Synthesis of Organic-Inorganic Hybrid Aluminum Hypophosphite Microspheres Flame Retardant and Its Flame Retardant Research on Thermoplastic Polyurethane

Aluminum hypophosphite microspheres(AHP) were synthesized by hydrothermal method using NaH2PO2·H2O and AlCl3·6H2O as raw materials, and then the AHP microspheres were polymerized by surface polymerization of micro-nanospheres with cyclic cross-linked poly(cyclotriphosphazene-co-4,4'-sulfonyldiphenol)(PZS). A new organic-inorganic poly(phosphonitrile)-modified aluminum hypophosphite microspheres(PZS-AHP) were synthesized by encapsulation and applied to flame retardant thermoplastic polyurethane(TPU). The microstructure and chemical composition of the PZS-AHP microsphere were characterized by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy and X-ray spectroscopy. The thermal stability of PZS-AHP microsphere was explored with thermogravimetric analysis. Thermogravimetric data indicate that the PZS-AHP microspheres have excellent thermal stability. The thermal and flame-retarding properties of the TPU composites were evaluated by thermogravimetric(TG), limited oxygen index tests(LOI), and cone calorimeter test(CCT). The TPU composite achieved vertical burning(UL-94) V-0 grade and LOI value reached 29.2% when 10 wt% PZS-AHP was incorporated. Compared with those of pure TPU, the peak heat release rate(pHRR) and total heat release(THR) of TPU/10%PZS-AHP decreased by 82.2% and 42.5%, respectively. The results of CCT indicated that PZS-AHP microsphere could improve the flame retardancy of TPU composites.

Effect of microwave treatment on tensile properties of sugar palm fibre reinforced thermoplastic polyurethane composites

The effect of microwave treatment on the tensile properties of treated sugar palm fibre with 6% NaOH reinforced thermoplastic polyurethane composites was investigated. Firstly, the sugar palm fibres were treated by 6% alkali solution. Then, microwave treatment was used to treat the alkali treated sugar palm fibres. Three types of temperatures(i.e. 70, 80 and 90℃) were applied in microwave treatment. The extruder and hot press machines were used to mixing the sugar palm fibres and polyurethane resin, and fabricate the composites. Tensile properties(i.e. tensile strength, tensile modulus and elongation at break) were studied by following the ASTM D-638 standard. The highest tensile strength was recorded 18.42 MPa with microwave temperature at 70℃ and 6% alkali pre-treatment. Therefore, the temperature 70℃ of microwave treatment may consider the best degree cent grate.

Physical and damping properties of kenaf fibre filled natural rubber/thermoplastic polyurethane composites

The paper presents the investigation of the effect of alkaline treatment of sodium hydroxide(NaOH) on physical and dynamic mechanical analysis(DMA) viscoelastic properties of kenaf fibre filled natural rubber(NR)/thermoplastic polyurethane(TPU) composites.The treated kenaf fiber,NR and TPU were weighed and proportioned according to the required compositions and were blended using hot mixed Brabender machine.The polymer composites were then fabricated using the hot press to form a sample board.The sample was cut and prepared and water absorption,density,thickness swelling and DMA tests were performed.As far as physical properties are concerned,composites with the highest NR amount of shows the best results,which indicates good fiber bonding adhesion.The polymer composites with the highest amount of TPU shows the highest damping properties at high temperature.

Effect of Accelerated Xenon Lamp Aging on the Mechanical Properties and Structure of Thermoplastic Polyurethane for Stratospheric Airship Envelope

This study aimed to investigate the effect of artificial weathering test on the photoaging behavior of TPU films. Changes in mechanical properties, morphology and chemical structures are studied by tensile test, scanning electron microscopy, atomic force microscopy, Fourier-transformed infrared, and X-ray photoelectron spectroscopy. The results show that the photoaging negatively affects the initial modulus and stress at break values of TPU films. The surface of the specimen that is exposed to irradiation becomes rough, and some visible micro-defects such as blisters and voids can be detected. The morphology of the fracture surfaces illustrates that irradiation reduces the plasticity but increases the brittleness of the TPU films. The chemical structure analyses of the accelerated aged films prove that chemical structural changes in TPU films occur. The irradiation may break the long molecular chains on the surface of the specimens and form the lowmolecular weight oxygen-containing groups. The number of chain scissions increases with the increase in exposure time.

Synthesis and Properties of Non-isocyanate Crystallizable Aliphatic Thermoplastic Polyurethanes

A simple non-isocyanate route synthesizing thermoplastic polyurethanes（TPUs） with good thermal and mechanical properties is described. Melt transurethane polycondensation of dimethyl 1,6-hexamethylene dicarbamate with 1,4-butanediol and 1,6-hexanediol was conducted at different molar ratios under the catalysis of tetrabutyl titanate. A series of crystallizable non-isocyanate TPUs with high molecular weight were prepared. The TPUs were characterized by gel permeation chromatography, FT-IR, 1 H-NMR, differential scanning calorimetry, thermogravimetric analysis, wide angle X-ray diffraction, AFM, and tensile tests. The TPUs exhibited Mn ranging from 12 500 to 26 400 g/mol, Mw from 16 700 to 56 400 g/mol, Tm up to 151.4 °C, and initial decomposition temperature over 241.8 °C. Their tensile strength reached 42.99 MPa with a strain at break of 30.00%. TPUs constructed simply with butylene, hexylene, and urethane linkages were successfully synthesized through a non-isocyanate route.

Mechanical and Thermal Properties of Sugar Palm Fiber Reinforced Thermoplastic Polyurethane Composites:Effect of Silane Treatment and Fiber Loading

The aim of the present study was to develop sugar palm fiber(SPF)reinforced thermoplastic polyurethane(TPU)composites and to investigate the effects of fiber surface modification by 2%silane treatment and fiber loading(0,10,20,30,40 and 50 wt%)on the mechanical and thermal properties of the obtained composites.Surface treatment was employed to improve the fiber-matrix interface,which was expected to boost the mechanical strength of the composites,in terms of tensile,flexural and impact properties.Thermal properties were also investigated by thermal gravimetric analysis(TGA)and dynamic mechanical analysis(DMA)to assess the thermal stability of the developed composites.Furthermore,scanning electron microscopy(SEM)was used to study the tensile fracture samples of composites with a view towards evaluating the effects of fiber surface treatments on the fiber/matrix interfacial bonding.The findings of this study reveal that the silane treatment has determined good bonding and linkage of the cellulose fiber to the TPU matrix,hence contributing to enhanced mechanical and thermal properties of the composites.The composite formulation with 40 wt%sugar palm fiber loading showed optimum values such as 17.22 MPa for tensile,13.96 MPa for flexural,and 15.47 kJ/m^2 for impact strength.Moreover,the formulations with higher fiber content exhibited satisfactory values of storage modulus and thermal degradation,while their good interfacial adhesion was evidenced by SEM images.

Investigation of Temperature Dependency of Morphological Properties of Thermoplastic Polyurethane using WAXS and SAXS Monitoring

Polyether and polyether/ester based TPU （thermoplastic polyurethanes） were investigated with wide-angle XRD （X-ray diffraction） and SAXS （small angle X-ray scattering）. Furthermore, SAXS measurements were performed in the temperature range of 30 ℃ to 130 ℃. Polyether based polymers exhibit only one broad diffraction signal in a region of 2 θ 15° to 25°. In case of polyurethanes with ether/ester modification, the broad diffraction signal arises with small sharp diffraction signals. SAXS measurements of polymers reveal the size and shape of the crystalline zones of the polymer. Between 30 ℃ and 130 ℃ the size of the crystalline zone changes significantly. The size decreases in most of investigated TPU. In the case of Desmopan 9365D an increase of the particle size was observed.

Improving the Compatibility of Biodegradable Poly (Lactic Acid) Toughening with Thermoplastic Polyurethane (TPU) and Compatibilized Meltblown Nonwoven

Poly (Lactic Acid) (PLA) is a biodegradable polymer which originates from natural resources such as corn and starch, offering excellent strength, biodegradability, nevertheless its inherent brittleness and low impact resistance properties have limited its application. On the other hand, Thermoplastic Polyurethane (TPU) has high toughness, durability and flexibility, which is one of the most potential alternatives for enhancing the flexibility and mechanical strength of Poly (Lactic Acid) (PLA) by blending it with a compatibilizer. With the aim to improve the mechanical and thermal properties of Poly (Lactic Acid) (PLA) meltblown nonwovens, The Thermoplastic Polyurethane (TPU) was melt blended with Poly (Lactic Acid) (PLA) at the different corresponding proportions for toughening the Poly (Lactic Acid) and the corresponding PLA/TPU MBs (meltblown nonwovens) were also manufactured. Joncryl ADR 4400 is mixed into the PLA matrix during processing. It was found that Joncryl had a much higher chain extension that substantially increased the molecular weight of the PLA matrix. SEM study revealed that Joncryl ADR 4400 is a good compatibilizer. Moreover, in this study, the crystallization, thermal and rheological behaviors of the corresponding PLA and TPU blends were also investigated. PLA/TPU MBs were also characterized by morphology and mechanical properties. The rheological property of the PLA/TPU meltblown nonwoven revealed that the viscosity is increasing as the amount of TPU is increasing in the blend, PLA/TPU meltblown nonwovens exhibited excellent mechanical properties;they are soft, elastic, and have certain tensile strength. New materials have potential applications in the medical and agricultural fields. Joncryl ADR 4400 compatibilized blends showed higher strength than simple PLA/TPU blends at the same PLA/TPU ratio.

HYDROGEN BOND EFFECT IN THERMOPLASTIC POLYURETHANE ELASTOMERS

Hydrogen bond effects in thermoplastic polyurethane elastomers (TPU) with different chain extender structures and hard segment contents have been studied quantitatively by dynamic mechanical analysis. It has been found that the hydrogen bond effects in TPU decrease with the increase of temperature. The temperature dependence of hydrogen bonding in TPU’s can be described by the Arrhenius equation, and the activation energy of hydrogen bonding as well as the physical cross-link density have been calculated.

Hydrogen Bonding in Thermoplastic Polyurethane Elastomers:IR Thermal Analysis

The hydrogen bond percentage and its temperature dependence of the three TPU samples synthesized from polytetrahydrofuran, 4,4'-diphenylmethane diisocyanate, N -methyl diethanol amine or 1,4-butane diol were studied by means of IR thermal analysis. The enthalpy and the entropy of the hydrogen bond dissociation were determined by the Van't Hoff plot.

Fabrication and Characterization of Poly(Styrene-Butadiene-Styrene)/Thermoplastic Polyurethane Blends

This investigation presents thermoplastic elastomers (TPEs) based on poly (styrene-butadiene-styrene) (SBS) and thermoplastic polyurethane (TPU) materials were prepared with varying compositions. A series of works were conducted on the relationships between rheological, optical properties, morphology, mechanical properties, abrasion resistance and thermostability given. The results showed that the shear viscosity of SBS not obvious effect with TPU content. The optical properties of the SBS/TPU blend that its uniform transparency. The morphology characteristics indicating the phase diversion and the variation in the size of the SBS domains from large to small as the TPU contents increased, with heterogeneous domain dispersions. Additionally, the mechanical properties, abrasion resistance and thermal resistance are improved as the amount of added TPU is increased, suggesting that the blending of SBS with TPU is consistent with the compound rule.

Design and Multicriteria Optimization of a Two-Stage Reactive Extrusion Process for the Synthesis of Thermoplastic Polyurethanes

This paper presents the implementation of two multicriteria optimization methods based on different approaches, namely, Rough Set Method (RSM) and Net Flow Method (NFM), to the manufacture by reactive extrusion of linear thermoplastic polyurethanes (TPUs), appropriate for medical applications. A preliminary study allowed determining the process operating conditions for which the polymerization time and the average residence time of the reactants in the extruder are of the same order of magnitude. Prior to the optimization, a neural network model able to predict with acceptable accuracy the effect of the operating conditions on the output process variables, was constructed and validated. This model was then used to determine, using Pareto’s concept, a set of non-dominated solutions constituting Pareto’s domain. These solutions were then ranked according to the preferences of a decision maker using NFM and RSM. This allowed providing the 10% highest ranked solutions of Pareto’s domain and proposing a set of optimal operating conditions for the production, with the lowest energy consumption, of TPUs with targeted properties and high purity. Experimental validation runs carried out under similar operating conditions gave rise to criteria values confirming the su- perior performance of NFM, without rejecting, at the same time, the values obtained using RSM.

Mechanical, Thermal and Morphology Properties of Thermoplastic Polyurethane Copolymers Incorporating α,ω-Dihydroxy-[poly(propyleneoxide)-poly (dimethylsiloxane)-poly(propyleneoxide)] of Varying Poly(propyleneoxide) Molecular Weight

Novel segmented thermoplastic polyurethane (TPU) copolymers were synthesized using two-step solventless bulk polymerization. 4,4’-methylenediphenyl diisocyanate (MDI) and 1,4-Butanediol (BDO) were used to form hard segment of TPU and α,ω-dihydroxy-[poly(propyleneoxide)-poly (dimethylsiloxane)-poly(propyleneoxide)] (α,ω-dihydroxy-(PPO-PDMS-PPO)) was used to form soft segment of TPU, where the molar ratio of the –N=C=O/OH was 1.02 and the hard segment weight percentage was 30%. A series of TPUs were characterized by fourier transform infrared spectroscopy (FT-IR). The investigation of triblock oligomer’s PPO molecular weight impact on the derived TPU’s mechanical properties, thermal performance, surface water repellency and morphology performance was carried by Instron material tester, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), water contact angles (WCA), scanning electron microscope and energy dispersive X-ray spectroscopy (SEM-EDX) and wide angle X-ray diffraction (WAXD), respectively. FT-IR confirmed α,ω-dihydroxy-(PPO-PDMS-PPO) well cooperating into urethane structure and analyzed hydrogen bonding between N-H group with hard segment C=O group and N-H group with soft segment C-O-C group. DSC and WAXD results showed α,ω-dihydroxy-(PPO-PDMS-PPO) segments crystallization. SEM-EDX results showed that the presence of a spherulitic morphology, which arose from the crystallization of the PPO segments. The thermal properties measured by TGA and DSC were slightly affected by molecular weight of PPO and microphase separation. The weight loss of TPUs started between 294°C and 300°C, and Tg was in the range of -70°C to -107°C. TPU copolymers’ surface hydrophobicity property was excellent with WCA range of 95°?to 112°. TPU-3 with 1000 molecular weight PPO has the optimized mechanical properties with tensile strength 16.4 MPa and the modulus at 100% elongation 6.2 MPa and elongation 398%.

Chain Extender-induced Hydrogen Bonding Organization Determines the Morphology and Properties of Thermoplastic Polycarbonate Polyurethane

Thermoplastic polycarbonate polyurethanes(PCUs) are multiblock copolymers that have been applied for medical devices for long time. Aliphatic diols are common chain extenders(CE) involved in the composition of the hard segments of PCU. However, limited knowledge was discovered about how the chemical structure of CE affects the hydrogen bonding organization within PCUs and their mechanical properties.To investigate this problem, a group of PCUs were synthesized respectively by extending the polymer chain with 1,4-butanediol(BDO),aminoethanol(MEA), ethanediol(EO) as three kinds of chain extenders. Tiny differences in the CE chemical structure results in remarkable variations in phase separation, condensed morphologies, thermal and mechanical properties, which are characterized by Fourier transform infrared spectrometer, atomic force microscopy, small-angle X-ray scattering, differential scanning calorimetry, and tensile tests. The microstructural evolution during unilateral deformation and the different mechanism induced by the different CEs was probed and unveil by in situ wide-and small-angle X-ray diffraction. Symmetry of CE can improve the organization of the hydrogen bonding. The coherence strength of the urethane/urea group also plays a key role by comparing the two PCUs with ethanediol and aminoethanol.

Tribological evaluation of thermoplastic polyurethane-based bearing materials under water lubrication:Effect of load,sliding speed,and temperature

Polymers are widely used in bearing applications.In the case of water-lubricated stern tube bearings,thermoplastic polyurethane(TPU)-based composites are used due to their excellent wear resistance,corrosion resistance,and tunable mechanical properties.Their tribological performance,however,depends on operating conditions.In this work,TPU was blended with carbon fiber,graphene platelet,and ultra-high molecular weight polyethylene(UHMWPE).Friction tests of TPU based-composites against copper countersurface were carried out in water to mimic the actual operating conditions of the bearing.Most of the resulting contacts were in the boundary lubrication regime,in which friction was attributed to both contact mechanics of asperities as well as water lubrication.Our results show that the viscoelasticity of TPU has a considerable impact on its tribological performance.Water lubrication at 50°C promotes the softening of polymer surface material during sliding,resulting in higher fluctuation in the coefficient of friction and wear loss.This is attributed to the reduced thermomechanical properties.In addition,Schallamach waviness is observed on worn surface.The tribological properties of TPU are significantly improved by the inclusion of carbon fiber,graphene platelet,and UHMWPE.The formation of graphene transfer-layers and UHMWPE transfer film reduces friction and wear loss,while the inclusion of carbon fiber enhances wear resistance due to improved mechanical properties and load bearing capacity.

Temperature-induced Evolution of Micro-structure and Chain Dynamics in Thermoplastic Polyurethane with Low Hard Segment Content as Studied by In Situ Synchrotron SAXS and Time-Domain NMR Experiments

The microstructural evolution of a thermoplastic polyurethane(TPU)with low hard segment content has been monitored utilizing in situ real-time synchrotron small angle X-ray scattering(SAXS)and time-domain nuclear magnetic resonance(NMR)measurements.The TPU is composed of 23 wt% of[4,4-methylenediphenyl diisocyanate(MDI)]-[1,4-butanediol(BD)]chain segments,which form hard domains,as[polytetrahydrofuran(PTHF)]forming soft domains.The number and distribution of monomer units in hard blocks is determined by the successive self-nucleation and annealing thermal fractionation technique.In situ SAXS method reveals heating-induced increase in the spacing of hard and soft domains,while time-domain ^(1)H-NMR characterizes the changes in the phase composition and chain dynamics in these domains.A glassy fraction of short MDI-BD chain segments in hard domains passes through T_(g) above ambient temperature.At higher temperatures,MDI-BD nanocrystals start to melt.Sequence length distribution of MDI-BD chain segments causes a distribution in crystal sizes and wide melting temperature range.The melting is accompanied by the mixing of MDI-BD with PTHF segments in soft domains,and by increase in segmental mobility in these domains.Above 180℃,the TPU melt is homogeneous on the scale above nanometers according to SAXS data.

CPE增容TPU/PVC共混弹性体及相形态

为提高热塑性聚氨酯弹性体(TPU)与聚氯乙烯(PVC)的相容性,以氯化聚乙烯(CPE)为增容剂,经双螺杆挤出机熔融共混制备TPU/PVC共混型热塑性弹性体,测试了不同CPE用量的共混弹性体的拉伸强度、断裂伸长率和硬度等力学性能,以及动态流变性能、动态力学性能和热稳定性。通过扫描电子显微镜(SEM)对共混弹性体的相态结构进行研究。结果表明,当TPU/PVC质量比为70/30时,共混弹性体综合力学性能最佳,拉伸强度为19.92 MPa,断裂伸长率为972%。随着CPE用量的增加,TPU/PVC共混弹性体的拉伸强度、断裂伸长率、硬度等均先增大后减小;CPE用量为6份时,TPU/PVC共混弹性体拉伸强度达到最大,为23.73 MPa,相较未加CPE时提高19.1%。加入CPE的共混弹性体复数黏度和储能模量均呈下降趋势。此外,CPE的加入还能有效提升弹性体高温热稳定性,TPU和PVC两种组分的损耗因子峰内移靠近,共混弹性体液氮脆断面的SEM照片显示PVC相筹明显变小且更为均匀,以上说明CPE对共混弹性体的增塑、增容作用明显,且CPE用量为6份时增容效果最佳。

具有双螺旋结构的超弹性柔性导体研究

柔性电子器件由于其稳定、高导电性和高拉伸性等特点而受到广泛的关注。本文制备了一种由热塑性聚氨酯(TPU)线和铜(Cu)丝组成的双螺旋柔性导体(DHFC),导体初始电导率为5.71×10^(7) S/m。通过增大螺旋直径,使其拉伸性能增加,DHFC可恢复的最大形变量可达6706%。在弹性应变范围内,DHFC在重复形变(1000次循环的拉伸,应变为2200%)下表现出较高的稳定性,电阻的增加可以忽略不计。此外,由于导体外部涂有水性聚氨酯(WPU)而使其具有优异的防水性能,在水中所测的电阻值与在空气环境中所测的电阻值基本一致。

热塑性树脂增韧环氧树脂复合材料研究进展

为了解决环氧树脂固化导致严重脆弱,低韧性和恶劣的内冲击性缺点,在特定范围内限制适用的问题,本文通过整理近年来环氧树脂增韧的相关文献,研究了热塑性树脂的改性方法和改性后界面情况的进展,对聚砜、聚醚砜、聚醚醚酮、聚酰亚胺等热塑性树脂增韧环氧树脂研究现状进行了分析。研究发现:热塑性树脂增韧环氧树脂的共混体系从均相状态到高交联结构的固定相形态,这种转变极大程度提高了材料的性能。

DOPO基反应型阻燃剂的制备及其阻燃热塑性聚氨酯

以10-(2,5-二羟基苯基)-10-氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO-HQ)和甲苯二异氰酸酯(TDI)为原料,通过加成反应成功制备了含端异氰酸酯基的DOPO基反应型阻燃剂(DRFR),并将其引入到热塑性聚氨酯(TPU)基体中,从而制备阻燃TPU复合材料,并对TPU/DRFR复合材料的阻燃性能、燃烧行为、热降解性能和力学性能进行研究。结果表明,当DRFR的质量分数为26%时,TPU/DRFR复合材料的阻燃等级达到UL 94 V-0级,极限氧指数达27.6%,且熔滴得到了明显的抑制。DRFR的引入促进了TPU基体的提前降解炭化,从而使TPU/DRFR复合材料表面形成了致密、均一且坚硬的炭层,其有效地在固相中发挥了“挡板”作用,使得TPU/DRFR复合材料的热释放速率峰值和总热释放量与纯TPU相比分别降低了49.64%和34.65%。与此同时,DRFR在分解过程中,产生的含磷自由基和惰性气体有效地在气相中发挥了抑制作用,从而使得TPU/DRFR复合材料获得了优异的火安全性能。此外,DRFR的引入对TPU分子链段起到了交联作用,显著增强了TPU复合材料的拉伸强度。