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本文研究了剂量、辐照气氛、升温速率对γ-辐照聚乙烯的热释光曲线的影响。当剂量在9×10~5拉特以下时,在77到273°K 之间出现三个主峯;当增高剂量(2×10~6拉特以上)时则仅呈现二个主峯。低剂量时,氧对释光曲线有显著影响,但对峯Ⅰ(低温峯)则观察不到明显的影响。 在辐照聚乙烯的差热分析中,我们观察到一个由辐照引起的吸热峯。虽然该差热峯的温度位置与释光峯峯Ⅰ相近,但与释光峯在反复辐照时仍可出现的情况相反,在反复测试差热或反复辐照时该吸热峯却不再出现。这表明产生这两种峯的因素不是同一的,而决定这两种峯的温度位置的因素却可能是相同的。 用分峯法将热释光曲线的主峯分开,由此求得峯Ⅰ和峯末的活化能分别为0.22及1.2电子伏;与由变更升温速率法所求得的活化能相比较,对峯末由两种方法所得的结果相近,对峯Ⅰ则相差较大。通过与理论计算曲线相比较,表明分峯法所得的结果较为合理。 相似文献
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就自制的稜状和针状两种结晶状态的三聚甲醛进行了固态辐射聚合,制得特性粘数为0.8和K_(222)值力3.4%/分(未酯化的)的聚合物,经酯化后,可压制成膜。 在不同剂量率下研究了聚合转化率与辐照时间的关系,当累积剂量在 2×10~5拉特之前,聚合转化率与剂量呈线性关系,随后转化率出现一极限值(74%以上)。聚合物的特性粘数随剂量的增加而减小。在所研究的剂量范围内(4.1—89拉特/秒)聚合初速率与剂量率呈线性关系。剂量率对聚合物的特性粘数影响不大。 在-78℃到65℃温度范围内进行了温度对聚合速率影响的试验,在0℃以下时不聚合,接近熔点时聚合速率最快,超过熔点(62℃)时,则几乎不聚合。单体的结晶状态及晶体的大小对聚合速率有较大的影响。 相似文献
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利用凝胶渗透色谱(GPC)、傅里叶变换红外光谱(FTIR)和示差扫描量热(DSC)等手段对不同剂量γ射线辐照后等规聚丙烯(iPP)的分子链结构及结晶行为的变化进行了研究.结果表明,γ射线辐照使iPP的分子量下降,并在其分子链中产生羟基和羰基等极性基团,从而影响其结晶行为.在非等温结晶过程中,当辐照剂量≤50 kGy时,iPP的热结晶温度略有升高;增大辐照剂量,iPP的热结晶温度明显降低.iPP的熔融温度则随辐照剂量的增大而降低,且分裂成双峰.利用Avrami方程研究了辐照前后iPP的等温结晶动力学,发现辐照前后样品的Avrami指数n都在3左右,表明iPP的结晶遵循异相成核机理,且不受辐照剂量和等温结晶温度的影响,但总结晶速率随等温结晶温度和辐照剂量的升高而逐渐减小.探讨了iPP经过γ射线辐照后,分子链断裂、链结构变化和结晶速率之间的关系. 相似文献
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ZHOU Li-Juan ZHANG Xiu-Qin LI Rong-Bo SU Yun-Lan ZHAO Ying WANG Du-Jin XU Duan-Fu 《高等学校化学学报》2012,33(4)
利用凝胶渗透色谱(GPC)、傅里叶变换红外光谱(FTIR)和示差扫描量热(DSC)等手段对不同剂量γ射线辐照后等规聚丙烯(iPP)的分子链结构及结晶行为的变化进行了研究.结果表明,γ射线辐照使iPP的分子量下降,并在其分子链中产生羟基和羰基等极性基团,从而影响其结晶行为.在非等温结晶过程中,当辐照剂量≤50 kGy时,iPP的热结晶温度略有升高;增大辐照剂量,iPP的热结晶温度明显降低.iPP的熔融温度则随辐照剂量的增大而降低,且分裂成双峰.利用Avrami方程研究了辐照前后iPP的等温结晶动力学,发现辐照前后样品的Avrami指数n都在3左右,表明iPP的结晶遵循异相成核机理,且不受辐照剂量和等温结晶温度的影响,但总结晶速率随等温结晶温度和辐照剂量的升高而逐渐减小.探讨了iPP经过γ射线辐照后,分子链断裂、链结构变化和结晶速率之间的关系. 相似文献
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以左旋聚乳酸(PLLA)为研究对象,以多官能团单体三烯丙基异氰酸酯(TAIC)为交联剂,采用反应挤出技术制备了PLLA-TAIC体系,并利用60Co-γ射线源,在较低辐照剂量(Dose≤25kGy)范围内,对所制备的聚合物进行了γ-辐照。研究了γ-辐照剂量、交联剂含量对PLLA分子量和结晶形态的影响。结果表明,在0~25kGy辐照剂量范围内,PLLA-TAIC的粘均分子量(-Mη)随γ-辐照剂量的增加呈现出先升高后降低的变化趋势,辐照剂量为10kGy、TAIC含量为3份时,PLLA的-Mη提高的幅度最大;随着辐照剂量的增加,原料PLLA形成的球晶尺寸有所增大;对于γ-辐照的PLLA-TAIC体系,随着TAIC含量的增加,PLLA的结晶能力有所下降。 相似文献
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以前,不少人认为高聚物的结晶形态和结晶过程与低分子化合物比较起来有着原则性的差别.但是从1957年Till,Keller和Fischer分别独立地从聚乙烯的二甲苯稀溶液中培育出单晶体以来,大量的研究工作都表明尽管高聚物有着许多不同于低分子 相似文献
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三维荧光光谱法连续测定苯胺、二苯胺和N-甲基苯胺 总被引:3,自引:0,他引:3
本文比较了苯胺、二苯胺、N-甲基苯胺的二维荧光光谱和三维荧光光谱。提出了同时测定苯胺,二苯胺和N甲基苯胺的分析方法,它们的浓度分别在2.0×10~(-7)~5.0×10~(-6)mol/L,9.0×10~(-8)~7.4×10~(-6)mol/L,1.3×10~(-7)~2.0×10~(-8)mol/L范围内有良好的线性关系,检出限为1.0×10~(-7)mol/L,8.0×10~(-9)mol/L,1.0×10~(-7)mol/L.相对标准偏差分别为5%,7%,7%.此方法用于混合样品和工业废水的分析,获得较满意的结果. 相似文献
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Abstract— In dimethylsulfoxide the emission spectrum of luminol chemiluminescence is red-shifted by 300 cm-1 from the photoexcited fluorescence of the product 3-aminophthalate dianion, while in aqueous solvent the two spectra are identical. The spectral properties of the product dianion have been measured in aqueous solvent and in a number of aprotic solvents, both at room temperature and at 77°K. The ground states and the excited states from which emissions are observed are characterized. Two alternatives are presented to explain the aprotic emission spectra. 相似文献
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WielA. G. BrulsJoop A. J. Faber†Jan C. van der Leun 《Photochemistry and photobiology》1982,36(5):531-535
The minimal erythema dose (MED) is often used as a quantity by which the influence of certain treatments of the skin can be measured. Differential measurements are performed by assessing the difference of the MED on the skin treated in some way and the untreated skin.
As the MED-measuring scale is discrete, the question is sometimes raised whether it is possible to measure differences smaller than one scale unit. In the present paper it is shown that this is indeed possible; in principle the discreteness of the scale does not impose any restriction on the smallest value of the difference that can be measured. The discreteness of the scale introduces an extra random variation into the measurement. This variation is estimated theoretically. It is automatically included in the usual error analysis.
The discreteness variance is small when compared to other variance components, which are computed from an analysis of variance of actual experiments. Reducing the discreteness variance, by reducing the dose decrement of the MED-measuring scale, therefore, does not enhance the overall accuracy considerably. Finally, it is found that the assessments of the MED by the various observers do not differ significantly from each other, and that multiple assessments do increase the accuracy, especially for small effects. 相似文献
As the MED-measuring scale is discrete, the question is sometimes raised whether it is possible to measure differences smaller than one scale unit. In the present paper it is shown that this is indeed possible; in principle the discreteness of the scale does not impose any restriction on the smallest value of the difference that can be measured. The discreteness of the scale introduces an extra random variation into the measurement. This variation is estimated theoretically. It is automatically included in the usual error analysis.
The discreteness variance is small when compared to other variance components, which are computed from an analysis of variance of actual experiments. Reducing the discreteness variance, by reducing the dose decrement of the MED-measuring scale, therefore, does not enhance the overall accuracy considerably. Finally, it is found that the assessments of the MED by the various observers do not differ significantly from each other, and that multiple assessments do increase the accuracy, especially for small effects. 相似文献
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分光光度法低浓度区不成线性关系的探讨 总被引:3,自引:0,他引:3
本文研究分光光度法低浓度区不成线性的有关因素及其克服方法,以铝-二甲酚橙体系为例,通过对体系不同条件下吸收光谱及其等色点的研究,发现当体系pH渐变时(铝,二甲酚橙浓度固定不变),曲线簇现两个等色点.从对等色点的分析,证明体系形成络合物须按一个反应式进行才能出现等色点,而与反应式是否涉及到两个或三个有色化合物无关.若同时按两个反应式进行,则不能得到等色点,测定时也无线性关系.所以用这个体系进行铝的测定,铝浓度的变化范围只能限于存在等色点的区间才有线性关系. 为了克服常法测定铝时不符线性的现象,本文采用的方法是在二甲酚橙中预先加适量的铝作为显色剂,使反应严格按一个反应式进行,所得结果为一直线. 相似文献
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对苯二胺衍生物的光催化氧化 总被引:1,自引:0,他引:1
以TiO2作为催化剂,利用波长>330nm的光辐照研究了N-取代的对苯-二胺衍生物的光催化氧化。研究表明,氧分子与光生电子 反应生成羟基自由基,羟基自由基氧化PPDs,生成醌二亚胺,后者在羟基的进攻下脱氨生成苯醌,苯醌继续光解无机化。PPDs光催化氧化近似遵循一级反应动力学,醇类和硫酸根离子可抑制PPDs的光催化氧化。催化剂表面荷影响电子转移速率,从而控制光催化氧化的反应速率。 相似文献
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Abstract— The complexity of the room-temperature emission spectrum of Chlorella was investigated by a matrix analysis method. This approach revealed the presence of two independently fluorescent components in the short-wave region of the spectrum. These components, maximal at about 687 and 695 nm, appeared to correspond to the fluorescence of the bulk pigments of PS II and PS I respectively. The analysis was insensitive to the individual species within the photosystems. As such, other minor fluorescent species, usually observed at low temperatures, which presumably correspond to fluorescence from the trapping centres, did not appreciably complicate the analysis. The absorption spectra of the two photosystems were calculated from the fluorescence data. The results were similar to those that have been obtained by other workers from oxygen evolution and DCMU poisoning data but differed from those obtained by computer analysis of the absorption spectrum. Addition of reduced DCPIP was observed to reverse the increase in fluorescence yield and changes in the spectral distribution of emission taking place on poisoning the algae. The correlation between this and the catalysis of photophos-phorylation in aged or poisoned chloroplasts was noted. This correlation was tentatively interpreted as evidence for a direct interaction between the donor system and the photochemical apparatus associated with PS II, rather than with a member of the electron transport chain as is normally assumed. 相似文献
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The kinetics of the decomposition of cyclohexyl hydroperoxide(CHHP) in benzene catalyzed by vanadyl dibenzoylmethane[V0(DBM).,] has been studied.It was found that the products of decomposition of CHHP were cyclohexanol and cyclohexanone,which are produced in about equimolar amount,and the product cyclohexanol obviously inhibited the decomposition of CHHP.The kinetics data can be satisfactorily described by the following equation (with [CHHP]0>>[VO(DBM)2]0)R0=kK[CHHP]0[VO(DBM)2]0/(1+k[CHHP]0)This is the kinetic evidence for the formation of a catalyst-hydro-peroxide intermediate.In the equation K is the stability constant of the catalyst-hydroperoxide intermediate complex;k is the rate constant for the decomposition of the complex.The rate constant K at 500℃ may be expressed as follows:k=1.9×108exp(-53.7×103/RT)S-1 with the activation energy Ea=53.7kJ mol-1 相似文献