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.

Mechanical, Thermal and Crystallization Properties of Polypropylene (PP) Reinforced Composites with High Density Polyethylene (HDPE) as Matrix

Our work aims to evaluate a complete outlook of virgin high density polyethylene (HDPE) and polypropylene (PP) polyblends. Virgin PP of 20, 30 and 50 weight% is compounded with virgin HDPE. The properties like tensile strength, flexural strength, Izod impact strength are examined. Scanning electron microscopy (SEM) and polarised light microscopy (PLM) are used to observe the surface and crystal morphology. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) tests verify the non compatibility of both polymers. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) techniques are used to study the thermal behaviour of composites. The results manifest co-occurring spherulites for polyblends;indicating the composite to be a physical blend of continuous and dispersed phases, but on the other hand PP improves the tensile and flexural properties of HDPE.

RHDPE/RHES复合材料的组织结构及增韧机理研究

以回收高密度聚乙烯(RHDPE)为基体、自制的复合改性剂HES为增韧剂,采用熔融共混的方式制备了RHDPE/RHES复合材料(简称RPES),研究了RPES的结晶形态、力学性能及熔体流动性,并探究了其增韧机理。结果表明:HES中RHDPE为连续相,橡胶为分散相,体系整体呈现“海岛”结构,分散相呈现“胞状”结构;随着橡胶含量的增加,RPES结晶越来越细化,晶粒尺寸逐渐减小;冲击强度逐渐增大,拉伸屈服强度和弯曲弹性模量有所下降,RPES熔体流动速率(MFR)逐渐减小。当橡胶含量为8%时,RPES的冲击强度达到45.24kJ/m^(2),是纯RHDPE的9.75倍,拉伸屈服强度和弯曲弹性模量保持率分别为83.24%和64.78%。RHDPE/橡胶试样缺口冲击断裂主要由银纹-空化损伤机理引起的,而PRES试样缺口冲击断裂主要是由银纹-剪切带屈服形变损伤机理引起的。

HDPE/改性蛭石复合材料的制备与气体阻隔性能研究

利用改性后的蛭石作为填充材料,通过熔融共混法制备了高密度聚乙烯(HDPE)/改性蛭石复合材料。研究了改性蛭石的添加量对复合材料热稳定性能、结晶性能、力学性能和氧气阻隔性能的影响。结果表明,相比纯HDPE,HDPE/改性蛭石复合材料仍能保持较好的拉伸强度,当含量为1%时拉伸强度为24.1 MPa,断裂伸长率先提高后下降,当含量为0.5%时断裂伸长率达到最高为535%;改性蛭石的加入提升了材料的韧性,当改性蛭石含量为1%时材料缺口冲击强度达到最高为45.8 kJ/m^(2);HDPE/改性蛭石复合材料的氧气阻隔性能明显提升,当改性蛭石含量为1%时材料的氧气阻隔性能达到最优,氧气渗透系数为6.9×10^(-15)cm^(3)·cm/(cm^(2)·s·Pa)。

低MFR双峰HDPE标准试样的研制及应用

以低熔体流动速率(MFR)、相对分子质量分布呈双峰(简称双峰)的高密度聚乙烯(HDPE)100N粉料为原料,先用筛网除去大颗粒和微小粉末,再加入0.2%(w)抗氧剂1010和0.2%(w)抗氧剂168混匀造粒,并除去大、小粒子及异形粒子制备标准试样。对标准试样进行均匀性、稳定性检验,并进行了氧化诱导时间、熔点、结晶点、白度的稳定性实验,以及对标准试样进行了定值及统计允许区间值的确定。结果表明:低MFR双峰HDPE标准试样的MFR标称值为(0.226±0.007)g/10 min,标准试样MFR均匀、稳定。

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.

闪蒸纺UHMWPE/HDPE共混纤维的制备及性能研究

为提高闪蒸纺纤维束的力学强度,将力学性能更为优异的超高相对分子质量聚乙烯(UHMWPE)与高密度聚乙烯(HDPE)共混,通过闪蒸纺丝方法制备UHMWPE/HDPE共混纤维束,采用扫描电子显微镜、差示扫描量热仪、X射线衍射仪和万能试验机等探究UHMWPE的引入对共混纤维束形貌、熔融结晶行为、聚集态结构和力学性能的影响。结果表明:闪蒸纺丝制备HDPE/UHMWPE共混纤维束时,随着纺丝液中UHMWPE质量分数由1%增至5%,溶液黏度增大,共混纤维束单丝直径逐渐增大,当UHMWPE质量分数为7%时,纺丝液会因黏度过大而无法纺丝;随着UHMWPE含量的增加,HDPE/UHMWPE共混纤维束的结晶度和取向度降低,力学性能增大,当纺丝液中UHMWPE质量分数为5%时,共混纤维束结晶度和取向因子分别为74.2%和0.46,拉伸强度为118.9 MPa,较纯HDPE纤维束提高了84.9%。

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.

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.

CNT的质量分数和管径对CNT/HDPE复合材料微观结构及力学性能的影响

碳纳米管(CNT)在CNT/高密度聚乙烯(HDPE)复合材料中发挥着重要作用。本文通过测试结晶度、缺口冲击强度以及拉伸强度,研究了CNT的质量分数和管径对复合材料的微观结构的影响机理。结果表明,改变CNT的质量分数能够提高复合材料的结晶度、缺口冲击强度和拉伸强度,0.2%CNT/HDPE的缺口冲击强度(53.1 kJ/m^(2))比HDPE的缺口冲击强度(31.5 kJ/m^(2))提高了68.57%;0.6%CNT/HDPE的结晶度(52.15%)比HDPE的结晶度(37.1%)提高了40.57%;0.8%CNT/HDPE的拉伸强度(25.97 MPa)比HDPE的拉伸强度(19 MPa)提高了36.68%。引入CNT后,复合材料的缺口冲击强度比HDPE低,但是能够提高复合材料的结晶度和拉伸强度,D5CNT(CNT管径为4~6 nm)/HDPE的结晶度(56.77%)比HDPE的结晶度(37.1%)提高了53.01%,改变管径对复合材料的拉伸强度提升不明显。本研究通过改变CNT质量分数与管径,提升了CNT/HDPE复合材料的冲击性能和拉伸性能,为制备性能优异的CNT/HDPE复合材料提供了理论指导。

HDPE/钛酸钾晶须复合材料的制备与性能研究

利用双螺杆挤出制备了高密度聚乙烯(HDPE)/钛酸钾晶须(PTW)复合材料,研究了PTW不同填充量对HDPE复合材料性能的影响。结果表明:HDPE/PTW复合材料的弯曲模量和弯曲强度随PTW含量的增加而明显增加,拉伸强度略有增加,抗冲击强度有所降低,说明钛酸钾晶须对HDPE具有较好的增刚增韧作用。同时,PTW提高了材料的耐热性能,在PTW质量含量为25%,复合材料的负荷热变形温度提高了近20℃。另外,DSC分析表明,PTW对HDPE有结晶成核作用,结晶峰温度随PTW的增加而增加,在PTW质量含量为20%时,结晶峰温度提高了3.7℃。

HDPE与木屑热等离子体共蒸汽气化研究

以高密度聚乙烯(HDPE)和木屑为研究对象,结合热力学分析和实验研究,探究等离子体气化过程中输入功率、HDPE质量分数以及水碳比(S/C)3种工况参数对氢气产率、合成气组分、氯的产物分布等影响规律,并基于吉布斯最小自由能原理进行热力学计算。模拟分析表明:输入功率由7.5 kW增至34.0 kW过程中,氢气占比在20 kW(对应温度为800℃)时达到最大值59%;随着原料中HDPE质量分数由0增至100%,氢气占比由65%减少至56%;S/C为0时,氢气占比最高(80%),随着S/C由0增至3.0,氢气占比呈现不断减小的趋势;氯在气相中产物主要以KCl(g)、(KCl)_(2)(g)为主。实验研究表明:输入功率、HDPE质量分数和S/C对产氢量的影响趋势与热力学分析一致,在输入功率为22 kW、HDPE质量分数为80%、S/C为1.0时,最优产氢量分别达到1.52、1.51、1.38 m^(3)/kg。氯的气相占比分别在功率为22 kW、HDPE质量分数为20%、S/C为1.4时达到最高。通过对比实验结果验证了热力学模拟对等离子体气化产物特性进行定性定量分析的潜力,探索了采用热力学计算模拟生物质和HDPE等离子体共气化的可行性,并可为等离子体气化的操作优化和氯控制提供借鉴。

基体性质对HDPE/SEBS共混物脆韧性转变的影响——验证Leibler增韧模型

为了研究高密度聚乙烯(HDPE)基体性质对共混物脆-韧转变的影响,本文通过熔融共混的方法制备了苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物(SEBS)/HDPE共混物,利用扫描电子显微镜观察了分散相的粒子尺寸及分布,明确了基体性质与临界粒子间距(ID_c)之间的定量关系。结果表明,随着基体HDPE熔体质量流动速率的减小,共混物发生脆-韧转变时需要的临界弹性体质量分数越小,分散相SEBS的粒子尺寸越小,越有利于共混物脆-韧转变的发生。同时,聚合物共混物的脆-韧转变与基体材料断裂强度(σ_(B))、屈服强度(σ_(Y))有很大的关系,(σ_(B)/σ_(Y))^(2)越大,ID_(c)越大,共混物的脆-韧转变越容易发生,验证了Leibler增韧模型的正确性,并通过线性拟合得到相邻两个微裂纹平均距离(ξ*)和系数(C)。

EFFECT OF PAN-MILLING STRESS ON CRYSTAL STRUCTURES OF HIGH DENSITY POLYETHYLENE

A detailed study was performed on the crystal structures of pan-milled high-density polyethylene (HDPE) using differential scanning calorimetry (DSC) and X-ray diffraction. The crystallinity of HDPE first decreased slightly, followed by a gradual increase with increasing milling times. Monoclinic crystals appeared after 4 cycles of milling. With increasing times of milling, the proportion of monoclinic crystals increased significantly while the proportion of orthorhombic crystals decreased gradually. With increasing times of milling, the crystallite size of orthorhombic form decreased greatly, while the size of monoclinic crystallites kept almost constant during milling.

One step graft copolymerization of acrylic acid and sodium styrene sulfonate onto high-density polyethylene film by preirradiation method

High-density polyethylene (HDPE) films were irradiated by 60Co gamma ray with a dose of 100 kGy in air and then immersed in aqueous solution of acrylic acid (AA) and sodium styrene sulfonate (SSS) at different temperature. The effects of grafting conditions such as temperature, reaction time, Mohr’s salt concentration, and total concentration of monomer on grafting yield were studied. Both grafting yield of AA and SSS onto HDPE respectively increases with total concentration of monomers. The highest grafting yield was observed at 3 mol/L monomers where the grafted PE swelled to the largest extent in the monomers mixture. The grafting yield increases with reaction time and then levels off. At higher temperature, the grafting yield decreases with Mohr’s salt concentration, but increases at low temperature when Mohr’s salt concentration is 0.083%. Which can be interpreted that in the presence of Fe2+ diperoxides and hydroperoxides may decompose at low temperature to form radical which can initiate the grafting. The physical and chemical properties of grafting films were also investigated.

HDPE管内衬盾构隧道复合式衬砌结构极限承载力试验研究

为研究采用HDPE双壁缠绕管作为内衬的盾构隧道复合衬砌结构的破坏机理,依托桃浦污水处理厂初期雨水调蓄工程涉铁段排水隧道工程,开展整环足尺试验研究,得到如下结论:(1)复合衬砌结构破坏过程经历协调变形阶段和各自承载阶段,弹性极限点为顶底部纵缝处界面的剥离脱开,各纵缝及管片本体相继发生破坏,纵缝处填充层混凝土发生拉剪或压剪破坏;(2)复合衬砌结构的薄弱位置为各纵缝处的界面及填充层混凝土,其中顶部和腰部纵缝处最为薄弱;(3)复合衬砌结构不同位置纵缝处的界面破坏和填充层破坏形态均源自于纵缝转动变形导致刚度差异引起的界面应力和填充层应力突变。

HDPE/EUG弯曲样条的受热形状回复行为

用挤出机将高密度聚乙烯(HDPE)与杜仲胶(EUG)进行熔融共混,研究了共混比对HDPE/EUG的熔融、结晶和热力学性能及弯曲形状回复性能的影响。结果表明,随着HDPE中EUG含量的增加,结晶峰向低温方向移动,而HDPE含量的增加诱导EUG结晶温度提高。当二次升温时,当HDPE中的EUG添加量增大时,熔融峰向高温偏移,当HDPE的含量增大时,EUG的熔融峰向低温偏移。热力学测试和弯曲样品受热回复过程中,变形呈现3个温度区间分别为低温慢速区、中温快速回复区和高温下中速回复区。随着EUG含量的增加,区间转变向低温偏移,这是由于,低熔点EUG更容易发生受热活化回复现象,因此,调整共混比例可以控制形状回复速度,回复程度随加热温度而改变。

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.

Characterization and Comparison of Rheological Properties of Agro Fiber Filled High-Density Polyethylene Bio-Composites

The rheological behavior of composites made with high-density polyethylene (HDPE) and different agro fiber by-products such as corncob (CCF), Rice hull (RHF), Flax shives (FSF) and Walnut shell (WSF) flour of 60 - 100 mesh were studied. The experimental results were obtained from samples containing 65 vol.% agro fiber and 3 wt.% lubricant. Particle sizes distribution of the agro fibers was in the range of 0.295 mm to ?0.125 mm. SEM showed evidence of complete matrix/fiber impregnation or wetting. The melt rheological data in terms of complex viscosity (η*), storage modulus (G'), loss modulus (G"), and loss tangent (tanδ) were evaluated and compared for different samples. Due to higher probability of agglomeration formation in the samples containing 65 vol.% of agro fillers, the storage modulus, loss modulus and complex viscosity of these samples were high. The unique change in all the samples is due to the particle size distribution of the agro fibers. The storage and loss modulus increased with increasing shear rates for all the composites, except for Walnut shell composite which exhibited unusual decrease in storage modulus with increasing shear rate. Damping factor (tanδ) decreased with increasing shear rate for all the composites at 65 vol.% filler load although there were differences among the composites. Maximum torque tended to increase at the 65 vol.% agro fiber load for all composites. Corncob and Walnut shell composites gave higher torque and steady state torque values in comparison with Flax shives and Rice hull composites due to differences in particle sizes distribution of the agro fibers.