Tailored bimodal ultra‐high molecular weight polyethylene particles

A single molecular catalyst system supported on MgCl₂ has been developed and combined with a simple two‐stage fed‐batch polymerization process to produce tailored bimodal polyethylene reactor blend particles of UHMWPE. By varying and controlling the process conditions in the first stage and second stage, bimodal HMWPE:UHMWPE reactor particles are obtained with independent control over the individual molar masses, the mass ratio of the HMWPE and UHMWPE components, and the reactor powder particle size. This allows multidimensional control over the individual UHMWPE reactor particle properties. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1645–1656     

Surface modification of ultra‐high molecular weight polyethylene fibers by chromic acid

Ultra‐high molecular weight polyethylene (UHMWPE) fibers were modified by chromic acid. The effects of surface modification were evaluated with Fourier transform infrared spectroscopy (FTIR), X‐ray photoelectron spectroscopy (XPS), contact angle measurement, and scanning electron microscope (SEM). The results showed that both the content of O‐containing functional groups and surface roughness of modified fibers increased. The polar groups on the modified fiber surface decreased the contact angles with water and ethylene glycol, as evidenced by contact angle measurement. The tensile test results showed the strength and the elongation at break of UHMWPE fibers decreased but the modulus increased after chromic acid modification. Copyright © 2016 John Wiley & Sons, Ltd.     

Structure transfer from a polymeric melt to the solid state. Part I: The influence of chain entanglements in linear polyethylene

Melt-spinning experiments were carried out at high quenching rates. Mechanical properties (elongation at break, natural draw ratio, and elastic recovery) have been measured. Significant variations of these quantities were observed when extrusion conditions were changed. This has been attributed to different states of the entanglements within the melt, which are directly transferred into the solid state. This intercorrelation between melt and solid-state properties has been substantiated in the case of rapidly cooled samples, where a poor crystallization on one side and a simultaneous good conservation of melt history on the other side are provoked.     

Modification of ultra‐high‐molecular weight polyethylene by various fluorinating routes

Chemical–physical properties of ultra‐high‐molecular weight polyethylene (UHMWPE) treated by direct fluorination, direct fluorination accompanied with UV irradiation, by XeF₂ and by TbF₄, were tested by FTIR spectroscopy, visible spectroscopy, 19F and 13C NMR, scanning electron microscopy, XRD, and EPR. Surface energy measurements were carried out. The direct fluorination of UHMWPE is a diffusion‐controlled process, but treatment with XeF₂ is a kinetically controlled one. Direct fluorination and direct fluorination accompanied with UV irradiation results mainly in a formation of ? CF₂? groups. On the contrary, ? CHF? groups are prevailing in UHMWPE treated with XeF₂ and TbF₄. Surface texture of UHMWPE treated with XeF₂ and with F₂ is quite different. Direct fluorination results in a higher polarity of the polymer surface when compared with treatment with XeF₂. For the case of direct fluorination, both long‐lived peroxy and fluoroalkylradicals are formed. For the case of treatment with XeF₂, only fluoroalkylradicals were detected. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49:3559–3573, 2011     

Surface studies of ultra‐high molecular weight polyethylene irradiated with high‐energy pulsed electron beams in air

Ultra‐high molecular weight polyethylene (UHMWPE) was irradiated in air with high‐energy (9 MeV), pulsed electron beams to doses ranging from 2.5 to 100 Mrad and subsequently heat treated at 120°C for a time period of 120 min. Surface characterization of the target side of irradiated UHMWPE samples was carried out both before and after the heat treatment by means of attenuated total reflection Fourier‐transform infrared (FTIR/ATR) spectroscopy and microhardness measurement. The obtained results provided further evidence supporting our earlier observation (Tretinnikov, O. N.; Ogata, S.; Ikada, Y. Polymer 1998, 39, 6115) that thermal decomposition of hydroperoxides formed upon irradiation of UHMWPE with high‐energy, pulsed electron beams in air leads to surface crosslinking, and the subsequent surface hardening of the irradiated polymer. Importantly, we found that this phenomenon has the highest contribution to the surface hardness enhancement of the polymer when the radiation dose is in the range of 10–30 Mrad. In addition, we found that this irradiation and subsequent heat treatment of UHMWPE in air does not lead to formation of carbonyl‐containing products unless the radiation dose exceeds 20 Mrad. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1503–1512, 1999     

Melt drawing of ultra‐high molecular weight polyethylene: Comparison of Ziegler‐ and metallocene‐catalyzed reactor powders

The drawing behavior of the ultra‐high molecular weight polyethylene (UHMW‐PE) melts has been studied by comparing the stress/strain curves for two types of samples as polymerized using conventional Ziegler and newer metallocene catalyst systems. Two UHMW‐PE samples, having the same viscosity average molecular weight of 3.3 × 10⁶, but different molecular weight distribution, have been drawn from melt at special conditions. The sample films for drawing were prepared by compression molding of reactor powders at 180°C in the melt. Differences in the structural changes during drawing and resultant properties, ascribable to their broad or narrow molecular weight distribution, were estimated from tensile tests, SEM observations, X‐ray measurements and thermal analyses. The metallocene‐catalyzed sample having narrower molecular weight distribution, could be effectively drawn from the melt up to a maximum draw ratio (DR) of 20, significantly lower than that obtained for the Ziegler‐catalyzed sample, ∼ 50. The stress/strain curves on drawing were remarkably influenced by draw conditions, including draw temperature and rate. However, the most effective draw for both was achieved at 150°C and a strain rate of 5 min⁻¹, independent of sample molecular weight distribution. The efficiency of drawing, as evaluated by the resultant tensile properties as a function of DR, was higher for the metallocene‐catalyzed sample having narrower molecular weight distribution. Nevertheless, the maximum achieved tensile modulus and strength for the Ziegler sample, 50–55 and 0.90 GPa, respectively, were significantly higher than those for the metallocene sample, 20 and 0.65 GPa, respectively, reflecting the markedly higher drawability for the former than the latter. The stress/strain behavior indicated that the origin of differences during drawing from the melt could be attributed to the ease of chain relaxation for the lower molecular weight chains in the melt. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1921–1930, 1999     

Surface treatment of ultra‐high molecular weight polyethylene fibers using potassium permanganate and mechanical properties of its composites

Potassium permanganate was applied to improve the surface properties of the ultra‐high molecular weight polyethylene (UHMWPE) fibers. The results suggested that the surface oxygen atoms increased dramatically and the O/C ratio increased from 0.030 to 0.563 after treatment. The increased surface roughness and the O‐containing groups on the treated fiber surface decreased the contact angles with water and ethylene glycol. The crystallinity and the crystallite size of the treated fibers increased, and the DSC results indicated that chain scission and the formation of ―C═O chemical defects in the amorphous region were the main mechanisms of the deterioration of the treated UHMEPE fibers. The breaking strength and the elongation at break of the fibers decreased, but the modulus increased after treatment. The treated fibers exhibited better adhesion with epoxy matrix. An improvement of 27.6% from 101.4 to 129.4 MPa in ILSS confirmed the improvement in the interfacial adhesion strength of composites. The impact and bending strength of composites were both improved.     

Towards advanced circuit board materials: adhesion of copper foil to ultra‐high molecular weight polyethylene composite

Polyethylene based composites are attractive materials for advanced circuit board applications because of their unique combination of properties: low dielectric constant and loss factor, light weight, high flexural modulus and low thermal expansion coefficient controlled in all spatial directions. This investigation describes a process to consolidate chopped fibers of ultra‐high molecular weight polyethylene concurrently with its bonding to a copper foil. Bonding is affected by a thin sheet of low‐density polyethylene, incorporating a crosslinking agent with a concentration gradient across the sheets thickness. In this single step process, the composite material is formed and bonded to the metal foil, achieving good adhesion without the use of extraneous glue. Copyright © 2002 John Wiley & Sons, Ltd.     

Effects of molecular characteristics and processing conditions on melt‐drawing behavior of ultrahigh molecular weight polyethylene

The effects of molecular characteristics and processing conditions on melt‐drawing behavior of ultrahigh molecular weight polyethylene (UHMW‐PE) are discussed, based on a combination of in situ X‐ray measurement and stress–strain behavior. The sample films of metallocene‐ and Ziegler‐catalyzed UHMW‐PEs with a similar viscosity average MW of ～10⁷ were prepared by compression molding at 180 °C. Stress profiles recorded at 160 °C above the melting temperature of 135 °C exhibited a plateau stress region for both films. The relative change in the intensities of the amorphous scattering recorded on the equator and on the meridian indicated the orientation of amorphous chains along the draw axis with increasing strain. However, there was a substantial difference in the subsequent crystallization into the hexagonal phase, reflecting the molecular characteristics, that is, MW distribution of each sample film. Rapid crystallization into the hexagonal phase occurred at the beginning point of the plateau stress region in melt‐drawing for metallocene‐catalyzed UHMW‐PE film. In contrast, gradual crystallization into the hexagonal phase occurred at the middle point of the plateau stress region for the Ziegler‐catalyzed film, suggesting an ease of chain slippage during drawing. These results demonstrate that the difference in the MW distribution due to the polymerization catalyst system dominates the phase development mechanism during melt‐drawing. The effect of the processing conditions, that is, the including strain rate and drawing temperature, on the melt‐drawing behavior is also discussed. The obtained results indicate that the traditional temperature–strain rate relationship is effective for transient crystallization in to the hexagonal phase during melt‐drawing, as well as for typically oriented crystallization during ultradrawing in the solid state. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2455–2467, 2006     

Effects of different ultrahigh molecular weight polyethylene contents on the formation and evolution of hierarchical crystal structure of high-density polyethylene/ultrahigh molecular weight polyethylene blend fibers

In this paper, the blend fibers of ultrahigh molecular weight polyethylene (UHMWPE) and high-density polyethylene (HDPE) were prepared by solution blending and gel spinning process. The uniformity of the blend fibers has been confirmed by rheological data and thermodynamic unimodal curve. They were further characterized by single fiber strength test, scanning electron microscopy, wide-angle X-ray diffraction, small-angle X-ray scattering, and so forth, to explore the structural evolution mechanism with the change of UHMWPE content. The results showed that when the molar content of UHMWPE was only 2.9 mol%, entanglement appeared in the structure of shish-kebab, and when the proportion reached 20 mol%, an interlocking structure could be observed. With the increase of UHMWPE content, kebab began to be networked, and when the content reached 33 mol%, kebab's orientation reached its peak. After that, the interlocking network structure gradually improved. When the content reached 50 mol%, the shish's orientation reached saturation, and the shish-kebab network became perfect. In addition, with the increase of UHMWPE content, stress-induced recrystallization occurred on the wafer, some kebab would be converted into shish crystals, and when the content exceeded 50 mol%, the microfibers began to merge, and the wafer became denser, but still had entanglements. Our work has proposed a quantitative explanation for the evolution of hierarchical crystal structure of HDPE/UHMWPE blend fibers.     

Moderately branched ultra‐high molecular weight polyethylene by using N,N′‐nickel catalysts adorned with sterically hindered dibenzocycloheptyl groups

Five examples of unsymmetrical 1,2‐bis (arylimino) acenaphthene ( L1 – L5 ), each containing one N‐2,4‐bis (dibenzocycloheptyl)‐6‐methylphenyl group and one sterically and electronically variable N‐aryl group, have been used to prepare the N,N′‐nickel (II) halide complexes, [1‐[2,4‐{(C₁₅H₁₃}₂–6‐MeC₆H₂N]‐2‐(ArN)C₂C₁₀H₆]NiX₂ (X = Br: Ar = 2,6‐Me₂C₆H₃ Ni1 , 2,6‐Et₂C₆H₃ Ni2 , 2,6‐i‐Pr₂C₆H₃ Ni3 , 2,4,6‐Me₃C₆H₂ Ni4 , 2,6‐Et₂–4‐MeC₆H₂ Ni5 ) and (X = Cl: Ar = 2,6‐Me₂C₆H₃ Ni6 , 2,6‐Et₂C₆H₃ Ni7 , 2,6‐i‐Pr₂C₆H₃ Ni8 , 2,4,6‐Me₃C₆H₂ Ni9 , 2,6‐Et₂–4‐MeC₆H₂ Ni10 ), in high yield. The molecular structures Ni3 and Ni7 highlight the extensive steric protection imparted by the ortho‐dibenzocycloheptyl group and the distorted tetrahedral geometry conferred to the nickel center. On activation with either Et₂AlCl or MAO, Ni1 – Ni10 exhibited very high activities for ethylene polymerization with the least bulky Ni1 the most active (up to 1.06  ×  10⁷ g PE mol^?1(Ni) h^?1 with MAO). Notably, these sterically bulky catalysts have a propensity towards generating very high molecular weight polyethylene with moderate levels of branching and narrow dispersities with the most hindered Ni3 and Ni8 affording ultra‐high molecular weight material (up to 1.5  ×  10⁶ g mol^?1). Indeed, both the activity and molecular weights of the resulting polyethylene are among the highest to be reported for this class of unsymmetrical 1,2‐bis (imino)acenaphthene‐nickel catalyst.     

Super‐fast oil uptake using porous ultra‐high molecular weight polyethylene sheets

This paper presents the oil uptake of porous sorbent polymer sheets consisting of ultra‐high molecular weight polyethylene. A comprehensive set of experiments are performed showing the saturation contact time, retention value, mechanical properties, oil pick‐up ratio, pick‐up density, and dynamic dripping profile. Kinetic modeling of the oil sorption is also provided. The experimental results show a good correlation with the pseudo‐second order model. The sheets exhibit high oil uptake speeds, requiring less than 2 min in contact with the oil to reach saturation. The sheets fulfill the criteria of high uptake kinetics, high sorption capacity, and high mechanical strength simultaneously. Those characteristics enable their use in practical spill response. Copyright © 2014 John Wiley & Sons, Ltd.     

Structural transformation from shish‐kebab crystals to micro‐fibrils through hot stretching process of gel‐spun ultra‐high molecular weight polyethylene fibers with high concentration solution

Structural evolution of gel‐spun ultra‐high molecular weight polyethylene fibers with high concentration solution via hot stretching process was investigated by in situ small‐angle X‐ray scattering, in situ wide‐angle X‐ray diffraction measurements, scanning electron microscopy, and differential scanning calorimetry. With the increase of stretching strain, the long period continuously increases at relative lower stretching temperature, while it first increases and then decreases rapidly at relative higher stretching temperature. The kebab thickness almost keeps constant during the whole hot‐stretching process and the kebab diameter continually decreases for all stretching temperatures. Moreover, the length of shish decreases slightly and the shish quantity increases although there is almost no change in the diameter of shish crystals during the hot stretching process. The degree of crystal orientation at different temperatures is as high as above 0.9 during the whole stretching process. These results indicate that the shish‐kebab crystals in ultra‐high molecular weight polyethylene fibers can transform continuously into the micro‐fibril structure composed mostly of shish crystals through the hot stretching process. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 225–238     

Effect of molecular architecture on quiescent and shear‐induced crystallization of polyethylene

The aim of this work is to investigate the effect of the molecular structure of polyethylene on the crystallization kinetics. In static conditions, the increase of the degree of branching leads to the decrease of the crystallization temperature, the melting temperature, and the crystallinity. Indeed, the crystal thickness is controlled by the length of PE segments between branching. The effect of preshear on crystallization kinetics was studied by following the dynamic modulus along the time after a treatment of constant shear rate. Particularly, the effect of the shear rate was investigated. The enhancement of crystallization kinetics appears directly linked to the relaxation time of the melt polymer. Expressed by the Weissenberg number, a “master curve” is obtained independent of the amount and length of branching, leading to the conclusion that the nucleation due to shear is conditioned by the molecular architecture mainly via its effect on the relaxation time. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1597–1607, 2006     

Critical review of the molecular topology of semicrystalline polymers: The origin and assessment of intercrystalline tie molecules and chain entanglements

Intercrystalline molecular connections in semicrystalline polymers have been the subject of numerous discussions and controversies. Nevertheless, there is one point of agreement: such intercrystalline tie molecules have a prime role in the mechanical and use properties of the materials, notably the resistance to slow crack growth. This article is a critical review of the mechanisms of generation of the tie molecules during the stage of crystallization and of the experimental and theoretical assessment of their concentration. Polyethylene and related materials are mainly studied. The contribution of chain entanglements is also discussed in parallel with tie molecules. Particular attention is paid to Huang and Brown's statistical approach, which appears to be the most appropriate one for predictive purposes and has aroused much interest from various authors. Attempts are made to provide solutions to the shortcomings of this model. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1729–1748, 2005     

A calorimetric study of normal high density and ultra-high molecular weight polyethylene blends

The melting and the crystallization of blends of ultra-high molecular weight polyethylene (UHMWPE) and polyethylene high density with normal molecular weight (NMWPE) are investigated by means of differential scanning calorimetry (DSC). Mixing the components at a temperature below the flow temperature of UHMWPE (215 °C) results in segregated melting and crystallization. The segregated melting and crystallization temperatures of both components do not depend on composition of the blend. The extreme enthalpy dependence on blend composition is explained in terms of mutual influence exhibited by the components with respect to each other. It is due to the inner stresses in nonflowing UHMWPE characterized with a lot of entangled tie molecules. Mixing the components above the flow temperature of UHMWPE results in only one peak of melting and crystallization respectively. Complete mixing and probably co-crystallization between the components takes place on mixing NMWPE with flowing UHMWPE.     

Studies of non-isothermal crystallization and melting of ultra high molecular weight polyethylene

The non-isothermal crystallization and melting of ultra high molecular weight polyethylene (UHMWPE) were observed by means of differential scanning calorimetry and compared with those of ordinary high-density polyethylene (HDPE). The crystallization temperature (T _c ) and melting point (T _m ) of UHMWPE were found to be higher thanT _c andT _m of HDPE, and the latent heat of crystallization (δH _c ) and fusion (δH _m ) of UHMWPE are smaller thanδH _c andδH _m of HDPE. The results were explained in terms of the theory of polymer crystallization and the structure characteristics of UHMWPE. The relationships between the parameters (T _c ,T _T ,δH _c andδH _m ) and the molecular weight (M) of UHMWPE are discussed. Processing of the experimental data led to the establishment of four expressions describing the above relationships.     

Steered molecular dynamics simulation of elastic behavior of adsorbed single polyethylene chains

We investigate the dynamics of the detachment of single polyethylene (PE) chains from a strongly adsorbing surface in vacuum using a united atom model. Various statistical properties, including the mean‐square end‐to‐end distance 〈R²〉, the mean‐square radii of gyration , , the shape factor , the torsion angle distribution, the average surface adsorption energy , the average total energy , and the average force , are analyzed. The relationship between the average force and the pulling velocity v shows two distinctive regions: a weakly dependence region at Å/ps and a strongly dependence region at Å/ps. Remarkably, the PE chain manifests force hysteresis under sequential stretching and releasing. These investigations may provide some insights into the elastic behavior of adsorbed polymer chains. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2322–2332, 2007     

Strain hardening of high density polyethylene

The introduction of true stress strain measurements, at constant strain rate, has promoted the development of empirical or semiempirical models for large deformations in thermoplastics. One such theory, which proposes that the post yield deformation process can be represented by equations derived from the theories of rubber elasticity, has been successfully applied to several glassy polymers. Unexpectedly, it can also model the post yield deformation of many different grades of polyethylene, even when rubber theory is employed in the simplest Gaussian form. Strain hardening is then represented by the single strain hardening coefficient Gp. Examples are given of this equation, which can be modified to give the true engineering or nominal stress σ_n and then be differentiated to give dσ_n/dλ = Gp ? Y₀ / λ² + 2Gp / λ³, where Y₀ is the yield stress and λ the extension ratio. Negative values of this differential then predict the onset of necking in tension and positive values stabilization of the neck. The relation of Gp to molecular weight is then discussed using literature measurements for polyethylenes of differing molecular weight and similar molecular weight distributions. When these results are then plotted, a strong dependency of Gp on molecular weight is observed. Some implications of these measurements are then considered. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1090–1099, 2007     

Synthesis of polyethylene with bimodal molecular weight distribution by supported iron‐based catalyst

Through immobilization of two iron‐based complexes, [((2,6‐MePh)N = C(Me))₂C₅H₃N]FeCl₂ ( 1 ) and [((2,6‐iPrPh)N = C(Me))₂C₅H₃N]FeCl₂ ( 2 ), on SiO₂ pretreated with tetraethylaluminoxane (TEAO), two supported iron‐based catalysts, 1 /TEAO/SiO₂ ( 3 ) and 2 /TEAO/SiO₂ ( 4 ), were prepared. These two supported catalysts 3 and 4 could be used to catalyze ethylene polymerization with moderate polymerization activity and prepare linear high‐density polyethylene with bimodal molecular weight distribution (MWD). It was demonstrated that immobilization of catalyst could significantly improve molecular weight (MW) of high‐MW fraction of the resultant polyethylene, as well as maintain bimodal MWD of polyethylene produced by the corresponding homogeneous catalysts. Such bimodal MWD of polyethylene produced by supported iron‐based catalysts could be well tailored by varying polymerization conditions, such as ethylene pressure and molar ratio of Al to Fe. It has been proven that TEAO is an efficient activator for both homogeneous and heterogeneous iron‐based catalysts for producing polyethylene with bimodal MWD. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5662–5669, 2004