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纸质出版日期:1965-12-20,
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周啸, 张志平. 聚乙烯的辐照效应与结晶性能之间的相互影响[J]. 高分子学报, 1965,7(6):386-395.
CHO SHIAW, CHANG CHIH-PING. MUTUAL INFLUENCE BETWEEN THE EFFECTS OF RADIATION AND THE CRYSTALLIZATION PROPERTIES OF POLYETHYLENE[J]. Acta Polymerica Sinica, 1965,7(6):386-395.
1.经五种不同剂量(10×106、2×107、5×107、1×108和2×108)的γ-射线辐照过的聚乙烯样品
在它们的二甲苯稀溶液中于同一个结晶条件下培养出来的一组晶体
在形态方面随着剂量的增大而发生有规律的变化。凝胶点以前
得到的是单晶体;凝胶点以后
随剂量的增大得到越来越不规则的树枝晶。但是
若降低恒温的温度或减慢冷却的速率
则可以得到较为规则的树枝晶或单晶体。因而作者认为:上述这种形态上的有规律变化
并不是由构成这些晶体的分子随着剂量的增大
在结构上发生有规律的变化所造成的
而是由于凝胶分量的增大使得形成上述晶体的过饱和度有规律地增大所造成 的。 2.经辐照过的聚乙烯可以产生线型分子、支化分子和交联分子所特有的三类结晶形态。因而这就十分形象地说明了在一定的剂量范围内
辐照过的聚乙烯
确实同时存在有这三类分子。 3.聚合物的稀溶液结晶过程也是一个不同结构分子的自动分离和各自归并的过程。 4.对同一批培养出来的聚乙烯单晶体经不同剂量(5×106、2×107、5×107、1×108和2×108拉特)的γ-射线辐照以后
用电子显微镜进行了形态观察。发现其中一部分单晶体有许多褶痕
而另一部分则可以基本上没有什么褶痕,也发现同一个单晶体上的某几块扇面有许多褶痕,而另几块扇面却可以几乎没有褶痕,作者认为,这种褶痕产生的不均匀性说明了一个完整的晶格结构有较好的抵抗γ-射线的能力;也说明了对于空心稜锥状晶体来说,每一个扇面是一个较为完整的晶格结构。
1.The samples of polyethylene irradiated with 1,20,50,1 00,and 200 megarad γ一ray were crystallized from dilute xylene solutions under the same conditions.The mot-phology of a series of crystals obtained changes regularly as the dose increases.Below the gel point
single crystals could be obtained. Beyond this point,dendritic crystals (becoming more and more irregular with increasing dose) were obtained.But when the crystallizing temperature was lowered or the cooling rate Was decreased,regular dendritic crystals or even single crystals could again be obtained.Therefore this change of morphology with increasing dose is due not to the change of the structure of the mole-cules,but to the increasing of the degree of supersatu.ration during crystallization.The higher the gel fraction is,the higher is the degree of supersaturation.2.Three kinds of typical crystalline morphology(they belong tO the linear,bran-ched,and three-dimensional network molecules) were observed from irradiated poly-ethylene.This indicates that within suitable range of dose.these three kinds of mole-cules do exist in irradiated polyethylene at the same time.3. The crystallization process of the polymer from dilute solution is also a process of spontaneous separation of the unlike molecules and a process of congregation of the like molecules.4. Single crystals of polyethylene prepared under the same conditions had been ir-radiated separately with 5,20,50,100,and 200 megarad γ-ray.The morphology of these irradiated crystals was studied with an electron microscope
Some of them re-mained unchanged,but.there were Iots of wrinkles on the others.Moreover,even in the same single crystal,many wrinkles were found in some sectors,but none in the others. The unequal distribution of the wrinkles indicates that a perfect crystal lattice has higher resistance to γ-radiation.It also indicates that every sector in a hollow pyramid crystal is a structural unit of more perfect crystalline lattice.
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