LLDPE/POE共混物的交联行为研究

采用过氧化物交联研究了线性低密度聚乙烯(LLDPE)/乙烯-α-辛烯共聚物(POE)共混物。研究了工艺、配方对LLDPE/POE共混物凝胶含量的影响,以及凝胶含量与材料力学性能的关系。结果表明,LLDPE/POE共混物的凝胶含量随引发剂的用量、交联温度和交联时间的增加而增加,达到一定程度后不再增加。在170℃,30min的条件下DCP能充分分解引发交联反应,DCP用量为1.5%时,共混物的凝胶含量可以达到80%以上,再增加时凝胶含量不再增加。DCP的加入顺序对共混物的凝胶含量影响不大。共混物的凝胶含量对其动态力学行为有影响。共混物的凝胶含量对拉伸性能影响不大。     

硅烷交联PP/POE共混材料的性能研究

采用反应性挤出法制备了硅烷交联聚丙烯/聚烯烃弹性体(PP/POE)共混材料。研究了过氧化二异丙苯(DCP)用量对硅烷交联PP/POE共混材料凝胶含量、热稳定性、结晶行为、耐溶剂性及力学性能的影响。结果表明:随着DCP用量的增加,硅烷交联PP/POE共混材料的凝胶含量、热稳定和耐溶剂性均逐渐提升。随着交联程度的增大,共混材料中PP相的结晶度逐渐减小。扫面电子显微镜(SEM)分析结果显示,硅烷交联反应能够改善PP和POE相之间的相容性。力学性能测试结果显示,相比于未改性PP/POE共混材料,硅烷交联PP/POE共混材料的各项性能均有不同程度的提升。     

过氧化物交联聚乙烯的力学性能研究

采用过氧化物交联方法研究了交联聚乙烯的工艺、配方和性能，探讨了过氧化物用量对材料力学性能及凝胶含量的影响，以及炭黑、氧化锌、抗氧剂对材料性能的影响。结果表明，过氧化物交联聚乙烯的力学性能有一定的提高，随着DCP含量的增加，交联PE的凝胶含量提高，而随着凝胶含量的提高，交联PE的拉伸强度提高，断裂伸长率下降；炭黑对材料有一定的补强作用，氧化锌的加入有助于交联反应和拉伸强度的提高。     

VTMS含量对硅烷交联PP/POE共混材料性能的影响

采用一步法挤出工艺制备了硅烷交联聚丙烯/聚烯烃弹性体(PP/POE)共混材料。研究了乙烯基三甲氧基硅烷(VTMS)含量对硅烷交联PP/POE共混材料凝胶含量、热稳定性、结晶行为和力学性能的影响。结果表明:硅烷交联结构能够有效提升PP和POE相之间的相容性。随着VTMS含量的增加,硅烷交联PP/POE共混材料的凝胶含量和热稳定性呈上升趋势,而共混材料中PP相的结晶度却逐渐减小。力学测试表明,过氧化二异丙苯(DCP)在引发硅烷接枝反应的同时也会使PP发生降解。随着VTMS含量的增加,硅烷交联PP/POE共混材料的拉伸强度逐渐增大,断裂伸长率及缺口冲击强度则均呈先升后降趋势。     

EPDM/NBR共混胶硫化体系的研究

研究了过氧化物DCP、DCP/S并用硫化体系及共交联剂ZDMA的加入对三元乙丙胶/丁腈胶(EPDM/NBR)共混胶性能的影响。研究表明:在过氧化物硫化体系中,随DCP用量的增加,共混胶综合性能先提高后降低,DCP用量为3份时性能达到最佳;DCP/S并用硫化体系中,随硫磺和促进剂加入量的增加,共混胶硫化速度提高,但综合力学性能降低;共交联剂ZDMA由0份增加至15份,共混胶力学性能显著增加,老化性能没有改善。     

共混型TPU/LDPE交联体系的制备与性能

以热塑性聚氨酯(TPU)及低密度聚乙烯(LDPE)为基体,过氧化二异丙苯(DCP)为交联剂,采用熔融共混技术制备了具有交联结构的TPU/LDPE形状记忆共混物,并对共混物的凝胶含量、力学性能、形状记忆性能进行了研究。结果表明,DCP的加入使共混物的凝胶含量增大、力学性能提高,并在DCP的质量分数为0.3%时,TPU/LDPE共混物的力学性能达到最佳。形状记忆性能研究表明,DCP的加入使TPU/LDPE共混物的形状回复率呈先上升后下降的趋势,并在DCP的质量分数为0.5%时形状回复率达到最大。TPU/LDPE共混物形状固定率的变化趋势与形状回复率基本相反。相比于纯TPU,DCP的加入使TPU/LDPE共混物的形状回复率和形状固定率均有所上升。而且,TPU/LDPE共混物的拉伸应变越低,形状回复率越高。     

乙烯-醋酸乙烯共聚物的硅烷交联及无卤阻燃研究

采用过氧化物为引发剂,用熔融法制备了硅烷交联EVA和无卤阻燃硅烷交联EVA.用红外方法(IR)和差示扫描量热法(DSC)对EVA的硅烷接枝反应进行了表征.研究了过氧化物含量对体系凝胶含量,相对接枝率和力学性能的影响,同时还研究了交联对体系阻燃性能的影响.DSC实验表明,硅烷A171比硅烷A151更容易接枝到EVA上.随DCP含量增加,体系的凝胶含量,相对接枝率,拉伸强度增加,而断裂仲长率降低.氧指数结果表明,交联以后可以适当提高氧指数值,改善阻燃性能.     

BPO/DCP复合硫化体系对硅橡胶泡沫性能的影响

以BPO/DCP为复合硫化剂制备硅橡胶泡沫,研究了DCP用量对硅橡胶泡沫性能的影响规律.结果表明,在BPO/DCP复合硫化体系中,硅橡胶泡沫试样的密度、拉伸强度、撕裂强度没有随着DCP用量的增加而发生明显的变化;随着DCP用量的增加,试样的凝胶含量逐渐增大,当DCP用量超过1.5份时,硅橡胶泡沫的交联体系基本维持稳定;随着DCP用量的增加,硅橡胶泡沫材料的σ(ε=0.4)值先增后减,当DCP用量为2.O份时,σ(ε=0.4)值最大;DCP用量增加,硅橡胶泡沫试样的压缩应力松弛性能有降低的趋势,其DCP用量为1.5份时,压缩应力松弛性能最好;在松弛曲线的开始阶段(10 min以内)材料的载荷下降很快,随着时间的延长,载荷降低的速度明显降低,曲线逐渐趋于平缓;硅橡胶泡沫材料的短时间(20 min)应力松弛特征可以用公式Ft=F0(klogt+m)+at1/2+6来描述,拟合曲线与实验测试曲线具有较好的一致性.     

DCP对动态硫化EPDM/PP性能的影响

以过氧化二异丙苯(DCP)为硫化剂,通过双螺杆挤出机进行三元乙丙橡胶/聚丙烯(EPDM/PP)的共混挤出制备动态硫化EPDM/PP热塑性弹性体,采用转矩流变仪对EPDM/PP热塑性弹性体进行硫化特性测试,运用抽提法测试EPDM/PP热塑性弹性体的凝胶含量,研究了不同DCP含量下EPDM/PP热塑性弹性体的硫化特性及凝胶含量的变化情况,并对EPDM/PP热塑性弹性体材料性能进行分析研究。结果表明:当DCP含量为0.6%时,EPDM能完全交联,共混体系黏度最大,扭矩最高;当DCP含量为0.9%时,EPDM/PP热塑性弹性体综合性能最佳;当DCP含量为1.2%时,EPDM/PP热塑性弹性体的凝胶含量最大,但PP的降解程度逐渐增加,拉伸性能开始降低;当DCP含量为1.5%至1.8%时,PP的降解程度剧烈,EPDM/PP热塑性弹性体性能较差。     

EPDM/NR共混橡胶的性能研究

采用硫黄硫化体系和过氧化物(硫化剂DCP)硫化体系对EPDM/NR并用胶实施复合交联,考察了不同共混比EPDM/NR共混胶的硫化特性、硫化胶的物理机械性能、耐水性及耐溶剂性能。结果表明:复合交联后,胶料的硫化特性、物理机械性能均有所提高;EPDM母炼胶中DCP的用量要高于NR;胶料共混比为80/20(EPDM/NR),其耐水性和耐溶剂性能达到最佳。     

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.