细旦尼龙6纤维加工过程中的晶型转化行为

通过引入富镧稀土化合物等添加剂,成功实现了细旦尼龙6纤维的熔融纺丝．考察了在纺丝卷绕成型以及牵伸过程中尼龙6纤维的晶型变化．借助XRD和FT－IR等研究手段,发现尼龙6在纺丝过程中可以生成亚稳态的B晶型晶体．这种β晶型经过沸水处理后很容易转化为α晶型,而γ晶型尼龙6经沸水处理后不发生相转变．因此可以通过沸水热处理的方法区分尼龙6的β和γ晶型．在纤维的卷绕过程中,当熔体拉伸倍数较高时,尼龙6可能产生β晶型;当熔体拉伸倍数较低时,则以γ晶型为主．在纤维的牵伸过程中,γ晶型经过β晶型中间态向α晶型相转变．上述结果对于指导改进细旦尼龙6纤维的加工工艺以及提高产品性能有指导意义．     

尼龙6与半芳香性非晶尼龙原位共混物的结构与性能

一种半芳香的非晶尼龙共聚物溶解于熔融的己内酰胺中,引发后者负离子开环聚合原位制备尼龙6与非晶尼龙的共混物.与纯尼龙6相比较,此原位共混物的强度与模量显著提高.非晶区呈现单一的玻璃化转变,表明共混物为均相体系,其组分的相容性源于负离子聚合过程中链交换反应引起的共聚.与纯尼龙6相比较,此共混物的熔点与结晶度显著降低.此外,与纯尼龙6只存在α晶不同,共混物中伴生有大量的γ晶.当非晶尼龙含量为20 wt%时,绝大部分晶体为γ晶.然而,共混物中球晶仅有一定程度细化.共混物强度和模量的提高被认为主要源于非晶区分子活动能力降低以及γ晶相对含量的提高.     

尼龙1012的Brill转变

作为一类重要的结晶性聚合物 ,尼龙在加热或冷却过程中的晶型转变 [1,2 ]一直为人们所关注 .其中对尼龙 66的晶型转变研究得最多 [3～ 6 ] .在加热过程中尼龙 66室温下三斜的α晶型转变为高温下的假六方晶型 ,尼龙 66的这一晶型转变称为 Brill转变 [3] .在变温 X射线衍射测试中可明显观察到 Brill转变 :室温下α晶型的两个强的衍射峰随温度升高逐渐靠近 ,并在某一温度下合并为一个峰 ,这一温度称为 Brill转变温度 .近年来研究表明 ,许多脂肪族的尼龙升温时均表现出 Brill转变 ,并且 Brill转变温度随尼龙结晶条件及其结构的不同而不同 [7…     

牵伸作用对尼龙6纤维晶型结构及力学性能的影响

利用广角X射线衍射仪(WAXD)、傅里叶变换红外光谱仪(FTIR)、示差扫描量热仪(DSC)、声速取向测量仪、扫描电镜(SEM)以及纱线强伸度仪研究了不同牵伸倍数尼龙6复丝的晶型结构、熔融行为、取向度、表面形貌以及力学性能.结果表明,随着牵伸倍数的增加,伴随着γ晶型片晶的生长以及非晶区链段重排诱导α晶型的生成,尼龙6复丝的结晶度不断的提高,在牵伸倍数达到3倍时,样品中出现了α晶型的特征衍射峰,导致了其熔融温度的提高以及多重熔融峰的出现.同时,牵伸作用也增加了分子链沿纤维轴向的取向程度,消除了纤维表面的残余应力,改善了纤维的表面缺陷.在这些因素的共同作用下,尼龙6复丝的力学性能得到了一定程度的提高,当牵伸倍数为3倍时,拉伸强度与拉伸模量分别达到了5.0 c N/dtex和28.9 c N/dtex,与较低牵伸倍数相比较均有所提高.     

尼龙1010的拉伸结晶行为及Brill转变

摘要 :本文通过示差扫描热分析,广角X射线衍射分析及二维广角X射线散射等手段研究和讨论了尼龙1010在不同的拉伸比率(λ)及拉伸温度（Td）下拉伸诱导的晶体转变及结晶取向行为。实验表明,在拉伸条件下,尼龙1010易于从α晶型向δˊ晶型转变,而拉伸比率的提高,有利于促进这种Brill转变。而在相同的拉伸比率下,随着拉伸温度的提高,发现了尼龙1010从δˊ晶型向α晶型的独特转变,而这种过程刚好与无拉伸状态下的尼龙1010晶型和温度的相互关系截然相反。二维广角X射线散射实验研究结果表明尼龙1010的晶体取向度主要和拉伸比有关,并且（002）的晶面间距随着拉伸比率的提高而增大,表明了长轴尺寸的增大对拉伸取向的依赖关系。     

不同温度下尼龙6性能和结构变化的原位研究

利用拉伸热台对尼龙6在不同温度下的拉伸性能进行了测试和分析.随着拉伸温度的升高,尼龙6样品的屈服强度和杨氏模量逐渐下降.采用了一个阿伦尼乌斯模型来描述尼龙6屈服强度与拉伸温度之间的关系,并描述了尼龙6样品黏度、玻璃化温度对屈服强度的影响.通过原位同步辐射广角衍射分析,我们发现未拉伸的尼龙6样品中的α相与γ相的相对比率随温度升高而下降.在拉伸条件下,随着拉伸温度的升高,样品的结晶部分容易产生滑移或晶区的熔融,有序程度下降,因而样品承载外力的能力下降,体现为屈服强度和杨氏模量的下降.     

尼龙-6和尼龙-6合金的球晶结构与破坏性能的研究

成型冷却速度即结晶速度对单纯尼龙 ６和尼龙 ６合金的拉伸破坏性能具有不同的影响．结晶速度慢，球晶尺寸大，单纯尼龙 ６的拉伸破坏强度高，破坏形变和破坏能量减小；尼龙 ６／热塑性聚酰胺弹性体／增容剂合金不仅拉伸破坏强度高，而且破坏形变和破坏能量都有所增加．研究表明，虽然球晶尺寸影响尼龙 ６的破坏性能，但球晶的性质即球晶的界面上和片晶 片晶间的非晶部分结构、微小分散粒子的空洞化及相与相之间的界面结合强度是影响尼龙 ６破坏性能的主要因素．     

热处理对尼龙6及其与聚酰胺嵌段共聚物共混体系晶体熔融行为和结晶结构的影响

采用溶液共混-共沉淀的办法获得尼龙6及聚酰胺嵌段共聚物/尼龙6共混体系粉末,样品在260℃下熔融之后经程序降温的方法得到非淬火样品,然后分别在190℃下高温退火不同时间(0~48 h),采用示差扫描量热仪(DSC)、广角X射线衍射仪(WAXD)、偏光显微镜(POM)等表征手段研究热处理对体系晶体熔融行为和结晶结构的影响.结果表明,(1)在相同的热历史条件下,嵌段共聚物的存在影响了尼龙6的结晶行为及结晶结构;(2)退火处理对两种样品有着不同的影响,对于尼龙6体系,退火处理促进了非晶相向晶相的转变,大大提高样品的结晶完善程度和结晶度;对于共混体系,退火处理同样促进了非晶相向晶相的转变,同时形成新的α型和γ型结晶,体系的结晶完善程度明显提高,退火48 h后,结晶度比原始样品提高约84%.     

尼龙6/抗菌蛭石复合材料的制备及性能研究

通过离子交换法对蛭石进行载银和有机化改性,制备出3种抗菌蛭石,进一步采用熔融共混法制备了尼龙6/抗菌蛭石复合材料,测试了复合材料的抗菌性能和物理力学性能,利用TEM和SEM观察了蛭石在尼龙6中的分散情况和拉伸断面.研究结果表明,载银并有机化的蛭石与尼龙6的复合材料对大肠杆菌和金黄色葡萄球菌均具有明显的抑菌圈,对大肠杆菌...     

三氯乙酸刻蚀法观测尼龙球晶形态

筛选出特效刻蚀剂——三氯乙酸溶液,建立了简便、可靠且十分有效的表征本体尼龙-6球晶形态的方法,借助SEM首次对MC尼龙及其改性样品的结晶形态进行了直接观测,三维结构的球晶清晰可见,球晶直径为几十微米.利用三氯乙酸及其溶剂与各种添加剂的物理或化学作用,可有效地研究改性尼龙的球晶缺陷.     

Crystal structure,morphology, and mechanical properties of biaxially oriented polyamide-6 films toughened with poly(ether block amide)

Biaxially oriented polyamide-6 (BOPA) film has been widely used in many packaging applications. However, the BOPA film with excellent toughness is still required when utilizing in the field of soft-packaged lithium - ion batteries, pharmaceutical blister packaging, or frozen food packaging especially for vacuum packaging of irregular-shaped food products. The purpose of this study was to improve the toughness of BOPA films by toughening with poly(ether block amide) (PEBA) (BOPA/PEBA films) based on the simultaneous biaxial stretching technology. The crystal structure, morphology, optical properties, barrier, and mechanical properties of BOPA/PEBA films were investigated. The results showed that the incorporation of PEBA into BOPA films slightly decreased the melting temperature and crystallinity of PA6, and the BOPA/PEBA films exhibited only α-form crystals and no preferential orientation in the machine direction (MD) and transition direction (TD). The morphological observation showed that higher addition of PEBA led to the formation of microvoids due to the poor compatibility between PA6 and PEBA. As a result, the transmittance and oxygen barrier properties of the BOPA/PEBA films decreased. In addition, mechanical analysis suggested that the addition of PEBA could effectively improve the toughness of BOPA film.     

The influence of “two-phase” synthesis conditions on blown film extrusion of LDPE

LDPE synthesized under two-phase conditions is known to have a good balance of blown film properties. Good optical properties and high impact strength are characteristic for two-phase LDPE grades. In order to obtain systematic information, LDPE was synthesized at several different pressures with two different melt index levels. Blown film was extruded at different output rates and melt temperatures. The influence on haze and dart drop impact was studied. Two-phase conditions were found to improve haze and dart drop impact and the improvement was impressive, especially for the low melt index grades. By increasing the output rate, the dart drop values were further improved. The influence of melt temperature on dart drop impact goes through an optimum and overall haze decreases with increasing melt temperature. For films made from two-phase grades, dart drop impact decreases as internal haze increases. For corresponding internal haze values, the films made from single-phase grades have lower dart drop values and they are somewhat scattered.     

Effect of surface modification of montmorillonite on the properties of aromatic polyamide/clay nanocomposites

The surface modification of montmorillonite clay was carried out through ion‐ exchange reaction using p‐phenylenediamine as a modifier. This modified clay was employed to prepare aromatic polyamide/organoclay nanocomposite materials. The dispersion behavior of clay was examined in the polyamide matrix. Polyamide chains were synthesized from 4‐aminophenyl sulfone and isophthaloyl chloride (IPC) in dimethylacetamide. These amide chains were suitably end‐capped with carbonyl chloride end groups to interact chemically with modified montmorillonite clay. The resulting nanocomposite films containing 2–20 wt% of organoclay were characterized by TEM, X‐ray diffraction (XRD), thin‐film tensile testing; thermogravimetric analysis (TGA), differential scanning calorimetric (DSC) and water absorption measurements. Mechanical testing revealed that modulus and strength improved up to 6 wt% organoclay loading while elongation and toughness of nanocomposites decreased with the addition of clay content in the matrix. Thermal decomposition temperatures of the nanocomposites were in the range 225–450 °C. These nanocomposites expressed increase in the glass‐transition temperature values relative to pure polyamide describing interfacial interactions among the phases. The percent water uptake of these composites reduced upon the addition of modified layered silicate depicting improved barrier properties. Copyright © 2008 John Wiley & Sons, Ltd.     

Mechanical properties and enzymatic degradation of poly[(R)-3-hydroxybutyrate] fibers stretched after isothermal crystallization near Tg

Poly[(R)-3-hydroxybutyrate] (P(3HB)) fibers with high tensile strength were prepared by stretching the fibers after isothermal crystallization near the glass transition temperature. Two samples with different molecular weights (M_w = 0.7 × 10⁶ and 4.3 × 10⁶) were used to investigate the effect on tensile strength. Increasing the time for isothermal crystallization of P(3HB) fibers resulted in a decrease in the maximum draw ratio. But, the tensile strength of P(3HB) fibers increased remarkably when the isothermal crystallization time was prolonged to more than 24 h. The tensile strength of low-molecular-weight drawn fibers was higher than that of high-molecular-weight fibers. Therefore, it can be concluded that this procedure does not increase the tensile strength of the high-molecular-weight drawn fibers. This is because, in this drawing method, small crystal nuclei grow initially during the isothermal crystallization process. Then, the molecular chains between the small crystal nuclei that acted as the entanglement points are oriented by stretching. In the case of the high-molecular-weight fibers, because the molecular length between the entanglement points of the small crystal nuclei is too long, the molecular chains are not sufficiently oriented by the stretching process. However, in the case of the low-molecular-weight fibers, the molecular length is suitable for generating the extended chains. Based on the result of X-ray analysis of P(3HB) fibers stretched after isothermal crystallization, fibers have the oriented α-form crystal with 2₁ helix conformation and β-form with planar zigzag conformation. The enzymatic degradation of the stretched P(3HB) fibers was performed by using an extracellular PHB depolymerase purified from Ralstonia pickettii T1. The enzymatic erosion rate of β-form was faster than that of α-form in the P(3HB) fibers stretched after isothermal crystallization.     

Effect of intercalating agents on structure and properties of dimer acid‐based polyamide modified by in situ doping of Na‐montmorillonite

Under the condition of 0.4% (mass), the effects of intercalating agents on conglomeration structure and thermal and mechanical properties of dimer acid‐based polyamide (DAPA) were investigated. The results show that layer‐stripped Na‐montmorillonite (MMT) with octadecyl trimethyl ammonium chloride caused a sharp decrease of content of the γ crystal phase in DAPA, thus bringing out decrease in mechanical properties and increase in IZOD notched impact strength while a sharp increase of content with the γ crystal phase in DAPA modified by Na‐MMT with dioctadecyl dimethyl ammonium chloride. Thus, it brought out a large increase in mechanical properties and a limited increase in IZOD notched impact strength. The decomposition reaction processes of DAPA modified by Na‐MMT and Na‐MMT with octadecyl trimethyl ammonium chloride were one step ranging from 410 to 500°C, respectively. The thermal decomposition reaction processes of DAPA modified by Na‐MMT with dioctadecyl dimethyl ammonium chloride were two steps. Copyright © 2016 John Wiley & Sons, Ltd.     

Multiple melting behavior of isotactic polypropylene and poly(propylene-co-ethylene) after stepwise isothermal crystallization

The multiple melting behavior of several commercial resins of isotactic polypropylene (iPP) and random copolymer, poly(propylene-co-ethylene) (PPE), after stepwise isothermal crystallization (SIC) were studied by differential scanning calorimeter and wide-angle X-ray diffraction (WAXD). For iPP samples, three typical melting endotherms appeared after SIC process when heating rate was lower than 10 °C/min. The WAXD experiments proved that only α-form crystal was formed during SIC process and no transition from α1- to α2-form occurred during heating process. Heating rate dependence for each endotherm was discussed and it was concluded that there were only two major crystals with different thermal stability. For the PPE sample, more melting endotherms appeared after stepwise isothermal crystallization. The introduction of ethylene comonomer in isotactic propylene backbone further decreased the regularity of molecular chain, and the short isotactic propylene sequences could crystallize into γ-form crystal having a low melting temperature whereas the long sequences crystallized into α-form crystal having high melting temperature.     

Nanocomposite nonwoven materials based on polyamide-6 and montmorillonite,prepared by electrospinning of the polymer melt

The effect of montmorillonite on the structure and properties of nonwoven microfibrous materials based on polyamide-6 and prepared by electrospinning of the polymer melt was studied. Addition of 3% montmorillonite into the melt increases its viscosity and electrical conductivity, with the mean diameter of the formed fibers increasing from 8 to 12 μm. As shown by X-ray diffraction, IR spectroscopy, and differential scanning calorimetry, pellets of the pristine polyamide are characterized by prevalence of crystals of the stable α-form, whereas in the composites and nonwoven materials the metastable γ-form prevails. Addition of montmorillonite only slightly influences the contact angles, and the resulting materials exhibit nearly superhydrophobic properties.     

Crystal Transformation and Development of Tensile Properties upon Drawing of Poly(L-lactic acid) by Solid-State Coextrusion: Effects of Molecular Weight

Melt-crystallized films of poly(L -lactic acid) (PLLA) with M_v in the range of 3.8 ∼ 46 × 10⁴ consisting of α-form crystals were uniaxially drawn by solid-state coextrusion. The effects of M_v, extrusion draw ratio (EDR), and extrusion temperature (T_ext) on the crystal/crystal transformation from α- to β-form crystals and the resultant tensile properties of drawn products were studied. The crystal transformation proceeded with EDR and more rapidly for the higher M_v's. Furthermore, the crystal transformation proceeded most rapidly with EDR at a T_ext around 130 °C, independently of the M_v's. As a result of the optimum combination of processing variables influencing the the crystal transformation (M_v, T_ext, and drawability), highly oriented films consisting of β-form crystals alone were obtained by coextrusion of higher M_v samples at T_ext's slightly below the melting temperature (150 ∼ 170 °C) and at higher EDR's > 11. Both the tensile modulus and strength increased rapidly with EDR. The modulus at a given EDR was slightly higher for the samples with higher M_v's. In contrast, the strength at a given EDR was remarkably higher for the higher M _v's. The highest tensile modulus of 8.0 GPa and strength of 500 MPa were obtained with the sample of the highest M_v of 46 × 10⁴ coextruded at 170 °C to the highest EDR of 14.     

Development of PE/PCL Bilayer Films Modified with Casein and Aluminum Oxide

The studied samples were prepared from polyethylene (PE) polymer which was coated with modified polycaprolactone (PCL) film in order to obtain bilayer films. Thin PCL film was modified with casein/aluminum oxide compound to enhance vapor permeability as well as mechanical and thermal properties of PE/PCL films. Casein/aluminum oxide modifiers were used in order to achieve some functional properties of polymer film that can be used in various applications, e.g., reduction of water vapor permeability (WVTR) and good mechanical and thermal properties. Significant improvement was observed in mechanical properties, especially in tensile strength as well as in water vapor values. Samples prepared with aluminum oxide particles indicated significantly lower values up to 60%, and samples that were prepared with casein and 5% Al₂O₃ showed the lowest WVTR value.     

Characterisation of spray-dried emulsions with mixed fat phases

Fat encapsulation in spray-dried protein-stabilised emulsions is known to depend on the choice of protein, the emulsion droplet size, and the melting point of the fat. However, the fat encapsulation may also depend on the fat crystal habit. Fats may crystallise in three different forms , β′ and β, of which the β-form is thermodynamically stable. The -form is obtained in rapidly cooled fats, and it can then transform into the β′-form during storage, and this crystal form is finally transformed into the β-form. In order to investigate the effect of different fat phases on the spray-dried emulsions, two solid fats were studied: fully hardened rapeseed oil (β-stable) and fully hardened palm oil (β′-stable). The solid fats were used on their own or in mixtures with rapeseed oil, in order to provide fat phases with different properties. The emulsion composition was chosen as to mimic the composition of whole milk, i.e. 40% lactose, 30% sodium caseinate and 30% fat on a dry weight basis. The dried powders were stored under dry conditions at 4 or 37 °C in order to investigate the changes in the fat crystals and surface composition of the powders with time. The surface composition was analysed using electron spectroscopy for chemical analysis. Evaluation of the data showed that surface coverage of fat varied depending on the composition of the fat phase. The ratio of lactose to protein remained constant, which implies that the fat was present as ‘islands’ on a surface composed of lactose and protein. The hardened palm oil crystallised initially in the - or β′-form (depending on the ratio of hardened fat to oil), and during storage, the crystal form gradually changed into the β′-form. In powders containing hardened rapeseed oil only the stable β-form was found, even in fresh samples. The surface coverage of fat was reduced after storage, whereas the ratio of lactose to protein at the surface remained unchanged. The emulsion droplet size in emulsions prepared at a low homogenisation pressure was considerably increased after spray-drying and reconstitution, whilst the emulsion droplet size was well preserved in emulsions prepared at high homogenisation pressure.