本文選題：葉綠礬 + 高鐵硫酸鹽��； 參考：《山東大學》2011年博士論文

【摘要】：行星科學是一門綜合科學,它利用物理、化學以及地質等多種科學手段研究行星、衛(wèi)星、以及行星系統(tǒng)的各種性質。而人們通常講的行星科學主要以我們所在的太陽系的天體作為研究對象。行星科學的歷史可以追溯到希臘的哲學家Democritus。然而行星科學領域出現(xiàn)具有實際意義的進步是17世紀人類發(fā)明了望遠鏡,這以后人們通過望遠鏡發(fā)現(xiàn)了太陽系的大部分行星�；诳萍及l(fā)展,人們終于在上世紀50年代開始進入了深空探測的新時代,人們進行了包括對月球、火星、金星、水星、冥王星以及土衛(wèi)六等的非常多的深空探測任務。這些深空探測任務使人們得到了比地基望遠鏡所得到的更精確的大量行星數(shù)據(jù),使人們更進一步了解了我們地球周圍的天體。最近的十年,包括我國在內的很多國家都展示了它們對探索外太空天體(例如火星、月球以及其他天體等)的興趣。而本論文的工作中所涉及的月球返回樣品和火星相關礦物的三個研究工作則屬于行星科學領域中具有重要意義的基礎科學研究部分。第一個課題是對火星上很有可能出現(xiàn)的葉綠礬族礦物的光譜學研究。第二個課題則屬于對火星上觀測到的含水高鐵硫酸鹽的相圖的研究。第三個課題是研究兩種阿波羅返回月壤中的鈦含量分布。 火星探測車(Mars Exploration Rovers)和火星偵查者號軌道探測器(Mars Reconnaissance Orbiter)都在火星上觀測到了鐵硫酸鹽,這使得在實驗室中研究鐵硫酸鹽在火星表面類似條件下的性質變得十分重要。而葉綠礬族礦物是火星表面或者表面淺層可能存在的鐵硫酸鹽礦物之一,因此研究它的光譜學性質特別是其光譜在有陽離子替代情況下的變化將會非常有意義。我們在實驗室里合成了四種具有不同陽離子替換的葉綠礬族產物,它們分別是高鐵葉綠礬、葉綠礬、鎂代葉綠礬以及鋁代葉綠礬。我們用X射線衍射的方法對所合成的物質的物相進行了鑒別并確認了其純度。我們選擇性的對合成的樣品采集了喇曼光譜、中紅外光譜、可見近紅外光譜以及LIBS光譜。我們選擇使用的這些技術正在或者將要被應用在火星探測中。我們在所采集的喇曼光譜中發(fā)現(xiàn)了四種樣品的硫酸根的v1喇曼峰位隨著陽離子替換發(fā)生了有規(guī)律的變化。在LIBS光譜的研究中,我們發(fā)現(xiàn)光譜所展示的樣品中陽離子含量的相對比值與樣品本應該具有的比值是相洽的。在研究樣品X射線衍射譜的時候,我們發(fā)現(xiàn)葉綠礬族礦物的光譜中的三個最強的X衍射譜線的位置發(fā)生了有規(guī)律的變化,這種變化顯示由于陽離子替換導致了葉綠礬族礦物晶體結構發(fā)生了規(guī)律的變化。而在四種樣品的中紅外光譜中,我們發(fā)現(xiàn)了一個很強的硫酸根的v,峰,這表明了由于葉綠礬族礦物本身晶體結構中的硫酸根基團很低的晶位對稱性引起了硫酸根本身對稱性的改變,從而導致了選擇定則的破壞。和具有二價陽離子的葉綠礬族礦物相比較,具有三價陽離子的葉綠礬族礦物不僅具有葉綠礬族共有的兩個近紅外波段分別在1.4以及1.9微米附近的兩個很強的吸收峰外,還在2微米附近出現(xiàn)了兩個額外的小的吸收峰。在可見近紅外光譜中,有一個電子躍遷譜產生的吸收峰的峰位由高鐵葉綠礬的850納米左右偏移到了葉綠礬的866納米左右,這種偏移很有可能是由葉綠磯礦物中的亞鐵離子出現(xiàn)在900納米附近的電子躍遷吸收峰與850納米的吸收峰疊加導致的。 人們最近在火星表面發(fā)現(xiàn)了各種不同的高鐵硫酸鹽,這使得在與火星表面溫度相關的溫度條件下研究高鐵硫酸鹽的各種基礎性質(穩(wěn)定場、相圖、相變路徑和反應速率)變得更加有意義。在本論文的工作中,我們利用濕度控制器技術、重量測量技術以及喇曼光譜學技術確定了五水鐵礬和七水鐵礬在一個標準大氣壓下的相圖邊界上的兩個實驗點,然后我們對兩個實驗點進行了熱力學分析并得到了五水鐵礬和七水鐵礬之間相變的熱力學參數(shù)。基于這些熱力學參數(shù),我們又推得了五水鐵礬和七水鐵礬相圖邊界上在兩實驗點之間的所有點。我們對所得的實驗結果做的熱力學分析顯示在五水鐵礬和七水鐵礬相變的過程中每一個水分子結晶相應的反應物的焓的變化是-290.773±0.3447kJ/mol,而相應的吉布斯自由能的變化為-238.81±0.0219kJ/mol。這些結果與其他研究者的估計結果相符。 遙感光譜紫外-可見反射率比值是月球表面Ti元素含量(TiO2)估算中廣泛應用的一個參數(shù),目前,人們試圖通過正在運行的月球觀察者號(Lunar Reconnaissance Orbiter)航天器上所搭載的寬角相機(Wide Angle Camera)完成月全球Ti含量分布的測量(利用321納米以及360納米兩個波段)。為了更好的理解遙感光譜紫外-可見反射率比值與Ti含量之間的關系,我們在實驗室中利用一種復合的數(shù)字圖像方法(結合了反射電子圖像和X射線圖像)對月球返回樣品元素含量作了定量的分析。在此研究中,我們列出了兩種富含鈦元素月壤中鈦元素的分布。這兩種月壤分別是阿波羅11返回的樣品10084和阿波羅17返回的樣品71501。在這兩種富鈦月壤中,占主導地位的鐵鈦氧化物為鈦鐵礦,其他相關的礦物很少見(如阿姆阿爾柯爾礦、鈦尖晶石或者金紅石等)。在兩種月壤中,粘連物和角礫巖的體積含量都隨著月壤粒徑的減小而減少。但是,單礦物月壤顆粒所占的體積比例則隨著月壤粒徑的減小而增加。這種現(xiàn)象可以用多相共生的角礫巖碎裂為更小、單相的月壤顆粒來解釋。在相對更成熟的月壤10084中,更多的鈦元素存在于玄武巖中的較小的鈦鐵礦顆粒中。而在亞成熟的月壤71501中,更多的鈦元素分布于較大的單相鈦鐵礦顆粒中。這種不同可能反映了兩種月壤中鈦鐵礦的起源礦物的性質不同。我們沒有發(fā)現(xiàn)Ti元素的分布隨著月壤顆粒大小的改變而改變,然而我們卻發(fā)現(xiàn)月壤10084中鈦鐵礦顆粒的形狀隨之有較小的變化。 在分析火星軌道或者登陸探測器光譜儀所得到的光譜時,我們在實驗室中觀測到的葉綠礬族礦物的各種光譜特征可以幫助鑒別出火星上有可能存在的葉綠礬族礦物。而我們觀測到的不同葉綠礬族礦物之間的光譜特征的差別甚至可以進一步幫助鑒別火星上葉綠礬族礦物的詳細種類。在研究鐵硫酸鹽相圖的工作中,我們建立了一套比較完整的研究含水鐵硫酸鹽相圖的方法。我們得到的鐵硫酸鹽的熱力學參數(shù)和它們的相圖邊界可以幫助我們更好的理解鐵硫酸在火星的起源、演化以及分布。我們將把所得到的兩種典型月壤中Ti的分布的數(shù)據(jù)與這些月壤的紫外、可見光譜作比較,從而更好地理解月壤紫外、可見光譜強度與月壤中的Ti含量、含Ti礦物、以及鈦鐵礦形狀等因素之間的關系。
[Abstract]:Planetary science is a comprehensive science that uses a variety of scientific means, such as physics, chemistry, and geology, to study the various properties of planets, satellites, and planetary systems. The planetary science, which is generally spoken, mainly uses the celestial bodies in our solar system. The history of planetary science can be traced to the Greek philosopher Democrit. Us. however, a practical progress in the field of planetary science was the discovery of a telescope in seventeenth Century. After that, people discovered most of the planets in the solar system. Based on the development of science and technology, people began to enter the new generation of deep space exploration in the 50s of last century. People have included the moon, Mars, and Venus. Mercury, Pluto, and the very many deep space exploration missions, such as earth guard six. These deep space missions have enabled people to get more accurate data from the foundation telescope and make people know more about the celestial bodies around us. In the last ten years, many countries including China have shown them. Exploring the interest of outer space objects such as Mars, the moon and other celestial bodies, and the three research work on the return of the moon and the minerals associated with Mars in this paper is part of the fundamental scientific research in the field of planetary science. The first is a very likely leaf on Mars. The second subject is a study of the phase diagram of hydrous high iron sulfate observed on Mars. The third subject is to study the distribution of titanium in the two species of Apollo's lunar regolith.
The Mars Exploration Rovers and the Mars Reconnaissance Orbiter (Mars Reconnaissance Orbiter) all observed iron sulphates on Mars, making it important to study the properties of iron sulphate in similar conditions on the surface of Mars in the laboratory, and the green alum mineral is the surface of Mars or the superficial layer. One of the possible iron sulphate minerals is possible, so the study of its spectroscopic properties, especially in the presence of cation substitution, will be significant. We have synthesized four species of green alum products with different cation substitutions in the laboratory, which are high iron leaf green alum, leaf green alum, magnesium substitute green alum, and We used X ray diffraction to identify the phase of the synthesized material and confirm its purity. We selectively collected Raman, mid infrared, and LIBS spectra for the synthesized samples. The techniques we choose to use are or will be applied to Mars exploration. In the Raman spectra we found that the V1 Raman peak of the sulfate radical of four samples has changed regularly with the cation substitution. In the study of the LIBS spectrum, we found that the relative ratio of the cation content in the samples displayed in the spectrum is consistent with the ratio of the sample which should have been supposed to have. In the study of the sample X At the time of ray diffraction, we found that the position of the three strongest X diffraction lines in the spectrum of green alum minerals has changed regularly. This change shows that the crystal structure of the green alum mineral has changed regularly due to cation substitution. In the mid infrared spectrum of the four samples, we found one. The V, peak of the strong sulfate radical shows that the symmetry of the sulfate radical is caused by the low crystal position symmetry of the sulfate radical group in the crystal structure of the leaf green alum mineral itself, which leads to the destruction of the selection rule. Compared with the two valence cations, the leaf green alum family with trivalent cations Minerals not only have two very strong absorption peaks in two near infrared bands, which are near 1.4 and 1.9 microns, respectively, and there are two additional small absorption peaks in the vicinity of 2 microns. In the near infrared spectrum, there is a peak of the absorption peak of an electronic transition spectrum from 850 nanometers of high iron leaf green alum. The offset is about 866 nanometers of leaf chlorosunite, which is likely to be caused by the superposition of the electron transition absorption peaks in the vicinity of 900 nanometers and the absorption peak of 850 nanometers by the ferrous ions in the chlorophylla.
Different kinds of high iron sulphates have been discovered recently on the surface of Mars, which makes it more meaningful to study the basic properties of high iron sulfate (stable field, phase diagram, phase transition path and reaction rate) at temperature related to the surface temperature of Mars. In this paper, we use humidity controller technology, weight The measurement and Raman spectroscopy techniques determine the two experimental points on the boundary of the phase diagram of five ferric alum and seven ferric alum at a standard atmospheric pressure. Then we analyze the thermodynamic parameters of the two experimental points and obtain the thermodynamic parameters of the phase transition between five vitriol and seven ferric alum. Based on these thermodynamic parameters, we All points on the boundary between the five ferric alum and the seven ferric alum phase diagram on the boundary between the two experimental points are also pushed. The thermodynamic analysis of the results obtained shows that the enthalpy of the corresponding reactant of each water molecule during the phase transition of five ferric alum and seven ferric alum is -290.773 + 0.3447kJ/mol, and the corresponding Gibbs The change of free energy is -238.81 + 0.0219kJ/mol.. These results are consistent with the estimation results of other researchers.
The ultraviolet visible reflectance ratio of remote sensing spectrum is a parameter widely used in the estimation of the Ti element content (TiO2) on the surface of the moon. At present, people are trying to measure the monthly global Ti content distribution by the wide angle camera (Wide Angle Camera) on the running lunar observer (Lunar Reconnaissance Orbiter) spacecraft. With 321 nanometers and 360 nanometers two bands. In order to better understand the relationship between the ratio of the ultraviolet visible reflectance and the Ti content of the remote sensing spectrum, we used a complex digital image method (combining the reflected electronic image and X ray image) to make a quantitative analysis of the content of the elements in the return samples of the moon. In the study, we listed the distribution of titanium elements in two kinds of lunar soils rich in titanium. The two lunar soils were respectively Apollo 11 returned samples 10084 and Apollo 17 returned in 71501. of the two rich Ti rich lunar soils. The dominant titanium oxide was ilmenite, and other related minerals were rare (such as Amal Karl ore, titanium tip. The volume content of adhesions and breccia decreases with the decrease of the size of lunar soil in two lunar soils. However, the volume proportion of single mineral lunar soil increases with the decrease of the size of the lunar soil. This phenomenon can be solved by the fragmentation of polyphase conglomerate to smaller, monophasic lunar soil particles. In the relatively mature lunar 10084, more titanium elements are found in the smaller ilmenite particles in the basalt, and in the submature lunar 71501, more titanium elements are distributed in the larger monophasite particles. This difference may reflect the different properties of the origin of the ilmenite in the two months of soil. It was found that the distribution of Ti elements changed with the size of lunar soil particles. However, we found that the shape of ilmenite particles in lunar soil 10084 changed slightly.
In the analysis of the spectra obtained by the Mars Orbiter or the landing detector spectrometer, the various spectral features of the green alum minerals we observed in the laboratory can help identify the possible presence of green alum minerals on Mars. The spectral characteristics of the different leaf green alum minerals we observed can even be different. Further help identify the detailed species of green alum minerals in Mars. In the study of the iron sulfate phase diagram, we have established a relatively complete set of methods to study the sulfate phase diagram of hydrated iron. The thermodynamic parameters of the ferric sulfate and the boundary of their phase diagrams can help us to better understand the ferric sulphuric acid in the fire. We will compare the data of the distribution of Ti in the two typical lunar soils with the UV and visible spectra of these lunar soils, so as to better understand the relationship between the spectral intensity of the lunar soil and the Ti content in the lunar soil, the Ti minerals and the ilmenite shape.
【學位授予單位】：山東大學
【學位級別】：博士
【學位授予年份】：2011
【分類號】：P185

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