Regulating the Localization of Intumescent Flame Retardant for Improving the Flame Retardancy of Ethylene-vinyl Acetate Copolymer Using Polyamide 6 as a Charring Agent

Polyamide 6 (PA6) was employed as a charring agent of intumescent flame retardant (IFR) to improve the flame retardancy of ethylene-vinyl acetate copolymer (EVA). Different processing procedures were used to regulate the localization of IFR in the EVA matrix. Localizations in which IFR was dispersed in the PA6phase or in the EVA phase were prepared. The effect of the localization of IFR on the flame retardancy of EVA was investigated. The limited oxygen index (LOI), vertical burning (UL 94) and cone calorimeter test (CCT)showed that the localization of IFR in the EVA matrix exhibited a remarkable influence on the flame retardancy.Compared with EVA/IFR, a weak improvement in the flame retardancy was observed in the EVA/PA6/IFR blend withthe localization of IFR in the PA6 phase. When IFR was regulated from the PA6 phase to the EVA matrix,a remarkable increase in the flame retardancy was exhibited. The LOI was increased from 27.8%to 32.7%, and the UL 94 vertical rating was increased from V-2 to V-0. Moreover, an approximately 41.36%decrease in the peak heat release rate was exhibited. A continuous and compact intumescent charring layer that formed in the blends with the localization of IFR in the EVA matrix should be responsible for its excellent flame retardancy.

Flame retardant polyamide 6 by in situ polymerization of ε-caprolactam in the presence of melamine derivatives

An improved method for preparing melamine cyanurate （MCA） based flame retardant polyamide 6 （FRPA6） materials has been proposed. This processing method, i.e., improved in situ polymerization, was used to synthesize flame retardant PA6. In situ formed MCA nanoparticles were supposed to be linked to PA6 chains in the ε-caprolactam hydrolytic polymerization system to obtain startype polymers for the first time. Through TEM photographs, it can be found that the in situ formed MCA nanoparticles with diametric size of less than 50 nm, are nanoscaled, highly uniformly dispersed in the PA6 matrix. Synthesized flame retardant PA6 have good fire performance which can achieve UL-94 V-0 rating at 1.6 mm thickness with the presence of 7.34 wt.% MCA in the matrix.

Non-isothermal Crystallization Kinetics of Polyamide 6/Diaminemodified MWNTs Nanocomposite

The non-isothermal crystallization kinetics of polyamide 6/diamine-modified multi-walled carbon nanotube （PA6/D-MWNT） nanocomposite was investigated by differential scanning calorimetry （DSC）. The modified Avrami equation, the Ozawa equation and the combined Avrami/Ozawa equation were employed to analyze the non-isothermal crystallization data. The crystallization activation energies were also evaluated by the Kissinger method. It was found that the combined Avrami/Ozawa equation could successfully describe the non-isothermal crystallization process. The results showed that D-MWNTs not only acted as effective heterogeneous nucleating agents for PA6 and noticeably increased the crystallization temperature of PA6, but also influenced the mechanism of nucleation and crystal growth of PA6 and then reduced the overall crystallization rate of the neat PA6 matrix. The crystallization activation energy for the nanocomposite sample was greater than that of the neat PA6, which indicated that the addition of D-MWNTs hindered the mobility of PA6 chain segments.

INTERFACIAL MOLECULAR DESIGN OF A RIGID- PARTICLE TOUGHENED POLYAMIDE 6 COMPOSITE

The effects of interfacial modifier on the mechanical properties of kaolin-filled polyamide 6 (PA6) have been studied. The interracial interaction between polyamide 6 and kaolin has been character ized by means of infrared spectroscopy (IR) and scanning electron microscopy (SEM). The results show that the role of the interracial modifier lies in forming an elastic interlayer with good adhesion between kaolin and PA 6. A composite with high impact strength, high tensile strength and high elastic modulus can be obtained by inserting the elastic interfacial modifier into the rigid-particle-filled polymer system.

COMPARISON OF POLYAMIDE 66/MONTMORILLONITE NANOCOMPOSITES PREPARED FROM POLYAMIDE 6 AND POLYAMIDE 66 BASED MASTER-BATCHES

Two master-batches,polyamide 66 (PA66)/organo-montmorillonite (OMMT) and polyamide 6 (PA6)/OMMT, prepared by melt compounding with methyl methacrylate (MMA) as co-intercalation agent,have been used to prepare nearly exfoliated PA661montmorillonite (MMT) nanocomposites.The resulting nanocomposites are compared in view of their morphology and properties.Nano-scale dispersion of OMMT is realized in both types of nanocomposites,as revealed by XRD,TEM and Molau tests.PA66/MMT nanocomposites having superior mecha...

EFFECTS OF COUPLING AGENTS ON THE RHEOLOGICAL BEHAVIOR OF KAOLIN FILLED POLYAMIDE 6

An experimental study was carried out to investigate the effects of coupling agents on the rheological properties of kaolin filled polyamide 6(PA6). We have investigated the state of dispersion and interfacial interaction of the filled systems, using 'h:anning electron microscopy (SEM) and Molau test, respectively. It is found that the addition of the coupling agents to the PA6/ kaolin (20 wt percent) significantly decreases the melt viscosity and the melt elasticity (first normal stress difference). Moreover, the states of dispersion and the polymer/filler interactions have significant influences on the rheological properties of kaolin/PA6 systems. The rheological behavior of KH550 kaolin /PA6 system is different from that of KH560 kaolin/PA6 system, although chemical reactions have taken place between the surface of KH550 kaolin (or KH560 kaolin) and PA6 matrix during melt processing. This is attributable, in part, to the differences in the state of dispersion of kaolins in PA6 matrix and, to a great extent, to the differences in the extent of chemical reactions that have taken place between the filler and polymer matrix.

Flame Retardancy, Smoke Suppression Effect and Mechanism of Aryl Phosphates in Combination with Magnesium Hydroxide in Polyamide 6

The flammability, smoke emission behavior and mechanical properties of two oligomeric aryl phosphates [bisphenol A bis（diphenyl phosphate） （BDP） and resorcinol bis（diphenyl phosphate） （RDP）] combined with magnesium hydroxide （MH） in polyamide 6 （PA6） have been investigated. Combining 5 wt% BDP, 50 wt% MH imparts a limiting oxygen index （LOI） of 40.9% and UL94 V-0 rating to PA6, meanwhile the peak rate of smoke release （pRSR）, total release of smoke （TSR） and Izod notched impact strength are 41%, 33% and 233% relative to the corresponding value of 55 wt% MH without BDP, respectively. Dynamic mechanical analysis （DMA） indicates that the improvement of toughness attributes to the enhanced compatibility between MH and PA6 by adding BDP. Furthermore, based on the comprehensive analysis of thermogravimetry （TG）, cone calorimeter and SEM-EDX investigations, possible flame retardancy and smoke suppression mechanisms were revealed. Besides the fuel dilution and barrier effect of MH, the combination of MH and RDP shows an additional flame inhibition effect. The combination of MH and BDP results in a dominant condensed phase barrier effect which leads to obvious reduction on smoke emission and flammability.

Differential Scanning Calorimetry Study of Polyamide 6/Polycarbonate

Blends of polyamide 6 and polycarbonate were prepared by a Brabender mixer （ PLV- 151） at 240 ℃ with 30 rpm for time 15, 8 and 6 minutes respectively. The thermal properties of blends with constituent ratio of 100/0, 60/40 and 20/80 are examined by Differential scanning calorimetry. DSC measures the temperatures and heat flow associated with transitions in materials as a function of time and temperature. The melting point temperature （Tm）, crystalline temperature （Tc）, and glass transition temperature （Tg） are observed.

MODIFICATION OF POLYAMIDE 6 WITH POLYAMINOAMIDE-g-POLY(ETHYLENE GLYCOL)VIA HYDROLYTIC POLYMERIZATION

To enhance the impact strength of polyamide 6, hydrolytic polymerization modification by the polyaminoamide-g-poly(ethylene glycol) (PAAEG) derivatives with poly(ethylene glycol) (PEG) molecular weight of 400-10000 was studied. Amide groups of polyaminoamide segments were postulated to form hydrogen bonding with polyamide 6, and hydroxy groups of PAAEG units were expected to react with carboxylic acid groups of polyamide 6 forming copolymers during the polymerization. The improved compatibility in amorphous regions of blends has been confirmed by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) of fracture surfaces. The effects of PAAEG on the water absorption and notch sensitivity of blends were investigated, using water uptake measurement and mechanical testings, respectively. For comparison, pure polyamide 6 and the blend of PEG/polyamide 6 were also investigated. The addition of PAAEG retarded the crystallization of polyamide 6, but did not make remarkable influences on its crystalline structure. As a consequence of the strong interactions between the dispersed phases and polyamide 6 matrices, PAAEG was a more suitable additive for improving the notched impact strength of polyamide 6 than PEG.

Compatibility between Polyamide 6 and Polycarbonate Detected by SEM

Polyamide （PA6） and polycarbonate （PC） were prepared by a Brabender mixer （ PLV- 151） at 240℃ with 30 rpm for duration of 8 and 6 minutes respectively. The epoxy resin （E） addition can lead to substantial microstructural changes in the PA6/PC blends. Scanning electron microscope （SEM） was used to observe the mixtures characterized by the domains of clearly segregated homophases and voids between the two polymers. PA6/PC of polyamide 6 and polycarbonate with epoxy resin addition under the composition ratio of 20/80, 20/80/1, 40/60/1 and 40/60, were tested to verify the key role of epoxy in promoting the compatibility of PA6 with PC during blending.

Melting Behavior of PA6 and PA6/PE Blends Crystallized from Amorphous State

Aim To investigate the melting behavior of polyamide 6 in polyamide 6/polyethy lene blends crystallized from amorphous state. Methods DSC was used to test effects of annealing temperature, annealing time, DSC scan rate, and the step wise annealing on the melting peaks of the ice water quenched specimens. Results and Conclusion Varied melting peaks of PA6 component were obtained. The degree of perfection and the crystallization degree of PA6 crystals decreased in the blends, and the crystallization degree of PA6 increased with the increasing of the annealing time. The height of the upper melting peak of reference PA6 is higher than that in blends.

Effect of Thermal Treatment on the PA-6 in the Blends

Aim To investigate the multiple melting behavior of polyamide 6(PA 6) in polyamide 6/linear low density polyethylene blends crystallized from the crystal amorphous state. Methods\ The effects of annealing temperature, annealing time, heating rate, and the step wise annealing were measured by DSC. Results and Conclusion\ There exists a critical heating rate affecting the middle temperature melting peak. When annealed at the temperature close to the melting peak, the main melting peak of PA 6 shifted to a higher temperature. Within a short time, annealing time has much effect on neat PA 6 but little effect on PA 6 in the blends. Addition of PE results in a decreasing in the height of melting peak. These phenomenon show that the melting behavior of PA 6 was affected by PE, compatibilizer, as well as thermal treatment.

Analysis of photocatalytic degradation of polyamide microplastics in metal salt solution by high resolution mass spectrometry

Microplastic pollution has become one of the most concerned focuses in the world.Among many treatment methods,photocatalysis is considered to be one of the most environmentally friendly methods.In this work,the photodegradation behavior of polyamide microplastics is studied by using polyamide 6(PA6)as model microplastics and FeCl_(3) as catalyst.It is hoped that the PA6 fiber can be effectively degraded by utilizing the strong oxidizing active species that can be produced after FeCl_(3) is irradiated in water.The results shows that PA6 fiber can be almost completely degraded after 10 days of irradiation in FeCl_(3) aqueous solution,indicating that it is promising to use this new method to solve the problem of PA6type microplastics.In addition,the chain scission mechanism and degradation process of PA6 are analyzed in detail by ultra-high performance liquid chromatography-tandem mass spectrometry(UPLC-MS),which provides a new insight for the study of polymer degradation mechanism.

AMMONIUM SULFAMATE FLAME RETARDED POLYAMIDE 6:MORPHOLOGY AND THERMAL DEGRADATION

The effect of ammonium sulfamate （AS） content on the flame retardancy of polyamide 6 （PA6） was studied. It is found that the limiting oxygen index （LOI） of PA6 increases with the increase of AS content and the flame retardancy of PA6 is significantly improved. The morphology of the residues after combustion was examined by means of scanning electron microscopy （SEM）. SEM results show that AS facilitates the formation of the intumescent char layer with honeycomb-like structure, which inhibits the transfer of heat and mass, and thus improves the flame retardancy of PA6. The thermal degradation of AS flame retarded PA6 was studied by thermogravimetric analysis （TGA）. The Kissinger method was applied to estimate the activation energy （Ea） of the degradation. The activation energy of the thermal degradation of PA6 decreases by adding AS, indicating that AS can promote the degradation of PA6.

The Development of Thermal Conductive Polymer Composites for Heat Sink

The thermal and mechanical properties of the polyamide 6/boron nitride and polyphenylene sulfide/graphite composites have been investigated as a function of composition and size of fillers. The addition of highly thermal conductive h-BN and graphite gives rise to large increase （about 2 times） of thermal conductivity of individual polymer. In PPS/graphite system, the higher conductivity value was obtained when smaller graphites were added. Meanwhile, the tensile and flexural strength are reduced upon increasing filler loading.

Effects of Zinc Oxide Nanoparticles on the Morphology and Viscoelastic Properties of Polyamide 6/Poly(butylene terephthalate) Blends

The morphology of polyamide 6/poly(butylene terephthalate)(PA6/PBT, 70/30, W/W) blends filled with pristine Zinc oxide(ZnO) nanoparticles and ZnO surface-modified by γ-glycidoxypropyltrimethoxysilane(K-ZnO) was investigated. The incorporation of ZnO and K-ZnO by one-step compounding both resulted in a smaller size and narrower distribution of PBT domains and the effect of ZnO was greater than K-ZnO. To reveal the underlying mechanism, two-step compounding in which ZnO or K-ZnO was premixed with PA6 or PBT was conducted and the finest morphology was achieved when mixing PA6 with premixed PBT/ZnO. Transmission electron microscopy(TEM) demonstrated that ZnO was distributed in PBT in all cases and K-ZnO was enriched at the interface except when K-ZnO was premixed with PBT. ZnO and K-ZnO caused a deterioration in the melt rheological properties of PBT, which played a dominating role in the morphological changes. In addition, the interfacial localization of K-ZnO enhanced the dynamic rheological properties of PA6/PBT blends substantially.

Fabrication of high-stability Ni-PSF@PAO40 microcapsules and their lubricating properties in polyamide 6

Novel Ni-PSF@PAO40 microcapsules(NPPMS)with high stability were prepared by using a combined processing method of electroless nickel plating and solvent volatilization.The results indicate that Ni is completely assembled on the surfaces of PSF/PAO40 microcapsules with the encapsulation capacity of NPPMS achieved at 50%.Organic solvents immersion shows that NPPMS have an excellent chemical stability.Macro thermal stability tests reveal that the softening temperature of NPPMS is increased up to over 400℃ while it becomes lower than 200℃ for PSF/PAO40 microcapsules.Furthermore,NPPMS were embedded into polyamide 6(PA6)to prepare PA6/NPPMS composites.The cross-sectional morphology shows that NPPMS are intact in PA6 matrices.The microhardness of PA6 is effectively improved with the incorporation of NPPMS.As compared with neat PA6,the coefficient of friction(COF)for PA6/NPPMS composites with 10%NPPMS could be reduced by 87.7%(from 0.49 to 0.06)and the wear rate could be decreased by 96.8%(from 1.29×10^(-5) to 4.15×10^(-7) mm^(3)/(N·m)).Further studies confirmed that increasing test loads and test temperatures was beneficial to improve the lubrication performance of NPPMS despite the opposite trend occurred when increasing the sliding speeds.It has been demonstrated that synergistic effects between PAO40 and Ni layer play an important role in improving the tribological properties of PA6.Therefore,NPPMS significantly improve the ability of microcapsules to resist a harsh environment,which has important scientific significance for expanding the use of microcapsules more practically in self-lubricating composites.

Quantitative analysis of elements (C,N,O,Al,Si and Fe) in polyamide with wavelength dispersive X-ray fluorescence spectrometry

A wavelength dispersive X-ray fluorescence （WD-XRF） spectrometry combined with calibration curve method was estab- lished for simultaneously analyzing low-Z elements （C, N, O） and A1, Si, Fe in polyamide. To investigate the origin of plastic material causing deposition and blocking in instrument engines and pipelines, polyamide 6 （PA 6, an engineering plastic） was chosen as the study object on account of its common use in industry. The sample preparation with pressed powder disk has been developed for determination of six elements in PA 6. Pure Cu metal was used as the matrix and PA 6 was regarded as standard sample for C, N, O elements. PA 6 particles were firstly smashed to uniform powder in liquid nitrogen, and then mixed with inorganic standard powders （Fe203, A1203, SIO2, and Na2SiO3）. The mixture was ground to obtain homogeneous calibration materials for WD-XRF analysis. The quantitative property of the calibration curve method for each element was re- liable. The limits of detection （S/N≤3） of C, N, O, A1, Si and Fe using WD-XRF were 249, 120, 101, 6.2, 3.3, and 1.8 μg/g, respectively. To confirm the accuracy of the proposed WD-XRF calibration curve method, inductively coupled plasma optical emission spectroscopy （ICP-OES） detection for A1, Si, Fe and elemental analyzer （EA） analysis for C, N, O were utilized. A good correlation of the WD-XRF results with the measurements of ICP-OES and EA was observed.