色度学新技术方法研究辐射剂量学效应
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摘要
辐射计量学是发展国防建设和发展国民经济重要有效的质量控制手段,辐射剂量控制涉及许多新兴学科和研究生产行业,涉及医疗、药品和医疗器械消毒灭菌、高分子材料的改性等许多领域,鉴于辐射剂量学的重要性,国际原子能机构(IAEA)于1977年就制定了有关辐射剂量学标准的发展计划,这个计划包括了丫射线和电子辐射从10Gy到100kGy广泛的剂量范围,共资助了34个高剂量剂量计研究项目,已取得了显著的成果。
     辐射剂量学在我国是一个有待发展的专业领域,几乎全部测量原理和方法都是在国外首次建立,成熟后由国际行业机构介绍给国内,近年在国外出现的一些新技术和材料配方保密,使得我国不得不受制于人高价采购。具体从事辐射应用的单位,不仅缺少专门从事辐射加工剂量学工作的专业人员,也缺少适用我国实际情况的技术手段。简单快速较为准确的辐射剂量测量体系,是辐射从业者需求的基本工作条件
     电离辐射可导致很多物质及其溶液体系发生具有量效关系的色彩变化,尚无简便分析测试手段获取其包含的复杂辐射剂量信息。本课题根据色度学基本原理并尝试用新兴的技术方法进行辐射剂量学研究,以朗伯-比尔定律为指导,结合辐射剂量学工作实践,提出根据红绿蓝三基色变化和超微型全波普色度探测新技术获取辐射剂量信息的探索设想。主要研究内容包括两种染料和亚铁盐的三基色辐射剂量学效应,超微型阵列滤光分光技术用于辐射剂量学研究以及三基色检测装置的研制。尝试实现一种具有我国自主知识产权的新型液体化学辐射剂量学研究方法,在工农业生产、科学研究及国防建设各个领域可能有一定的应用前景。
     一、研究步骤、材料与方法
     (一)辐射变色物质研究
     筛选可发生辐射脱色的酸性湖蓝,弱酸性艳红B两种化学染料和辐射呈色变化的两种亚铁盐化合物以及呈色剂溶液配方体系;常规化学实验室操作方法和程序准备实验材料,试剂和溶剂,根据设计配制液体辐射剂量探头,接受不同剂量的60Coγ射线外照射。
     (二)受照射样品的检测
     将上述受照射样品分别使用委托研制的三基色探测装置(光线发射器、测试管固定装置、色度传感器模块光线接收器、带有模数转换功能的微处理器、输入/输出接口和显示器等)和超微型全波普光谱仪进行检测,获取相应的红绿蓝(RGB)数值和全波普吸光度变化数值;
     (三)数据处理
     根据受照实验样品三基色量值和全波普量值变化,计算机多因素分析软件数据处理。
     二、实验结果
     (一)三基色方法染料溶液实验结果
     1、溶液浓度和照射剂量是决定能否获得理想三基色数据的主要因素。在采用的0-13.5kGy照射剂量范围内,500mg/L酸性湖蓝,100mg/L弱酸性艳红B溶液溶的剂量效应关系全程变化明显。在试验剂量范围内随照射剂量增加,酸性湖蓝溶液红色(R)色度值强度逐渐增加,色度值与辐射剂量呈线性增加趋势;绿色(G)强度值在受照射剂量范围内变化不明显;蓝色(B)强度值随照射剂量增加而逐渐下降,与红色呈相反趋势变化;弱酸性艳红B溶液绿色(G)色度值强度逐渐增加,并与辐射剂量呈线性增加趋势;红色(R)强度值随照射剂量增加而逐渐下降,与绿色呈相反趋势变化;蓝色(B)强度值则变化不明显。
     2、在500mg/L以下的各酸性湖蓝浓度实验组,在上述照射剂量范围,红色(R)色度值和蓝色(B)色度值在较低剂量范围也会分别出现增加和降低的趋势变化,但是溶液浓度越低,色度值随照射剂量变化幅度越大,终于趋于平缓水平。依溶液浓度增加这个变化的拐点剂量分别为1、3、6kGy。弱酸性艳红B在50mg/L以下,0-2000Gy照射剂量范围内,绿色(G)色度值和红色(R)色度值在较低剂量范围也会出现同样的趋势变化,但是随着照射剂量增加会逐渐趋于平缓近于水平。这个变化的拐点剂量在500Gy左右。蓝色(B)强度值在0-2000Gy剂量范围内变化也不明显。
     3、在观察的酸性湖蓝A各浓度溶液中,受照后红(R),蓝(B)色度值变化明显且呈互补的此消彼长过程。而绿色(G)则变化均不明显。在观察的弱酸性艳红B各浓度溶液中,受照后红(R),绿(G)色度值变化明显且呈互补的此消彼长过程。而蓝色(B)则变化均不明显。
     4、将受照后浓度为250mg/L酸性湖蓝溶,100mg/L的弱酸性艳红B的实验样品在夏季常温环境(白天阳光直射,夜昼温度25-35℃)放置两周。再次测量RGB色度值,统计学分析显示没有明显差异,显示夏季气温存放两周对试验结果没有明显影响,说明这一类染料的辐射化学稳定性较好。
     (二)三基色方法亚铁盐溶液实验结果
     1、在0-80Gy照射剂量范围内二甲基酚橙,七水合硫酸亚铁复合溶液d的剂量效应关系表现为红色(R)色度值强度逐渐下降,蓝色(B)强度值随照射剂量增加而逐渐增加,与红色呈相反趋势变化;绿色(G)强度值在受照射剂量范围内变化不明显。
     2、在0-80Gy照射剂量范围内二甲基酚橙,氯化亚铁四水合物复合溶液绿色(G)色度值强度逐渐增加,蓝色(B)强度值随照射剂量增加而逐渐下降,与绿色呈相反趋势变化;红色(R)在O-80Gy剂量范围内变化不明显。
     (三)超微型全波谱技术方法实验结果
     1、200mg/L、100 mg/L、50mg/L、25mg/L 4种弱酸性艳红B各浓度溶液吸光率随波长变化非常明显。在本部分各实验采用的0-80Gy照射剂量范围内,照射剂量越大其与对照组吸光度变化幅度就越大。
     2、在试验采用的两种亚铁溶液复合体系中,吸光度(T)与波长的关系均大致呈“S”关系,波长600-700nm范围吸光度迅速增加,而较长和较短波长范围的吸光度增加较为平缓。
     3、0-80Gy照射剂量对硫酸亚铁复合溶液吸光率的影响主要表现为波长600nm以下吸光率变化和波长700nm以上吸光率变化。0.0085mmol/1二甲基酚橙,0.01mmol/1七水合硫酸亚铁复合溶液在上述波长范围吸光度辐射反应更为明显。
     4、与硫酸亚铁复合溶液吸光率受辐射影响的结果相比,0.0165mmo/1二甲基酚橙,0.025mmol/1氯化亚铁四水合物复合溶液吸光率变化在波长大于700nm以后较为明显,低于波长600nm以内吸光率随波长变化不甚明显。
     三、讨论
     化学辐射剂量计的基本方法是分光光度法,理论基础是朗伯-比尔定律。朗伯-比尔定律描述有色溶液对一定强度光的吸收与液层厚度和溶液中有色物质浓度的乘积成正比。放化产额G值是指带电粒子及其次级粒子在水中被阻止时,每损失100eV所产生的特定产物数目。一些产物会随时间减少,而一些会随时间而增加,利用分光光度计来测定溶液中某些辐射产物的量是辐射化学剂量计的基本工作原理。例如Fricke剂量计(硫酸亚铁剂量计)是最早用来作为辐射剂量测量仪器,被辐照时Fe2+被氧化成Fe3+产生蓝光,可被分光光度计测量。该方法是用一个特定的波长光线来分析一个特定单质物质溶液的线性吸光度变化来推算辐射剂量,能够满足这样分析条件的溶质种类并不多。
     许多物质在受照射后发生非单一色彩的变化,这样的变化也和辐射剂量相关,例如在环境保护领域,利用电离辐射降解技术处理染料废水是一种可行的方案。以60Coγ射线为辐射源,对偶氮染料甲基橙和活性艳蓝KNR水溶液进行的辐射降解研究显示脱色效果十分理想,染料水溶液在受辐照前后的紫外-可见光谱与辐射剂量有明确的相关变化。固态膜和液体凝胶作为辐射化学辐射剂量计的剂量检测范围已经达到相当低的水平,可用于测量各种辐射源的剂量,包括高能质子、高能电子、γ射线和X射线等。但是其机理和颜色变化复杂,难以用常规的分光光度技术进行准确的辐射剂量确定。比色法对非单一色彩变化显示比分光光度法优越的特性。近年来由于电子芯片工业的长足发展和新的光学部件的研发,使光电比色计发展为集光学、机械、电子于一体的系统。随着现代工业生产向高速化、自动化方向的发展,使用颜色测量仪器成为对产品进行客观评价的主要手段。例如一种采用世界上先进的高精度的RGB颜色传感器,在3x3mm的面积上集成了几十个R(红)、G(绿)、B(蓝)传感器。有色溶液透过光投射到RGB颜色传感器上就得到了三种不同的电流,经过转换获得三种正比于RGB的不同数据。建立了三维数阵算法模型和由量值传递原则组建的精密标样数据库,有效的克服了偏离所造成的误差。由此产生的快速水质测试技术引起国家环保部高度重视,其核心的检测管方法已纳入到国家的环保行业标准,在本次汶川地震灾区的水源安全保障以及我军的联勤卫生保障演习中都得到满意的实际应用效果。
     另一种更为先进的阵列滤光片分光技术是我国重点基础研究发展计划的研究成果,该技术设计全向性光子晶体异质结构分光器件,弥补普通光子晶体异质结构分光器件采光效率的不足,实现紫外可见近红外波段光谱设备的超微型化,将研制成功的128通道集成滤光片直接装配到探测器列阵上,共同构成一个体积不到l立方厘米的超微型光谱仪,是一项处于国际领先地位的新技术,计划于我国资源卫星上装配使用。在使用中不受环境振动影响,可以长时间不进行波长和能量标定,是野外恶劣环境光谱分析的最佳产品,目前此项技术在国外仅有相关概念。
     随着光学技术、计算机技术、微电子技术和材料学技术进展,改进液体化学辐射剂量研究的技术条件已经成熟。本课题利用上述两种色度学研究的新技术条件(三基色传感器技术和超微型阵列滤光分光技术)在近紫外-可见光-远红外全波谱范围内进行与辐射变色相关的辐射剂量学研究,得到了大量受照射物质色度变化与辐射剂量关系的实验数据,撰写数篇研究报告已经在国内核心期刊发表。初步研究结果提示,与传统的辐射化学剂量学方法相比,新的色度分析技术可以进行辐射剂量尤其是较低辐射剂量研究,可以分析电离辐射导致的非均一颜色变化。基于色度学原理的液体化学辐射剂量学研究具有理论和实践意义,这种研究设想无论从测量容器、剂量计溶液种类和配比成分以及数据测量原理和装置等重要环节都有别于目前国内外常规液体化学辐射剂量研究方法,完善后可具有完全的知识产权和快速、简便、经济、小型化的技术特点,有较强的应用价值。经检索在国内外尚未发现同样的研究报告,为此已经申报了专利保护(专利号ZL 200920066735.9)。
Radiation metrology is an important and effective means of quality control to develop national economy and national defense construction. Radiation dose control involves many emerging disciplines and research in the manufacturing industry, involving medical, pharmaceutical and medical equipment sterilization, polymer modified and many other fields. In view of the importance of radiation dosimetry, International Atomic Energy Agency (IAEA) made the development planning on the standards related to radiation dosimetry in 1977, The plan includes wide dose range from 10Gy to 100kGy of the y-ray and electron radiation, and a total funding of 34 high-dose dosimeter research projects which have achieved remarkable results.
     Radiation dosimetry in China is an emerging area of expertise; almost all principles and methods of measurement are established in abroad for the first time then introduced to the domestic by the international industry when matured. In recent years, the secrecy of the emergence of some new technologies and materials making me has had to be controlled by others as high-priced purchasing. Original works are also rare in several research units in Beijing, Shanghai, Mianyang. Specific units involved in radiation applications lack not only the professionals staff who specialized in radiation processing dosimetry working, but also the appropriate technical means to China's actual situation. Simple, rapid and more accurate radiation dose measurements system is the basic needs of radiation practitioners in the working conditions.
     According to the basic principles of chrominance, the issue tried to use today's new technology approach to radiation dose studies. Ionizing radiation can cause color variations in a lot of substances and their aqueous solution, in which have dose-effect relationship. There are no simple analytical methods to get their dose information contained in the complex. Guided by Lambert-Beer law, combined with radiation dosimetry work practice, the study suggests to obtain radiation dose information based on RGB chrominance change and supper-mini whole-spectrum spectrometer. Main research contents include three parts as the color detection devices, material with color-changed induced by radiation and data processing. Try to achieve new type research methods of liquid chemical radiation dosimetry with will have intellectual property rights of China's own, which maybe some application prospects in the industrial and agricultural production, scientific research and national defense fields.
     1 Study steps, materials and methods
     1.1 Study of color-changed material
     select two kinds of chemical dyes named Alphaurine A and Tracid Brilliant Red B which could fade when radiation, two kinds of ferrous salt compounds and its coloring-assistant system which could radiation coloration; Experimental materials, reagents and solvents are preparing by conventional chemical laboratory operations methods and procedures. According to the design, the liquid probes for radiation dose are prepared and receiving external irradiation of 60Co y ray with different doses.
     1.2detection for irradiated samples
     Detected the above irradiated samples using the primary colors detection devices which was composed with light transmitter, test tubes fixed installations or color sensor module with a light receiver, D conversion function of the microprocessor, input/output interface and displayer, accessed to the corresponding values in red, green and blue (RGB). The Super-mini whole-Spectrum spectrometer is used to obtain absorbance changes of the whole Spectrum.
     1.3data processing
     Based on three color value and changing of the whole Spectrum of experimental samples, multi-factor analysis of the computer software data are processing.
     2 Experimental results
     2.1 Results of the dye solution samples by three-color method
     2.1.1 Solution concentration and radiation dose was the main factors to determine the availability of an ideal three-color data. The whole dose-response relationship has changed markedly in 500mg/L Alphaurine A and 100mg/L Tracid Brilliant Red B radiated by 1.5-13.5kGy dose range. During the range, chrominance of Red (R) in Alphaurine A solution gradually increased with the dose increased, and increased linearly with the radiation dose trend. The changing of chrominance of green (G) is not obvious in irradiation doses; the chrominance of Blue (B) intensity increased with the dose gradually declining, with the red showed the opposite trend change; Chrominance of green (G) in Tracid Brilliant Red B solution gradually increased, and increased linearly with the radiation dose trend; Red (R) intensity declined with the dose gradually increasing, and the Green(G) showed the opposite trend of change; Chrominance of Blue (B) did not change significantly.
     2.1.2 The chrominance of red (R) and blue (B) in the experimental group of Alphaurine A with concentrations below 500mg/L are increasing and decreasing trend change respectively at the lower dose range. The lower the concentration is, the greater the changes of chrominnance with the radiation dose is, which finally flattening nearly horizontal. Turning points of this change are 1,3,6 kGy respectively according to concentration increasing. The chrominance of green (G) and red(R) gave rise to similar trends in change in Tracid Brilliant Red B below 50mg/L following irradiation dose range of 0-2000Gy,but would gradually flatten nearly horizontal as the dose increase. Dose of the turning point of this change was 500Gy around. Changes of Blue (B) intensity values were not evident in dose range of 0-2000Gy.
     2.13 Change of chrominance of red (R) and blue (B) was significantly and was complementary to counter-balance in Alphaurine A solution observed of different concentration after irradiation. And change of green (G) was no significant. Change of chrominance of red (R) and green (G) was significantly and was complementary to counter-balance in Tracid Brilliant Red B solution observed of different concentration after irradiation. And change of blue (B) was no significant.
     2.1.4 Put the experimental samples of 250mg/L Alphaurine A solutionand 100mg/L of Tracid Brilliant Red B solution in the summer environment (direct sunlight during the day and night daytime temperature is 25-35℃) for 2 weeks. Re-measured of RGB color values and statistical analysis showed no significant difference which indicating storage of two weeks in summer temperatures had no effect on the test results. It showed a better chemical stability of radiation of this type of dye.
     2.2 Results of ferrous salt solution by three-color method
     2.2.1 In the complex solution of errous sulfate green vitriol with xylenol orange, the dose-effect relationship showed as red (R) chroma values gradually decreased, while blue (B) intensity increased with the dose gradually increased, showing the opposite change in trend with the red; but green (G) intensity values did not change significantly in the irradiation dose range of 0-80Gy
     2.2.2In the complex solution of ferrous chloride tetrahydrate with xylenol orange, the dose-effect relationship showed as blue (B) chroma values gradually decreased, while green (G) intensity increased with the dose gradually increased, showing the opposite change in trend with the blue; but red(R) intensity values did not change significantly in the irradiation dose range of 0-80Gy
     2.3 Results by super-mini whole-Spectrum spectrometer method
     2.3.1Change of absorbance with wavelength was very obvious in Tracid Brilliant Red B solution with 4 various kinds of concentrations as 200mg/L,100 mg/L,50mg/L, 25mg/L. In various experimental dose range of 0-80Gy irradiation, the greater the radiation dose was, the greater the magnitude of changes of the absorbance was compared with the control group,
     2.3.2In the two kinds of composite solutions system with ferrous of the experiment, the relationship between absorbance (T) and wavelength was "S" shape generally. The absorbance of wavelength range of 600-700nm increased rapidly, while the absorbance of the longer and shorter wavelengths increased gently.
     2.3.3The influence in absorbance manifested mainly in changes of absorbance below wavelength of 600nm and above wavelength of 700nm of ferrous sulfate complex solution in 0-80Gy radiation dose. Reaction of absorbance becomes more apparent in complex solution of 0.0085mmol/l xylenol orange with 0.01mmol/l sulfate green vitriol in the range of wavelength above.
     2.3.4Compared with the results of complex solution of xylenol orange andsulfate green vitriol, the change of absorbance was more obvious in the wavelength greater than 700nm in complex solution of 0.0165mmo/l xylenol orange and 0.025mmol/l ferrous chloride tetrahydrate, while hardly evident in the wavelength less than the wavelength of 600nm.
     3 Discussion
     The basic method of chemical dosimeter is spectrophotometry, and the theoretical basis is Lambert-Beer law. Lambert-Beer law describes that light absorption of colored solution on certain intensity and liquid layer thickness as well as the product of the concentration of colored substances is proportional. Radiochemical yield G value refers to the number of specific products of each arising from loss of 100eV when the charged particles and their secondary particles in the water are blocked. Some products will decrease over time, while some will increase over time. Using spectrophotometry to determine the volume of solution in the product of some radiation is the basic working principle of chemistry dosimeter of radiation. For example, Fricke dosimeter (ferrous sulfate dosimeter) was among the first used as a dose of radiation measuring instruments. When it is irradiated, Fe2+is oxidized to Fe3+to produce Blu-ray, which can be measured by spectrophotometer. This method is to use a specific wavelength of light to analyze the linearity change of absorbance in a particular solution of single substances so as to estimate the changes in the projected dose of radiation. However, it is so few species of solution that can meet the conditions of analysis.
     Many substances occur the changes of a non-single color after irradiation, such changes also relates to the radiation dose. For example, in the field of environmental protection, treatment technology of dye wastewater using ionizing radiation degradation is a viable option. Taking 60Co y-rays as a radiation source, the azo dyes methyl orange and Reactive Brilliant Blue KNR aqueous solution of the radiation degradation of studies have shown that decolorization achieved very good results in the dye solution before and after irradiation by UV-visible spectra and radiation dose associated with clear change. Solid membranes and liquid-gel chemistry as a radiation dosimeter in the dose of radiation detection range has reached a very low level, and they can be used to measure the dose of a variety of sources, including the high-energy protons, high-energy electrons,γrays and X-rays and so on. But because of its complexity of mechanism and color change, it is difficult to use conventional spectrophotometric techniques to determine an accurate dose of radiation.
     Colorimetric method suggests the superior features to score spectrophotometry to non-single-color changes. In recent years, due to the rapid development of optical components and electronic chip industry, the development of photoelectric colorimeter becomes a set of optical, mechanical, and electronic in one system. As the modern industrial production to high-speed, automated direction, the use of color measuring instruments as the product of the principal means of objective assessment. For example, a use of the RGB color sensor of world's advanced precision, it gathers in an area of 3×3mm integrating dozens of R (red), G (green), B (blue) sensors. Colored solution through the light projected onto the RGB color sensor has been on three different currents through the three kinds of conversion was proportional to the different RGB data. Established a three-dimensional numerical matrix algorithm model and the standard sample database of principles established by the value of precision transmission, effectively overcome the deviation caused by errors. The resulting rapid rise to the water quality testing techniques attaches great importance to the State Environmental Protection Department; the core testing tube method has been incorporated into the country's environmental protection industry standards. In earthquake-stricken Wenchuan and the water security and health security of our military exercises, joint logistics have been satisfied with the practical application of results.
     Another more advanced spectral filter array technology is the research results of key basic research development program. The technical design, omni-directional photonic crystal heterostructure spectroscopic devices are to make up for ordinary photonic crystal heterostructure light spectral efficiency of the device insufficient to achieve UV-visible near-infrared spectra of ultra-miniaturized devices [7,8], will equip the successfully developed 128-channel to integrate filter assembly directly to the detector array, jointly constitute a volume of less than a cubic centimeter of the super-1 micro-spectrometer, which is an international leader in new technologies, planning to use our resources satellite assembly. Without environmental vibration in use can be a long time without calibration wavelength and energy, and it is the best product spectrum analysis in a harsh environment. At present this technology only has related concepts in foreign countries.
     With the technological advances of optical technology, computer technology, microelectronics and materials science, technologies improving study of liquid chemical dosimeter have developed sophisticated. In the near-ultraviolet-visible-infrared spectra within the framework of full-color,the subjects studied dosimeter associated with the radiation dose using the new technology conditions based on two kinds of chrominance study above(three primary colors sensor technology and ultra-micro-array spectral filter technology), then received a large number of the experimental data of chrominance changes of irradiated materials according to radiation dose. A number of written research papers have been published in the journal in the domestic core. Preliminary findings suggest that the new color analysis techniques can be used studying relatively radiation dose, especially low dose of radiation, also can be used analyzing ionizing radiation-induced non-uniform color change compared to chemical of the traditional methods of radiation dosimetry.
     Study of liquid chemical dosimeter based on new technique chrominance principles has theoretical and practical significance, such study vision is different from the current conventional research of liquid chemical dosimeter domestic and foreign in terms of measuring container, the type and ratio of dosimeter solution components as well as data measurement principle and devices After refining it could have the features with full intellectual property rights and may be fast, easy, economic and technical characteristics of miniaturization, and there will be a strong application value. The search have not yet found in the same study at home and abroad, for which patent protection has been declared (No. ZL 2009 2 0066735.9).
引文
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