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.

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.

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.

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 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.

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.

Thermal Degradation, Flame Retardance and Mechanical Properties of Thermoplastic Polyurethane Composites Based on Aluminum Hypophosphite

Aluminum hypophosphite （AP） was used to prepare flame-retarded thermoplastic polyurethane （FR-TPU） composites, and their flame retardancy, thermal degradation and mechanical properties were investigated by limiting oxygen index （LOI）, vertical burning test （UL-94）, thermogravimetric analysis （TGA）, cone calorimeter （CC） test, Fourier transform infrared （FTIR） spectroscopy, scanning electron microscopy （SEM） and tensile test. TPU containing 30 wt% of AP could reach a V-0 rating in the UL-94 test, and its LOI value was 30.2. TGA tests revealed that AP enhanced the formation of residual chars at high temperatures, and slightly affected the thermal stability of TPU at high temperatures. The combustion tests indicated that AP affected the burning behavior of TPU. The peak of heat release rate （PHRR）, total heat release （THR） and mass loss rate （MLR） greatly reduced due to the incorporation of AP. The tensile test results showed that both the tensile strength and the elongation at break slightly decreased with the addition of AP. The digital photos and SEM micrographs vitrified that AP facilitated the formation of more compact intumescent char layer. Based on these results mentioned above, the flame-retarding mechanism of AP was discussed. Both the self-charring during the decomposing process of AP and its facilitation to the charring of TPU led to the great improvement in the flame retardancy of TPU.

MORPHOLOGY AND PERFORMANCE OF UNSATURATED POLYESTER NANOCOMPOSITES MODIFIED WITH ORGANOCLAY AND THERMOPLASTIC POLYURETHANE

Unsaturated polyester（UPR）/thermoplastic polyurethane（TPU）/organoclay nanocomposites were prepared by melt compounding of thermoplastic polyurethane and unsaturated polyester prepolymer,and then mixing with the hybrids of styrene monomers and organoclay at ambient temperature.The crosslinking reaction eventually occurred through the unsaturated polyester prepolymer and styrene monomer.The morphology of the composites was investigated by scanning electron microscopy（SEM） and transmission electron microscopy（TEM）.The results show that the impact strength of UPR/TPU/organoclay nanocomposites increases obviously;the cure shrinkage decreases markedly,the glass transition temperature is enhanced and an elastic response to the deformation is prominent at the temperature above 10℃.

Surface decoration of Halloysite nanotubes with POSS for fire-safe thermoplastic polyurethane nanocomposites

Halloysite nanotubes(HNTs)have been considered as a promising flame retardant fillers for polymers.In this work,the polyhedral oligomericsilsesquioxane(POSS)containing amino group was covalently grafted on the surface of HNTs with 3-(2,3-epoxypropoxy)propytrimethoxysilane as a chemical bridge.The POSS modified HNTs(HNTs-POSS)dispersed uniformly in the thermoplastic polyurethane(TPU)matrix and endowed TPU nanocomposites with enhanced tensile properties and fire safety.Cone calorimeter tests revealed that the introduction of 2 wt%HNTs-POSS to TPU matrix remarkably reduced the peak of heat release rate(PHRR)and total heat release(THR)by 60.0%and 18.3%,respectively.In addition,the peak CO production rate and total smoke release(TSR)could be significantly suppressed by the addition of HNTsPOSS.The well dispersed HNTs in combination with the ceramified silicon network from the thermal decomposition of POSS contributed to the formation of a continuous and compact char layer,exhibiting a tortuous effect by inhibiting heat diffusion and evaporation of volatile gaseous.In addition,the released crystal water from HNTs could dilute the combustible volatiles and then decline the combustion intensity.The tensile tests demonstrated that introduction of 2 wt%HNTs-POSS would enhance the maximum stress of TPU nanocomposite with a slight decrease of elongation at break.The combination of HNTs and POSS through the construction of effective interfacial interactions provides a feasible way to effectively enhance the fire safety of TPU nanocomposites without scarifying ductility.

Dynamic Bonds Mediate π-π Interaction via Phase Locking Effect for Enhanced Heat Resistant Thermoplastic Polyurethane

Stimulus-responsive polymers containing dynamic bonds enable fascinating properties of self-healing,recycling and reprocessing due to enhanced relaxation of polymer chain/network with labile linkages.Here,we study the structure and properties of a new type of thermoplastic polyurethanes(TPUs)with trapped dynamic covalent bonds in the hard-phase domain and report the frustrated relaxation of TPUs containing weak dynamic bond andπ-πinteraction in hard segments.As detected by rheometry,the aromatic TPUs with alkyl disulfide in the hard segments possess the maximum network relaxation time in contrast to those without dynamic bonds and alicyclic TPUs.In situ FTIR and small-angle scattering results reveal that the alkyl disulfide facilitates stronger intermolecular interaction and more stable micro-phase morphology inπ-πinteraction based aromatic TPUs.Molecular dynamics simulation for pure hard segments of model molecules verify that the presence of disulfide bonds leads to strongerπ-πstacking of aromatic rings due to both enhanced assembling thermodynamics and kinetics.The enhancedπ-πpacking and micro-phase structure in TPUs further kinetically immobilize the dynamic bond.This kinetically interlocking between the weak dynamic bonds and strong molecular interaction in hard segments leads to much slower network relaxation of TPU.This work provides a new insight in tuning the network relaxation and heat resistance as well as molecular self-assembly in stimulus-responsive dynamic polymers by both molecular design and micro-phase control toward the functional applications of advanced materials.

Smoke suppressant in flame retarded thermoplastic polyurethane composites: Synergistic effect and mechanism study

Considerable smoke and toxic volatiles generation has compromised the application of thermoplastic polyurethane (TPU) and caused a great threat to human life. Here, nano-MgFe layered double hydroxide (MgFe-LDH) with uniform particle size was synthesized to reduce smoke density and toxic gases of TPU composites using ammonium polyphosphate (APP) as a flame retardant agent. The results show that the combination of 16 wt.% APP and 4 wt.% MgFe-LDH greatly decreased the smoke density (D20min and Ds, max), smoke production rate (SPR) and heat release rate (HRR) of TPU composites. Furthermore, the MgFe-LDH synergist demonstrated high efficiency in decreasing total volatiled products and toxic volatiles evolved, such as the CO, HCN and isocyanates. The reason was mainly attributed to the chemical reaction between MgFe-LDH and APP, which can promote the compactness of char layers with fine microstructure formed in the decomposition process of MgFe-LDH/APP/TPU composites. The protective char layers could act as barriers between combustion zone and matrix to protect the unburned substrate and promote smoke suppression effect.

Microcellular injection molding process for producing lightweight thermoplastic polyurethane with customizable properties

A three-stage molding process involving microcellular injection molding with core retraction and an ＂out-of-mold＂ expansion was developed to manufacture thermoplastic polyurethane into lightweight foams of varying local densities, microstructures, and mechanical properties in the same microcellular injection molded part. Two stages of cavity expansion through sequential core retractions and a third expansion in a separate mold at an elevated temperature were carried out. The densities varied from 0.25 to 0.42 g/cm3 （77% to 62% weight reduction）. The mechanical properties varied as well Cyclic com- pressive strengths and hysteresis loss ratios, together with the microstructures, were characterized and reported.

Boosting fire safety and mechanical performance of thermoplastic polyurethane by the face-to-face two-dimensional phosphorene/MXene architecture

Black phosphorus(BP), as one of the most promising fillers for flame retarding polymer, has been seriously limited in practical application, due to the agglomeration and poor structural stability challenges.Here, the BP was modified by MXene and polydopamine(PDA) via ultrasonication and dopamine modification strategy to improve the structural stability and dispersibility in the matrix. Then, the obtained(BP-MXene@PDA) nanohybrid was employed to promote the mechanical performance, thermal stability,and flame retardancy of thermoplastic polyurethane elastomer(TPU). The resultant TPU composite containing 2 wt.% of BP1-MXene2@PDA showed a 19.2% improvement in the tensile strength and a 13.8%increase in the elongation at break compared to those of the pure TPU. The thermogravimetric analysis suggested that BP-MXene@PDA clearly enhances the thermal stability of TPU composites. Furthermore,the introduction of the BP-MXene@PDA nanohybrids could considerably improve the flame retardancy of TPU composite, i.e., 64.2% and 27.3% decrease in peak heat release rate and total heat release, respectively. The flame-retardant mechanisms of TPU/BP-MXene@PDA in the gas phase and condensed phase were investigated systematically. This work provides a novel strategy to simultaneously enhance the fire safety and mechanical properties of TPU, thus expanding its industrial applications.

Antibacterial Thermoplastic Polyurethane/PL-DOSS Composite Films

Medical devices-related infections pose a great threat to patients and cause an increased morbidity and mortality. Herein, we prepare an antibacterial composite(TPU-x) through blending medical grade thermoplastic polyurethane(TPU) and the complex(PL-DOSS) of ε-polylysine(ε-PL) and docusate sodium(DOSS). >99% reduction of colony forming unit(CFU) can be obtained in TPU-x composite films even at relatively low content of PL-DOSS, e.g. 0.13% for Methicillin resistant S. aureus(MRSA) and 0.5% for E. coli. The excellent antibacterial activity is mainly attributed to the formation of PL-DOSS nanoparticles that are uniformly dispersed in the TPU matrix with a size of ~100 nm. TPU-x composite films exhibit long-term stability in saline and good biocompatibility, and retain mechanical properties of TPU.

Effect of LiTFSI and LiFSI on Cycling Performance of Lithium Metal Batteries Using Thermoplastic Polyurethane/Halloysite Nanotubes Solid Electrolyte

All-solid-state lithium batteries(ASSLB) are promising candidates for next-generation energy storage devices.Nevertheless,the large-scale commercial application of high energy density AS S LB with the polymer electrolyte still faces challenges.In this study,a thin solid polymer composite electrolyte(SPCE) is prepared through a facile and cost-effective strategy with an infiltration of thermoplastic polyurethane(TPU),lithium salt(LiTFSI or LiFSI),and halloysite nanotubes(HNTs) in a porous framework of polyethylene separator(PE)(TPU-HNTs-LiTFSI-PE or TPU-HNTs-LiFSI-PE).The composition,electrochemical performance,and especially the effect of anions(TFSI-and FSI-) on cycling performance are investigated.The results reveal that the flexible TPU-HNTs-LiTFSI-PE and TPU-HNTs-LiFSI-PE with a thickness of 34 μm exhibit wide electrochemical windows of 4.9 and 5.1 V(vs.Li+/Li) at 60℃,respectively.Reduction in FSI-tends to form more LiF and sulfur compounds at the interface between TPU-HNTs-LiFSI-PE and Li metal anode,thus enhancing the interfacial stability.As a result,cell composed of TPU-HNTs-LiFSI-PE exhibits a smaller increase in interfacial resistance of solid electrolyte interphase(SEI) with a distinct decrease in charge-transfer resistance during cycling.Li|Li symmetric cell with TPU-HNTs-LiFSI-PE could keep its stable overpotential profile for nearly 1300 h with a low hysteresis of approximately39 mV at a current density of 0.1 mA cm-2,while a sudden voltage rise with internal cell impedance-surge signals was observed within 600 h for cell composed of TPU-HNTs-LiTFSI-PE.The initial capacities of NCMITPU-HNTs-LiTFSIPEILi and NCMITPU-HNTs-LiFSI-PEILi cells were 149 and 114 mAh g-1,with capacity retention rates of 83.52% and89.99% after 300 cycles at 0.5 C,respectively.This study provides a valuable guideline for designing flexible SPCE,which shows great application prospect in the practice of ASSLB.

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.