth inside surface because of which there will be minimum flow head loss makes it one of the most used materials for pipelines. According to Ceresena a market intelligence consulting firm, by 2019 worldwide revenues generated with HDPE will raise dynamically to U.S. $ 70 billion .Blow molding applications such as bottles, industrial drums, automobile fuel tanks and household goods account for over 27% of the world demand. Its excellent electrical properties and moisture resistance makes it a suitable material for wire and cable coatings. Its Injection molding application includes crates, pallets, caps, house wares and toys. (Mark, January 29, 2007) Molecular Weight Measurement: Molecular Weight plays an important role determining the mechanical, solution and bulk properties of polymeric material. These properties effectively alter the polymer processing properties, end use properties and interaction with neighboring molecules of a polymeric compound. Polymerization gives rise to a product with chains of different length. Consequently the Molecular Weight of the polymer is distributed in a range i.e. there is no single molecular weight of a polymer rather a range. This range can be averaged to get the average molecular weight of the polymer; these averages are Mn, Mw and Mz. There are several techniques to measure the average molecular weight of a polymer namely Vapor Pressure Osmometry, Viscosimetry, Spectrometry, end group analysis. These methods give an average of the Molecular Weight Distribution diagram either on number or weight basis. The disadvantage of using the above methods is that the MWD is not obtained. So we can have two different polymers which have same average molecular weight but different MWD.

The technique which is extensively used and most convenient one is known as Gel Permeation Chromatography (GPC). The advantage of GPC over other methods is that it is the only method to get all the averages i.e. Mn, Mw and Mz along with the MWD. It also takes less time compared to other methods on the other had it may be GPC measurement lacks sensitivity in the high-molecular-weight domain. GPC is more commonly known as Size Exclusion Chromatography because the polymeric molecules are separated according to their hydrodynamic volume. Polymeric material is dissolved in an appropriate solvent and is passed through a column packed with particles of defined pores. The molecules elute through the column are collected with time. Larger molecules which do not fit into the pores elute through void volume of the column where as smaller molecules penetrate into the pores and get entrapped and takes longer time to elute compared to large molecules. Polymer is fractioned according to the hydrodynamic volume and not the molecular weight so it requires a calibration with a standard of known molecular weight and similar chemical composition as the sample. Each eluted sample is analyzed for molecular weight with the help of detectors. There are several types of detectors which are used nowadays in integration to get the accurate results. The most widely used detector is refractive index (RI) detector. To perform the GPC temperature is maintained at more than 140C so that it remains in liquid form. Using a PL-GPC210 chromatograph at ultrahigh temperature four HDPE samples are analyzed and the results obtained are shown in figure 3 & 4 and table 1 (Jian Xu, 1998). Chemical Composition Measurement:Properties of polymers for the end use are largely dependent on the chemical composition of the polymer, configuration of molecules and chains morphology. Chemical Composition measurement is done to study the type of monomers in the polymer, how the monomers are sequenced with any isomerism present, what are the end groups and the extent of branching, stereoisomerism, etc. There are several techniques used to measure the chemical composition like FITR, NMR and Raman Spectroscopy. Each method has its own benefit and limitations. We will use FTIR for measuring the chemical composition of HDPE. FTIR means Fourier Transform Infrared Spectroscopy. When a sample is exposed to the IR radiation bonds between the atoms vibrate by absorbing a particular wavelength of the IR radiation corresponding to the characteristic molecular vibration frequency. Two types of molecular vibrations are experienced namely stretching and bending. Only those vibrations which correspond to a net change in the dipole moment of a molecule are noticed in IR Spectroscopy. Spectrometer is calibrated using consistent standards such as polystyrene so that the frequency bands are observed at their appropriate frequencies. The range between 4000-1300 cm-1 is known as functional group region and corresponds to the characteristic vibration of functional group present in the sample. The range i.e. 1300-900 cm-1 is known as finger print region and is always unique for every compound. The advantages of using FTIR are that since a the entire radiation is passed through the sample rather than a monochromatic radiation so much time is saved and this is known as Felgetts Advantage. Secondly as the data is transformed from analog to digital so, IR results are easily manipulated. Results of more than two scans can be

combined to give very good quality spectra allowing getting an excellent spectra from even small samples. Another advantage which is in use nowadays is that FTIR can be used in integration with GPC. Like every process FTIR has a disadvantage that is of artifacts, these are peaks present in the spectrum of a sample which are not present in the sample like water vapor and carbon dioxide peaks. Pure HDPE sample is made and placed in sample cell using KBr disks and then it is exposed to the IR. Figure 2 is the IR spectrum of HDPE. The peak band near 3000 cm-1 corresponds to the symmetrical and asymmetrical stretching vibration of methylene which occurs at 2926cm-1 and 2853 respectively. The band at 1465 cm-1 corresponds to scissoring vibration of methylene. The band at 730 cm -1 indicates the rocking vibration of consecutive methylene groups in a crystalline chain of carbon bonds. The band at 1375 cm-1 attributes to symmetric banding of methyl group. There would have been two bands near 1375 cm -1 had there been significant branching in the polymer. So the band at 1375 cm-1 helps to indicate if there is significant branching in polyethylene. So from the FTIR spectra we conclude that HDPE consist of methylene chains terminating in methyl group. There is insignificant branching and it is crystalline compared to LDPE. Also there is no hydrogen bonding present. (Koenig, 1983) Synthesis, Mechanism and Production:Ethylene polymerization occurs at the interface between the solid catalyst and the polymer matrix, where active centers are located (9). Like other polymeric reactions the HDPE reaction also has three steps, Initiation, Propagation and Termination. Initiation step starts by the addition of monomer to an active center and proceeds through the insertion of ethylene molecule into a metal carbon bond. Propagation is the successive insertion of enthylene molecule into that site by virtue of which chain grows (Table 2). Termination or chain transfer occurs thorugh many different mechanisms. Chain Transfer with hydrogen is one of the most important terminations to control the molecular weight. Some of the most common chain transfer reactions are in Table 3. (Allison, 1956) The transition metal catalysts developed by Zeiglar, Natta and Philips gives several processes to produce linear polyethylene. These catalysts are used according to the desired M.W.D. Fig 6 shows the variation of M.W.D according to the catalyst used. Introduction of these catalysts changed the process conditions dramatically from high pressure to low pressure. The processes which are used to produce HDPE are: (1) Gas Phase (2) Solution and (3) Slurry The gas phase process as the name suggests operates in the gaseous state of ethylene and as the molecules polymerized, they precipitate as a solid (powder) dispersed as a fluid bed in the reactor (Fig.7). The gas is circulated in the polymerized fluidized bed. The reactor temperature is kept less than 115C with a pressure of 350psi so that the powder remains solid. The gas is recycled through the reactor and the polymer is removed from the bed into a separator to recover

the gas. The heat of reaction is compensated by injecting a cooled gas stream. The density of HDPE can be controlled by adding an alpha olefin commoner. Solution Process (Fig.8.) operates with ethylene and produced polymer in liquid state. Raw material is still the same as ethylene, hydrogen, co-monomer and catalyst. An organic dilutent is used to dissolve the reactant. The reactor is operated at more than 150 C (and 500 psi) to keep the polymer in solution sate. Small reactor and short residence time which allow swift transition between different grades and easy control of polymer properties are some of the benefits of this type of process. Slurry process operates with two phases one is the reactants ( ethylene+dilutent) which are in liquid phase and other is the polymer produced which remains suspended as a solid phase (Fig. 9.). Two types of slurry systems are widely used (1) light hydrocarbon loop reactor processes and (2) heavier hydrocarbon stirred tank reactor processes. Increase in temperature (in the presence of H2) increases the MW of the product obtained (Daftaribesheli, 2009). Temperature control is a critical process variable which if go extreme can lead to the decomposition of C=C into C, H2, CH4. MWD distribution can be decreased if the monomer is bypassed from the surface site to the inner site. The easiest way to achieve this is to kill the surface sites once it has reached the sufficient degree of polymerization (Merrill, 1971). Properties Mechanical Properties: HDPE properties can be varied significantly by controlling the molecular weight distribution, the degree of branching with its placement, crystallinity etc. Industries produce several grades of HDPE with different end use application and properties according to this principal. The end use properties are the stiffness, flexural modulus, gloss or clarity, chemical resistance, the impact, tensile properties, electrical insulation properties and more. Elongation of HDPE into film or rod brings out mechanical and structural changes (Mark, January 29, 2007).Molecular weight largely influences the stress-strain behavior of HDPE. Low molecular weight samples are brittle and break at low strain levels without a neck development. Increase in MW decreases the elongation at the breakpoint and an increase in tensile strength. . HDPE samples with M.W more than 1,500,000 have a very high tensile strength and can elongate to 400% without developing a neck. Molecular weight also affects the impact strength from low impact resistance to high as the MW is increased. Mechanical strength of a polymer depends to a large extent on intercrystallite links. These links are the weakest link in the structure and highly stretchable up to 40 times, thus to enhance the mechanical properties extent of these is increased Fig .10. (Mark, January 29, 2007). Chemical Resistance: HDPE is saturated hydrocarbon and thus has very low chemical reactivity. Also, high crystallinity leads to low permeability to most chemicals which makes it even more inert thus higher the degree of crystallinity of HDPE, greater the chemical resistance. This property of HDPE makes it suitable for applications involving aqueous solutions of salts, weak acids and bases, sewage and wastewater. However it cannot be used in handling Aromatic Hydrocarbons such as benzene and toluene, hydrocarbons in liquid state such as LPG, crude oil,

gasoline etc, because of their much greater solvating effects .Also increasing the temperature reduces the chemical resistance. (Institute) Degradation: Because of the high bond energy of C-C bond HDPE is quite stable as the temperature is increased above 295-300 C in an inert medium, breakage and cross linking of chains start. This reaction is almost similar to the Thermal Cracking of Hydrocarbons. On the other hand degradation of used HDPE can be done in the presence of certain solvents which are poor hydrogen donating agents to yield different hydrocarbons which can be further used. As an example Fig. 5 shows the effect of different solvents on the yield of hydrocarbons obtained at a temperature of 400C . (D.P. Serrano, January 2007) Research Advances:Polyethylene and Polypropylene are similar polymers but are thermodynamically immiscible. So their blend results to have extremely low fracture strain and poor toughness. There has been lot of work to bind these polymers via some chemical bonding using interfacial coupling reactions but binding these using physical methods or without chemical reaction has not been researched to that extent. One such paper has been represented by (Jie Song, 2012) where they have used lamination and co-extrusion processes to blend the PE and PP samples. Cooling rate is very important in terms of determining interfacial adhesion between the polymers. For all the samples blended with lamination ice water gives stronger adhesion compared to air cooling. Faster cooling rates in co-extrusion process also give rise to stronger adhesion. In another work done by (Lin Y.J., March 2010) adhesion of propylene ethylene (P/E) copolymers to polypropylene (PP) and high density polyethylene (HDPE) blends is investigated. The P/E copolymer has been used as compatibilizer. A good compatibilizer should be miscible with both the constituents so that it can cross the interface forming bridges that couple the two phases together. P/E may be a good compatibilizer for HDPE and PP blend because the propylene segments which are high are compatible with PP and high ethylene segments are compatible with HDPE.Carbon nanotubes (CNTs) are also being investigated for the same purpose. CNTs because of their extremely high tensile strength and modulus with similar chain structure as of polymers are a famous material among researchers. A similar work has been done by (Jie Chen, 8 January 2013). They have introduced functionalized multiwalled carbon nanotubes (FMWCNTs) at the interface of HDPE and Polyamide 6 interface. The peel adhesion strength is measured and the results obtained show an improvement in interfacial adhesion of the blend.

Works Cited
Allison, J. R. (1956). Polyethylene. New York: Interscience Publishers LTD. Cornelia Vasile, M. P. (2005). Practical Guide to Polyethylene. Shawbury: Rapra Technology Limited. D.P. Serrano, ,. J. (January 2007). Effects of hydrogen-donating solvents on the thermal degradation of HDPE. Journal of Analytical and Applied Pyrolysis , 194-199. Daftaribesheli, M. (2009). COMPARISON OF CATALYTIC ETHYLENE POLYMERIZATION IN SLURRY AND GAS PHASE. Twente: University of Twente-The Netherlands. Institute, P. P. Pastics Pipe Institue, Chapter 3 Material Properties plasticpipe.org/pdf/chapter03.pdf. Jaffer, A. (2012). FreeSnell: Polyethylene. http://people.csail.mit.edu/jaffer/FreeSnell/polyethylene.html. Jian Xu, P. J. (1998). Study on the determination of the molecular weight of. Macrornol. Rapid Commun , 115-118. Jie Chen, Y.-y. S.-h. (8 January 2013). Improving interfacial adhesion between immiscible polymers by carbon nanotubes. Polymer , 464471. Jie Song, A. B. (2012). Adhesion between polyethylenes and different types. Polymer Journal , 939945. Koenig, J. L. (1983). Fourier Transform Infrared Spectroscopy of Polymers. Advances in Polymer Science , 89-147. Lin Y.J., P. B. (March 2010). Adhesion of propylene-ethylene copolymers to high-density polyethylene. Polymer Engineering and Science , 592-605. Mark, H. F. (January 29, 2007). Encyclopedia Of Polymer Science and Technology. New Jersy: WileyInterscience; 3rd Edition edition. Merrill, D. S. (1971). Molecular Weight Distribution of Polyethylene Produced by Ziegler-Nat ta Catalysts. Macromolecules , 599-604. Shingo Kobayashi, J. S. (2011). Amino-Functionalized Polyethylene for Enhancing the Adhesion between Polyolefins and Polyurethanes. Ind. Eng. Chem. Res. , 32743279.

Fig.1. Schematics of FTIR

Fig.2. IR Spectra of HDPE (Jaffer, 2012)

Fig.3. Calibration curve for PE and PS at 160C

Fig.4. Chromatograms of HDPE at 160C

Fig .5. Effect of different solvents on the yield of HC obtained

Fig.6.Variation of HDPE MWD according to the type of catalyst used

Fig.7. Gas Phase Process

Fig.8. Solution Process

Fig.9. Slurry Process

Fig.10. Strength decreases as intercrystallite links decrease

Table 1:

Table 2:

(a) Catalyst Formation (b) Chain Propagation in which Cr d-orbitals interact with the pie electron cloud of ethylene. Tabel 3: Chain Termination: Transfer with monomer: Ti-CH2-CH2-polymer + C2H4Ti-CH2CH3 + CH2=CH-polymer Transfer with organometallic compounds: Ti-polymer + (C2H5)3AlTi-C2H5 + (C2H5)2Al-polymer Transfer with hydrogen:

Ti-polymer + H2Ti-H + polymer-H

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