Optimization of Extrusion Process Parameters of Recycled High-Density Polyethylene-Thermoplastic Starch Composite for Fused Filament Fabrication

High-density poly-ethylene (HDPE) is a nonbiodegradable recyclable plastic which is widely utilized in single use packaging applications. Consequently, it constitutes a significant amount of plastic waste found in landfills. From literature, it has been shown that parts produced using composites of HDPE with carbohydrate-based polymers, such as thermoplastic starch (TPS), experience mechanical degradation through hydrolytic degradation process. The possible utilization of recycled-HDPE (rHDPE) and TPS composite in nonconventional manufacturing processes such as Fused filament fabrication (FFF) has however not been explored. This study explores the potential application of rHDPE and TPS composites in FFF and optimizes the extrusion process parameters used in rHDPE-TPS filament production process. Taguchi method was utilized to analyze the extrusion process. The extrusion process parameters studied were the spooling speed, extrusion speed and the extrusion temperatures. The response variable studied was the filament diameter. In this research, the maximum TPS content achieved during filament production was 40 wt%. This filament was however challenging to use in FFF printers due to frequent nozzle clogging. Printing was therefore done with filaments that contained 0 - 30 wt% TPS. The experimental results showed that the most significant parameter in extrusion process was the spooling speed, followed by extrusion speed. Extrusion temperature had the least significant influence on the filament diameter. It was observed that increase in TPS content resulted in reduced warping and increased rate of hydrolytic degradation. Mechanical properties of printed parts were investigated and the results showed that increasing TPS content resulted in reduction in tensile strength, reduction in compression strength and increase in stiffness. The findings of this research provide valuable insights to plastic recycling industries and researchers regarding the utilization of recycled HDPE and TPS composites as substitute materials in FFF.

Study on fracture characteristic of welded high-density polyethylene pipe

Crack opening displacement(COD) was applied to characterize the fracture initiation of the tough high density polyethylene. Normal single side notched three point bend specimens and silica rubber replica techniques were used to study the characteristic COD of high density polyethylene pipe and its butt fusion joints including the weld fusion zone and heat affected zone at different temperature from -78 ℃ to 20 ℃ . Testing results show that the characteristic COD appears to depend on the structural features that are determined by welding process and the testing temperature. As the temperature is lowered, the characteristic COD of all zones studied decreases. Because the welding process significantly changes some structural feature of the material, characteristic COD of the weld fusion zone is the smallest one among those of the three zones. The results can be used for the engineering design and failure analysis of HDPE pipe.

MAPPING THE DAMAGED ZONE AROUND THE CRACK TIP IN HIGH DENSITY POLYETHYLENE WITH SYNCHROTRON MICROFOCUS SMALL ANGLE X-RAY SCATTERING TECHNIQUE

The structural changes around a crack tip in a high density polyethylene were investigated by means of scanning synchrotron microfocus small-angle X-ray scattering technique. The scattering data confirm the process of craze structure development near a crack tip based on the evolution of voids. In addition, it was found that the main stress in the plastic zone near a crack tip exhibited a gradient distribution with respect to its strength and direction. The whole damaged area showed a strain distribution indicating a flow behavior toward the crack tip.

PREPARATION OF HIGH DENSITY POLYETHYLENE/POLYETHYLENE-BLOCK-POLY(ETHYLENE GLYCOL)COPOLYMER BLEND POROUS MEMBRANES VIA THERMALLY INDUCED PHASE SEPARATION PROCESS AND THEIR PROPERTIES

High density polyethylene （HDPE）/polyethylene-block-poly（ethylene glycol） （PE-b-PEG） blend porous membranes were prepared via thermally induced phase separation （TIPS） process using diphenyl ether （DPE） as diluent. The phase diagrams of HDPE/PE-b-PEG/DPE systems were determined by optical microscopy and differential scanning calorimetry （DSC）. By varying the content of PE-b-PEG, the effects of PE-b-PEG copolymer on morphology and crystalline structure of membranes were studied by scanning electron microscopy （SEM） and wide angle X-ray diffraction （WAXD）. The chemical compositions of whole membranes and surface layers were characterized by elementary analysis, Fourier transform infrared spectroscopy-attenuated total reflection （FTIR-ATR） and X-ray photoelectron spectroscopy （XPS）. Water contact angle, static protein adsorption and water flux experiments were used to evaluate the hydrophilicity, antifouling and water permeation properties of the membranes. It was found that the addition of PE-b-PEG increased the pore size of the obtained blend membranes. In the investigated range of PE-b-PEG content, the PEG blocks could not aggregate into obviously separated domains in membrane matrix. More importantly, PE-b-PEG could not only be retained stably in the membrane matrix during membrane formation, but also enrich at the membrane surface layer. Such stability and surface enrichment of PE-b-PEG endowed the blend membranes with improved hydrophilicity, protein absorption resistance and water permeation properties, which would be substantially beneficial to HDPE membranes for water treatment application.

High density porous polyethylene material (Medpor) as an unwrapped orbital implant

Objective: To introduce the clinical effect among patients who received an unwrapped orbital implant with high density porous polyethylene material (Medpor) after enucleation or evisceration. Methods: Retrospective analysis of a series of 302 patients with anophthalmia who underwent placement of an unwrapped high density porous polyethylene orbital implant. We compared the patients (n=180) who accepted primary implant placement with those (n=122) who accepted secondary implant placement. Parameters evaluated included: age at time of surgery, date of surgery, sex, implant type and size, surgery type, the surgical procedure and technique performed, and complications. Results: The time of follow-up ranged from 2.0 to 58.0 months (mean 32.5 months). A total of 5 of 302 (1.66%) cases had documented postoperative complications. The following problems were noted after surgery: implant exposure, 3 patients (0.99%); implant removed due to orbital infection, 1 patient (0.34%); ptosis, 1 patient (0.34%). There were no significant complications observed in other 297 cases and all implants showed good orbital mo- tility. The clinical effect of primary implant placement is better than that of secondary placement. Conclusion: High density porous polyethylene material can be used successfully as an unwrapped orbital implant in anopthalmic socket surgery with minimal complications. The material is well tolerated, nonantigenic and has low rate of infection and migration.

Study on the Basic Mechanical Behaviors of High Density Polyethylene Electrofusion Welded Joints at Different Temperature

The basic mechanical behaviors of high density polyethylene electrofusion welded joint at different temperatures were studied by using differently designed specimens in this paper. The results show that the strength of weld bonding plane is higher than that of the pipe and socket materials at room temperature. In order to get the shear strength of electrofusion welded joint, the effective bond lengths were reduced by cutting artificial groove through the socket. The effective bonding length of welded joint to get the shear strength is decreased with decreasing testing temperature. The shear strength and the sensibility to sharp notch of HDPE material increased with decreasing temperature.

OLEOPHOBIC AND HYDROPHOBIC FEATURE EXPERIMENTS OF FLUORINATED HIGH DENSITY POLYETHYLENE

The surface performances of directly fluorinated high density polyethylene （HDPE） are studied with Fourier transform infrared （FT-IR） spectra, scanning electron microscopy （SEM） and contact angle （CA） system. The SEM images show that there is a three-layer structure called the reaction, virgin and boundary layer structure. The depth of fluorinated layer is 5.75 ~m with 1 h fluorination time and 7.86 b^m with 2 h. The depths are 5.46 /~m and 5.07 /~m when fluorine density is 2G and 1~/0, respectively. CA indicates that the HDPE surface property becomes more hydrophobic with the increasing water contact angle from 78.5~ to 104.5~. Oleophobic and hydrophobic features of HDPE are identified by comparison of mass change experiments. It is shown that the in- crement rate of fluorinated HDPE is much lower than that of un-fluorinated HDPE filled in neither distilled water nor jet fuel.

EFFECT OF PAN-MILLING ON RHEOLOGICAL PROPERTIES OF HIGH DENSITY POLYETHYLENE

The effect of pan-milling on the rheological properties of high density polyethylene (HDPE) was studied. An innovative milling apparatus, viz. an inlaid pan-mill, was used. Melt indexer, capillary rheometer, Haake Rheocord 90 single-screw extruder and Brabender rheometer were used to evaluate the rheological properties of HDPE. HDPE with higher initial molecular weight and larger particle size was easier to degrade under pan-milling stress, as indicated by the melt index. Pressure oscillation in capillary flow occurred at significantly higher shear stress and shear rate for milled HDPE than for unmilled HDPE. The apparent shear viscosity of HDPE decreased with increasing times of milling. After milling, the flow activation energy decreased and thus the sensitivity of viscosity to temperature was reduced. Die pressure and torque during single screw extrusion were reduced significantly after milling. Plasticizing time as measured in a Brabander mixer decreased markedly with increasing milling times.

A Study on the Impact of Chemical Structure on the Evolution of Aggregate Structure in Fiber-shaped High Density Polyethylene Vitrimer

Vitrimers have emerged as a prominent research area in the field of polymer materials.Most of the studies have focused on synthesizing polymers with versatile dynamic crosslinking structures,while the impact of chemical structure on aggregate structure of vitrimers,particularly during polymer processing,remains insufficiently investigated.The present study employed commercial maleic anhydride-grafted-high density polyethylene(M-g-HDPE)as the matrix and hexanediol as the crosslinker to facilely obtain fiber-shaped HDPE vitrimers through a reaction extrusion and post-drawing process.Through chemical structure characterization,morphology observation,thermal and mechanical properties investigation,as well as aggregate structure analysis,this work revealed the influence of dynamic bonds on the formation of aggregate structures during fiber-shaped vitrimers processing.A small amount of dynamic bonds in HDPE restricts the motion of PE chain during melt-extruding and post-drawing,resulting in a lower orientation of the PE chains.However,lamellar growth and fibril formation during post-drawing at high temperature are enhanced to some extent due to the competition between dynamic bond and chain relaxation.The uneven morphology of fibershaped HDPE vitrimers can be attributed to the stronger elastic effect brought by dynamic bonding,which plays a more dominant role in determining the mechanical properties of fiber-shaped vitrimers compared to aggregate structure.Abstract Vitrimers have emerged as a prominent research area in the field of polymer materials.Most of the studies have focused on synthesizing polymers with versatile dynamic crosslinking structures,while the impact of chemical structure on aggregate structure of vitrimers,particularly during polymer processing,remains insufficiently investigated.The present study employed commercial maleic anhydride-grafted-high density polyethylene(M-g-HDPE)as the matrix and hexanediol as the crosslinker to facilely obtain fiber-shaped HDPE vitrimers through a reaction extrusion and post-drawing process.Through chemical structure characterization,morphology observation,thermal and mechanical properties investigation,as well as aggregate structure analysis,this work revealed the influence of dynamic bonds on the formation of aggregate structures during fiber-shaped vitrimers processing.A small amount of dynamic bonds in HDPE restricts the motion of PE chain during melt-extruding and post-drawing,resulting in a lower orientation of the PE chains.However,lamellar growth and fibril formation during post-drawing at high temperature are enhanced to some extent due to the competition between dynamic bond and chain relaxation.The uneven morphology of fibershaped HDPE vitrimers can be attributed to the stronger elastic effect brought by dynamic bonding,which plays a more dominant role in determining the mechanical properties of fiber-shaped vitrimers compared to aggregate structure.

Structure,Characterization and Thermal Properties of the Form-Stable Paraffin/High-Density Polyethylene/Expanded Graphite/Epoxy Resin Composite PCMs for Thermal Energy Storage

The form-stable paraffin/high-density polyethylene/expanded graphite/epoxy resin composite phase change materials(CPCMs),exhibiting suitable thermal properties,including low melting temperature,high conductivity and high phase change enthalpy,was developed in this work.Herein,paraffin(PA)was utilized as a core PCM.High-density polyethylene(HDPE)was utilized for the shape stabilization and preventing the PCMs leakage.Expanded graphite(EG)was used to increase its thermal conductivity and act also in the porous supporting material.Epoxy resin(ER)was used to provide flexible encapsulated scaffold morphology and keep a highly tight network structure of the PCMs.However,the physical architecture,the chemical architecture and thermal behavior properties of specimens were investigated by using the spectroscopy and calorimetry techniques.The scanning electron microscope(SEM),X-ray diffraction(XRD)and fourier transform infrared spectrometer FTIR tests have shown good uniformity structure and good compatibility of components.In addition,the thermal conductivity tests revealed that the thermal conductivity of PA,initially 0.31 W/(m·K)improved up to 1.9 times by adding the 6 wt%mass fraction of EG in composite PCMs.Furthermore,the differential scanning calorimeter(DSC)measurements indicated that PA melting enthalpy,initially 231 J/g decreased up to 125 J/g with the increase of the amount of HDPE which was due to the limitation caused by the atomic network constructed by the base material.The thermogravimetric analyzer(TGA)and leakage-proof revealed the enhancement of the degradation of PA with the raise of amount of the HDPE into the CPCMs.Therefore,the proposed form-stable CPCMs are a great candidate for the thermal regulation and thermal energy storage employment.

The Influence of Unidirectional Pressure on Electrical Conductivity of Carbon Black Filled Polyethylene

High density polyethylene filled with condutuctive carbon black was prepared by conventional meltmixing method. The effect of unidirectional pressure on the conductivity was studied. Wide angle X-ray diffraction （ WAXD ） was used to slum： the influence of pressure on the aggregate structure of the polymer filled with carbon black （CB） fillers. A model on the basis of the formation and destruction of conductive networks was proposed to explain the change in the conductivity with the application of pressure.

Improvement of Mechanical,Dynamic-Mechanical and Thermal Properties for Noil Ramie Fiber Reinforced Polyethylene Composites

Noil discarded fibers from fiber production for textile industry have short length and are always considered less valuable.Here,noil ramie fibers/HDPE composite is prepared using twin-screw extruder and the dynamic mechanical and thermal properties are studied.The influence of ramie fiber and maleic anhydride-grafted polyolefin(MA-g-PO)on mechanical,dynamic mechanical and thermal properties is investigated.It is observed that the tensile,flexural and impact properties of the composites treated with MA-g-PO are all improved in comparison to the untreated composites.Dynamic mechanical properties of the composite with MA-g-PO show an increase in the storage modulus with a higherαrelaxation peak,together with the micromorphology analysis,indicating an improved interfacial bonding between fiber and matrix by the MA-g-PO addition.Furthermore,the change in TGA thermograms of composite caused by MA-g-PO exhibits that the addition of MA-g-PO is also helpful to increase the thermal stability of noil ramie fiber/HDPE composites.

HIGH SPEED INJECTION MOLDING OF HIGH DENSITY POLYETHYLENE—EFFECTS OF INJECTION SPEED ON STRUCTURE AND PROPERTIES

Thin wall samples of high density polyethylene （HDPE） were prepared via injection molding with different injection speeds ranging from 100 mm/s to 1200 mm/s. A significant decrease in the tensile strength and Young＇s modulus was observed with increasing injection speed. In order to investigate the mechanism behind this decrease, the orientation, molecular weight, molecular weight distribution, melt flow rate, crystallinity and crystal morphology of HDPE were characterized using two-dimensional wide-angle X-ray diffraction （2D-WAXD）, gel permeation chromatography （GPC）, capillary rheometry and differential scanning calorimetry （DSC）, respectively. It is demonstrated that the orientation, molecular weight, molecular weight distribution, melt flow rate and crystallinity have no obvious change with increasing injection speed. Nevertheless, the content of extended chain crystals or large folded chain crystals was found to decrease with increasing injection speed. Therefore, it is concluded that the decrease in tensile properties is mainly contributed by the reduced content of extended chain crystals or large folded chain crystals. This study provides industry with valuable information for the application of high speed injection molding.

A novel method for the management of sulfone-rich waste produced in the oxidative desulfurization(ODS) process

The oxidative desulfurization(ODS) process is one of the new desulfurization processes for the production of clean fuels. Despite the benefits of the ODS process, this process faces several important challenges. One of the most important challenges of this process is the management of a waste which is rich of sulfone compounds.In the present study, a new strategy which is the addition of waste to the bitumen with other solid waste such as high density polyethylene(HDPE) waste has been investigated. The experimental design method was applied to investigate the effect of addition of the sulfone and HDPE wastes to the properties of the bitumen blends including degree of penetration, softening point, and mass loss. It was found that the sulfone waste can be added to the bitumen as a softener. The results showed that several grades of bitumen including 50/60, 60/70, 85/100 can be produced through the addition of sulfone waste along with the HDPE waste to the base 60/70 bitumen.In general, the application of simple processes such as mixing the wastes with the bitumen can reduce the cost of waste management, considerably.

A New Kind of Shape-stabilized Phase Change Materials

Based on the lowest melting point and Schroeder’s theoretical calculation formula,nano- modified organic composite phase change materials（PCMs）were prepared.The phase transition temperature and the latent heat of the materials were 24℃and 172 J/g,respectively.A new shape-stabilized phase change materials were prepared,using high density polyethylene as supporting material.The PCM kept the shape when temperature was higher than melting point.Thus,it can directly contact with heat transfer media.The structure,morphology and thermal behavior of PCM were analyzed by FTIR,SEM and DSC.

Enhanced Interfacial Adhesion in HDPE/HA Composites by Surface Modification of HA Particles via in situ Polymerization and Copolymerization

Hydroxyapatite （ HA ）- reinforced high density polyethylene （HDPE） was developed as a bone replacement material,In order to enhaace the interfacial bonding between HA and polyethylene and improve the mechanical properties of HDPE/ HA composites, the surface of the micron-sized HA particles was modified by in situ polymerization of butyl acrylate （ BA ） and in situ copolymerization of vinyl triethoxyl silane （ VTES ） and BA , then the modifwd HA particles were compounded with HDPE. The effects of the surface modification of HA on morphology and mechanical properties of HDPE/ HA composites were investigated. The experimental results show that the presence of HA particles does tuft inhibit the polymerization of BA . The poly（ butyl acrylate） （ PBA ） segments on the HA surface enhance the compatibility between HA and HDPE, improve the dispersion of HA particles in HDPE matrix, and enhance the interfacial adhesion between HA and matrix. Surface modifieations , especially by in situ copolymerization of VTES and BA, significantly increase notch impact strengths and marginal stiffness and tensile strengths of HDPE/HA composites. And it is found that there is a critical thickness of PBA coating on HA panicles for optimum mechanical properties of HDPE / HA composites.

MECHANICAL PROPERTIES OF OZONIZED HDPE FILLED WITH SERICITE-TRIDYMITE-CRISTOBALITE

The mechanical properties of ozonized high density polyethylene(HDPE)blended with sericite-tridymite-cristobalite(STC)were studied in this paper.The experimental results show that some oxygen containing polar groups areintroduced on the molecular chain of HDPE through ozonization,the compatibility between HDPE and STC is thusimproved,the mechanical properties of the blend are markedly enhanced.Compared with untreated HDPE/STC(60/40)blend,the yield strength and notched impact strength of ozonized HDPE/STC(60/40)blend are increased from 27.0 MPa to29.5 MPa and from 2.8 kJ/m^2 to 13.3 kJ/m^2,respectively,the notched impact strength is close to that of HDPE(13.6 kJ/m^2),the yield strength is in excess of 3.9 MPa of that of HDPE.The yield strength and notched impact strength will be furtherincreased to 30.7 MPa and 32.4 kJ/m^2 in case the ozonized HDPE is blended with STC pretreated with silane coupling agent.

A STUDY ON MECHANICAL PROPERTIES OF γ-RAY IRRADIATED HDPE FILLED WITH SERICITE-TRIDYMITE-CRISTOBALITE

The effect of γ-ray irradiation on the mechanical properties of high densitypolyethylene(HDPE) filled with sericite-tridymite-cristobalite(STC) was studied. The ex-perimental results show that γ-ray irradiation can improve the affinity between HDPE andSTC, and the dispersion of STC in HDPE matrix. Compared with HDPE/STC (80/20)blend, the yield stress and impact strength of irradiated HDPE (10kGy)/STC (80/20) blendare increased from 22.8 MPa and 70J/m to 28.5 MPa and 144J/m. The yield stress andimpact strength of HDPE/irradiated HDPE/STC (48/32/20) are 27.8MPa and 210J/m,respectively.

Mechanical and Thermal Properties of Recycled Mixed Waste Polymers Reinforced with Reclaimed Newsprint Fibres

This study investigates the mechanical,thermal and morphological properties of rHDPE(Recycled High Density Polyethylene)and a mixture of rPE HD/LD(High and Low Density Polyethylene),both reinforced with rNP(Reclaimed Newsprint Paper)fibres.To enhance the composite properties,the addition of highly grafted maleic anhydride polyethylene wax,as CA(Coupling Agent),and semi crystalline copolymer of propylene and ethylene,as IM(Impact Modifier),was included into the material formulation by a twin-screw extruder.Mechanical and morphological properties were studied on tensile test specimens,prepared by injection moulding,by tensile testing machine and SEM(Scanning Electron Microscope),respectively.Thermal properties,i.e.melting and crystallization behaviour,were investigated by DSC(Differential Scanning Calorimetry).Mechanical analysis showed that the addition of rNP in both composites increased the young modulus and significantly decreased the elongation at break.The DSC results revealed that the addition of the rNP in the rHDPE matrix led to a substantial decrease of crystallinity,which consequently affects the tensile strength of the composite(17 MPa)in contrast to the neat rHDPE(25 MPa).On the contrary,fibre addition in rPE HD/LD matrix had no specific impact on the crystallinity index,but did contribute to the increased tensile strength(26 MPa)when compared with neat rPE HD/LD(16 MPa).SEM photomicrographs of the impact fracture surfaces demonstrated a solid adhesion bond between the natural fibres and the rPE HD/LD matrix.Reclaimed newsprint fibres can thus be considered as a perspective alternative to the inorganic fillers in the rPE HD/LD composite.

Molecular Mobility in the Amorphous Phase Determines the Critical Strain of Fibrillation in the Tensile Stretching of Polyethylene

The microstructural development of bimodal high density polyethylene subjected to tensile deformation was investigated as a function of strain after annealing at different temperatures by means of a scanning synchrotron small angle X-ray scattering(SAXS)technique.Two different deformation mechanisms were activated in sequence upon tensile deformation:intralamellar slipping of crystalline blocks dominates the deformation behavior at small deformations whereas a stress-induced crystalline block fragmentation and recrystallization process occurs at a critical strain yielding new crystallites with the molecular chains preferentially oriented along the drawing direction.The critical strain associated with the lamellar-to-fibrillar transition was found to be ca.0.9 in bimodal sample,which is significantly larger than that observed for unimodal high-density polyethylene(0.4).This observation is primarily due to the fact that the bimodal sample possesses a greater mobility of the amorphous phase and thereby a reduced modulus of the entangled amorphous network.The conclusion of the mobility of the amorphous phase as a determining factor for the critical strain was further proven by the 1H-NMR T2 relaxation time.All these findings contribute to our understanding of the excellent slow crack growth resistance of bimodal polyethylene for pipe application.