正交试验法优化ACR增韧PLA的制备工艺

采用乳液聚合法制备了一系列核壳型增韧改性剂ACR并用于聚乳酸(PLA)的增韧。利用L16(45)正交试验设计方法,研究了ACR粒子的核壳比、粒径、用量以及交联剂用量对共混体系结构和性能的影响。结果得出增韧PLA的最佳工艺条件为:ACR核壳比75/25,粒径约185.0 nm,用量20%,交联剂用量0.5%。此时PLA/ACR共混物的冲击强度为29.128 kJ/m~2,约为纯PLA的11倍。极差分析结果表明,ACR用量和核壳比是影响增韧效果的主要因素。     

ACR核层中交联单体对PC/ACR共混物性能的影响

用丙烯酸丁酯、交联单体和甲基丙烯酸甲酯经乳液聚合和后处理制备了聚丙烯酸丁酯(PBA)/聚甲基丙烯酸甲酯(PMMA)核壳结构的丙烯酸酯树脂(ACR),然后将ACR与聚碳酸酯(PC)共混进行增韧改性。研究了ACR核层中交联单体对PC/ACR共混物力学性能的影响,并用SEM对共混物冲击断面形貌进行了研究。结果表明:随着ACR核层中交联单体含量的增加,PC/ACR共混物的缺口冲击强度呈现先增加后降低的趋势,拉伸强度和弯曲强度变化很小。当交联单体B含量为10%时,PC/ACR共混物的冲击强度达到最大为50.4 kJ/m2,约是纯PC冲击强度的5倍。     

聚乳酸/液态聚异丁烯共混物的研究

为了改善聚乳酸(PLA)材料的脆性,且不影响其可降解性,选择了低分子量液态聚异丁烯(LPIB)和PLA进行共混改性,研究了LPIB用量对PLA/LPIB共混物性能的影响。结果表明,LPIB可提高PLA的韧性,但降低了其拉伸强度,当LPIB质量分数为12%时,共混物的缺口冲击强度达到最高,为5.3 k J/m2,比纯PLA提高了近一倍;LPIB在PLA中起到异相成核的作用,可提高其结晶度。采用扫描电子显微镜观察了共混物的微观形态,发现PLA与LPIB两相是分离的。为提高两者的相容性,采用缩水甘油酯(GMA)接枝LPIB(LPIB-g-GMA)作为增容剂,并研究了其用量对PLA/LPIB/LPIB-g-GMA共混物性能的影响。结果表明,LPIB-g-GMA对PLA/LPIB共混物有一定的增容作用,可使其相界面变得模糊,相容性有明显提高;当PLA,LPIB与LPIB-g-GMA的质量比为88/2/10时,PLA/LPIB/LPIB-g-GMA共混物的缺口冲击强度和拉伸强度达到最大,与未加LPIB-g-GMA的共混物相比,分别提高了20.7%和13.8%;少量LPIB-g-GMA的加入会提高PLA/LPIB/LPIB-g-GMA共混物的结晶度,但其用量过高时,会降低共混物的结晶度。     

酯交换反应对PLA/PBS共混物性能的影响

为提高聚乳酸(PLA)的韧性,以钛酸四丁酯(TBT)为酯交换剂,采用反应性挤出技术制备了PLA/聚丁二酸丁二酯(PBS)共混物,并通过万能试验机、扫描电子显微镜、动态热机械分析仪等研究了TBT用量对PLA/PBS共混物的力学性能、形貌结构及动态力学性能的影响。研究结果表明,加入0.15份TBT可改善PLA和PBS间的相容性,使得PBS在PLA基体中分散均匀且颗粒变小。随着TBT用量的增加,PLA/PBS共混物的拉伸强度变化不大,而其韧性得到明显提高。当TBT用量为0.15份时,与纯PLA相比,PLA/PBS共混物的断裂伸长率和冲击强度分别提高了25.6倍和2.0倍。随着TBT用量的增加,PLA/PBS共混物的储能模量增大,而PLA和PBS的玻璃化转变温度差值的绝对值变小。     

PVC/ACR共混物结构与性能的研究

采用乳液聚合技术合成一系列具有核-壳结构的丙烯酸酯类抗冲改性剂(ACR),将其与聚氯乙烯(PVC)进行熔融共混制备PVC/ACR共混物。研究ACR的核/壳比、橡胶的粒子尺寸和交联剂三烯丙基异三聚氰酸酯(TAIC)含量对PVC/ACR共混物力学性能与形态结构的影响。结果表明,随着核/壳比的增大,ACR的增韧效率有了明显的提高;交联剂的加入改变了ACR的刚性与韧性,进而对共混物的性能有了较大的影响,随着交联剂含量的增加,共混物的冲击强度先变大后减小,当交联剂的含量为4%,ACR的添加量为8 phr时,共混物的冲击强度达到了1 196.70 J/m;随着橡胶粒子尺寸的增加,共混物的韧性逐渐降低。扫描电子显微镜分析表明,ACR增韧PVC的主要增韧机理是橡胶的空洞化和基体的剪切屈服。     

PLA/PBS共混物增黏改性的研究

采用熔融反应共混法,通过引入过氧化二苯甲酰(BPO),对聚乳酸/聚丁二酸丁二醇酯(PLA/PBS)进行增黏改性。研究了该PLA/PBS反应共混物的流变性能、凝胶分数、热性能、力学性能和断面微观形貌。结果表明:随着BPO用量的增加,PLA/PBS反应共混物的转矩和凝胶分数均增大;PLA/PBS反应共混物的结晶性和熔点(Tm)随着BPO用量的增加而降低,且出现熔融双峰,当BPO用量增至1 phr时,熔融双峰消失,PLA和PBS间的相容性显著改善;随着BPO用量的增加,PLA/PBS反应共混物的断裂伸长率、拉伸强度、冲击强度均有所提高,而玻璃化转变温度(Tg)先降后升,体系的内耗则逐渐降低。     

ACR增韧聚碳酸酯/聚乳酸合金的制备与性能研究

以核壳结构的丙烯酸酯类树脂(ACR)作为增韧剂,对聚碳酸酯(PC/)聚乳(酸PLA)合金进行增韧改性,研究了ACR用量对合金力学性能、热性能和微观形态的影响。结果表明:加入一定用量的ACR,合金的冲击强度大幅度提高,而其他力学性能影响较小;合金比例为PC/PLA=90/10时,二者的相容性良好,体系只有一个玻璃化温度;ACR的用量对合金的微观形态有一定的影响。     

ACR增韧PBT/PC合金的研究

研究了“核-壳”结构的ACR对PBT/PC(质量比80/20)合金的力学性能和耐热性的影响。结果表明:随着ACR用量增加,共混物的缺口冲击强度不断增大,而拉伸强度、弯曲强度、维卡耐热度降低。当ACR的加入量为5份时,缺口冲击强度提高1倍,当ACR的加入量为30份时,缺口冲击强度约为纯PBT/PC合金的5倍。从增韧效果来看,FM50略好于KM355。     

环氧类增容剂反应增容PLA/PBAT共混体系的研究

以环氧类增容剂(REC)为增容剂,采用双螺杆挤出机熔融共混制备聚乳酸(PLA)/聚对苯二甲酸己二酸丁二醇酯(PBAT)共混物。研究了增容剂对共混体系微观结构、力学性能和热性能的影响。结果表明,添加适量REC可以提高PLA与PBAT的相容性,改善PLA/PBAT共混体系的综合力学性能;REC用量为1.4份时共混体系呈现出良好的相容性,此时共混物冲击强度由268 kJ/m2增加到621 kJ/m2、断裂伸长率提高由222 %增加到357 %。     

PLA-g-GMA的制备及其对PLA/PPC共混体系性能的影响

采用双螺杆挤出机将甲基丙烯酸缩水甘油酯(GMA)接枝到聚乳酸(PLA)上,而后将接枝产物(PLA-g-GMA)与聚乳酸(PLA)、聚碳酸亚丙酯(PPC)反应性共混,考察了接枝物中GMA加入量变化对PLA/PPC/PLA-g-GMA共混体系的力学性能、热稳定性能的影响,并对共混体系的断裂机理进行了研究。结果表明,PLA-g-GMA的引入能够在一定程度上改善PLA与PPC的相容性。随着接枝物中GMA加入量的增加,共混物的冲击强度、断裂伸长率及拉伸强度均呈现出先升高后降低的趋势,并在接枝物中GMA加入量为3%时达到最大值。扫描电镜结果显示,PLA-g-GMA引入后共混物的韧性断裂特征越发显著,其冲击断裂方式由脆性断裂过渡为韧性断裂。热失重分析结果显示,加入PLA-g-GMA后共混物的起始分解温度和完全分解温度均有一定程度的提高。     

Preparation and properties of poly(Nε,Nε-dicarboxymethyl-l-lysine)

A new ampholytic homopolypeptide, $\text{poly}\text{(N}{}^{\mathrm{\epsilon }}\text{,N}{}^{\mathrm{\epsilon }}\text{-}\text{dicarboxy-methyl-}\text{l}\text{-lysine}\text{)}$, which has one tertiary amino and two carboxyl groups in the side chain has been derived from a hydrochloride salt of poly(L-lysine). The polymer in aqueous solution seems to be in the coil form with locally extended structure (LES) at neutral pH. In both the acidic and alkaline regions, the molar ellipticity of the polymer changes as a result of change in net charge on the side chain. The conformational changes may be from the coil with LES to other coiled forms. 5–7 M NaClO₄ and 80% aqueous methanol induce the α-helix in the polymer at neutral pH. Divalent cations, Cu²⁺ and Ca²⁺, do not induce any remarkably ordered structures such as α-helix or β-structure in the polymer in aqueous solution at any pH. Ultraviolet absorption studies show an absorption peak of the polymer-Cu²⁺ complex near 240 nm. Dependence of the peak intensity on pH at various q values ($\text{q =}\text{[}\text{Cu}{}^{\mathrm{2+}}\text{]}\text{[}\text{residue}\text{]}$) indicates the two steps of the complex formation. At q less than 0.64, the formation is described only with the first step. An average coordination number for Cu²⁺ at the first step was calculated to be about 2 by the method of Mandel and Leyte. The association constant of Cu²⁺ with the residue at the step was determined from the absorption data to be far smaller than that for the Cu²⁺-EDTA complex. The second step of the formation occurs in the case of large q but the absorption data for the second step cannot be obtained exactly due to precipitation.     

Wet Milling of Fe/Al/Al2O3 and Fe2O3/Al/Al2O3 Powder Mixtures

Wet milling of Al₂O₃-aluminide alloy (3A) precursor powders in acetone has been investigated by milling Fe/Al/Al₂O₃ and Fe₂O₃/Al/Al₂O₃ powder mixtures. The influence of the milling process on the physical and chemical properties of the milled powders has been studied. Particle refinement and homogenization were found not to play a dominant role, whereas plastic deformation of the metal particles leads to the formation of dislocations and a highly disarranged polycrystalline structure. Although no chemical reactions among the powder components in Fe₂O₃/Al/Al₂O₃ powder mixtures were observed, the formation of a nanocrystalline, ordered intermetallic FeAl phase in Fe/Al/Al₂O₃ powder mixtures caused by mechanical alloying was detected. Chemical reactions of Fe and Al particle surfaces with the atmosphere and the milling media lead to the formation of highly porous hydroxides on the particle surfaces. Hence the specific surface area of the powders increases, while the powder density decreases during milling. The fraction of Fe oxidized during milling was determined to be 0.13. The fraction of Al oxidized during milling strongly depends on the metal content of the powder mixture. It ranges between 0.4 and 0.8.     

Participation of lewis base on vinyl chloride polymerization with Al(C2H5)3CCl4 catalyst system

The polymerization of vinyl chloride has been investigated using an $\text{Al}\text{(}\text{C}{}_2\text{H}{}_5\text{)}{}_3\text{CCl}{}_4$ catalyst system in the presence of various Lewis bases. Effective Lewis bases are γ-butyrolactone, diglyme and diethylenetriamine which are multidentate. The rate of polymerization is dependent not only on the basicity of the Lewis base used but also on a coordination number of one. The latter is the predominant factor. For the effect of polymeric amines, a tentative hypothesis is discussed.     

Sintering of Si3N4-Y2O3-Al2O3

Sintering kinetics of the system Si₃N4-Y2O₃-Al₂O3 were determined from measurements of the linear shrinkage of pressed disks sintered isothermally at 1500° to 1700°C. Amorphous and crystalline Si₃N₄ were studied with additions of 4 to 17 wt% Y₂O₃ and 4 wt% A1₂O₃. Sintering occurs by a liquid-phase mechanism in which the kinetics exhibit the three stages predicted by Kingery's model. However, the rates during the second stage of the process are higher for all compositions than predicted by the model. X-ray data show the presence of several transient phases which, with sufficient heating, disappear leaving mixtures of β ' -Si₃N₄ and glass or β '-Si₃N₄, α '-Si₃N₄, and glass. The compositions and amounts of the residual glassy phases are estimated.     

Synthesis and Characterization of Ti0.33Ta0.33Nb0.33C and Ti0.33Ta0.33Nb0.33CxN1-x Whiskers

Ta_0.33Ti_0.33Nb_0.33C and Ta_0.33Ti_0.33Nb_0.33C _x N_{1− x} whiskers were synthesized via a carbothermal vapor-liquid-solid growth mechanism in the temperature range 900°-1450°C in Ar or N₂. The optimum temperature was 1250°C. Whiskers were obtained in a yield of 70-90 vol%. The whiskers were 0.5–1 µm in diameter and 10–30 µm in length. The starting materials that produced the highest whisker yield were: TiO₂, Ta₂O₅, Nb₂O₅, C, Ni, and NaCl. C was added to reduce the oxides, and Ni to catalyze whisker growth. NaCl was used as a source of Cl for vapor-phase transportation of Ta and Nb oxochlorides and Ti chlorides to the catalyst. The catalyst metal was recycled several times during the synthesis and was transported as NiCl₂( g ) according to thermodynamic calculations. The rate of formation and the chemical composition of the whiskers depended on the synthesis temperature, the choice of catalyst, and the atmosphere. At low temperatures, the whiskers were enriched in Nb and Ta, whereas the Ti content increased with increased synthesis temperature.