冰洲石的矿物学特征及其褪色实验研究
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摘要
本文通过热处理的方法，对黄色和紫色冰洲石的颜色进行改善。实验表明，冰洲石在加热到一定温度时颜色会发生变化：浅黄色、深黄色和褐黄色冰洲石分别在360-370℃、440-450℃和460-470℃完全褪色；浅紫色、深紫色和深紫红色冰洲石分别在370-380℃、440-450℃和460-470℃时完全褪色。通过对褪色后冰洲石进行紫外-可见光吸收光谱测试表明：完全褪色后的冰洲石在紫外-可见光的吸收光谱上表现为一条近平行x轴的直线；紫外、可见光区的紫区的光透过率有了很大了提高。褪色后的冰洲石晶体外观完好，其双折率、偏光性等物理性质没有明显变化，完全符合它在工业上应用的要求，冰洲石的颜色改善取得了明显的效果。
对于黄色、紫色冰洲石颜色成因，本文初步研究认为，Mn、Pb和CO_3~(2-)对黄色有贡献；Mn、Pb、CO_3~(2-)和Ni对紫色有贡献，即黄色冰洲石的致色：CO_3~(2-)→CO_3~-+e(V心)，Mn~(2+)→Mn~+-e(F心)和Pb~(2+)→pb~+-e(F心)产生了色心，这些色心相互作用能吸收蓝区和紫区的波段，从而使冰洲石呈黄色；紫色冰洲石为CO_3~(2-)→CO_3~-+e(V心)，Mn~(2+)→Mn~+-e(F心)，Pb~(2+)→Pb~+-e(F心)和Ni~(2+)→Ni~+-e(F心)相互作用，使冰洲石呈紫色。加热使冰洲石的色心受到破坏，从而使冰洲石的颜色褪去。
In this paper, the yellow and purple Iceland spars are heated to remove their color. The experiments show that the color of the Iceland spar can be changed when heated to a certain temperature, that is , light yellow Iceland spars will fade when heated to 360-370℃, while dark yellow Iceland spar will fade at 440-450℃, brownish yellow Iceland spar at 460-470℃ ; And the color of light purple Iceland spar can be removed when heated to 390-400℃, while the color of deep purple Iceland spar can be removed at 440-450℃ , deep reddish purple Iceland spar at 460-470℃ .On base of the u-v absorption spectrum, we find that the u-v absorption spectra of the faded Iceland spars are paralleled to the X axis, the transmittance of them are also greatly improved . The courses of the enhancement don't damage Iceland spar or change its physical properties, such as birefringence index, optic chatacter. These show that the samples measure up to their industrial standards after the heating. The experiment is successful.
The study on the cause of the color shows that Mn, Pb and CO2-3 are contributed to the yellow in the Iceland spar , while the purple of the iceland is caused by Mn, Pb, CO32- and Ni . The yellow Iceland spar are thus colored : CO32- can form V center in this way , CO32-→CO3-+e; Mn forms F center, Mn2+→Mn+-e ; Pb forms F center , Pb2+→Pb+-e . These color centers can affect each other and so they can absorb the purple and blue part of the visible spectrum , and make Iceland spar yellow ; similarly, CO32- (CO32-→C03-+e) ,Mn2+(Mn2+→Mn+-e) , Pb2+(Pb2+→Pb+-e) and Ni2+(Ni2+→Ni+-e) can work together to cause Iceland spar purple . Heating can bleach these color centers, consequently, the color caused by them is removed, and iceland spars become colorless.
对于黄色、紫色冰洲石颜色成因，本文初步研究认为，Mn、Pb和CO_3~(2-)对黄色有贡献；Mn、Pb、CO_3~(2-)和Ni对紫色有贡献，即黄色冰洲石的致色：CO_3~(2-)→CO_3~-+e(V心)，Mn~(2+)→Mn~+-e(F心)和Pb~(2+)→pb~+-e(F心)产生了色心，这些色心相互作用能吸收蓝区和紫区的波段，从而使冰洲石呈黄色；紫色冰洲石为CO_3~(2-)→CO_3~-+e(V心)，Mn~(2+)→Mn~+-e(F心)，Pb~(2+)→Pb~+-e(F心)和Ni~(2+)→Ni~+-e(F心)相互作用，使冰洲石呈紫色。加热使冰洲石的色心受到破坏，从而使冰洲石的颜色褪去。
In this paper, the yellow and purple Iceland spars are heated to remove their color. The experiments show that the color of the Iceland spar can be changed when heated to a certain temperature, that is , light yellow Iceland spars will fade when heated to 360-370℃, while dark yellow Iceland spar will fade at 440-450℃, brownish yellow Iceland spar at 460-470℃ ; And the color of light purple Iceland spar can be removed when heated to 390-400℃, while the color of deep purple Iceland spar can be removed at 440-450℃ , deep reddish purple Iceland spar at 460-470℃ .On base of the u-v absorption spectrum, we find that the u-v absorption spectra of the faded Iceland spars are paralleled to the X axis, the transmittance of them are also greatly improved . The courses of the enhancement don't damage Iceland spar or change its physical properties, such as birefringence index, optic chatacter. These show that the samples measure up to their industrial standards after the heating. The experiment is successful.
The study on the cause of the color shows that Mn, Pb and CO2-3 are contributed to the yellow in the Iceland spar , while the purple of the iceland is caused by Mn, Pb, CO32- and Ni . The yellow Iceland spar are thus colored : CO32- can form V center in this way , CO32-→CO3-+e; Mn forms F center, Mn2+→Mn+-e ; Pb forms F center , Pb2+→Pb+-e . These color centers can affect each other and so they can absorb the purple and blue part of the visible spectrum , and make Iceland spar yellow ; similarly, CO32- (CO32-→C03-+e) ,Mn2+(Mn2+→Mn+-e) , Pb2+(Pb2+→Pb+-e) and Ni2+(Ni2+→Ni+-e) can work together to cause Iceland spar purple . Heating can bleach these color centers, consequently, the color caused by them is removed, and iceland spars become colorless.
引文
1．宋兆昌．我国首次发现冰洲石-方解石巨晶、超巨晶群及其形成机制探讨．中国岩溶，1994(4)：383-393
2．地质辞典(四)．地质出版社．1986
3．张相训．桂西下甲方解石脉水晶矿床特征及成因初步研究．广西地质，1990(3)：19-30
4．税哲夫等编著．碳酸盐岩中冰洲石成矿模式及经济技术开发研究．贵阳：贵州科技出版社，1999
5．[英]B.Henderson著，范印哲译．晶体缺陷．高等教育出版社，1984
6．R.C.伯恩斯著，任党、郭其悌译．晶体场理论的矿物学应用．科学出版社，1970
7．[苏]基耶夫连科、[苏]安得鲁先科．冰洲石矿床的普查与勘探．中国工业出版社，1962
8．邓世荣．水晶和冰洲石．建筑工程出版社，1958
9．西北大学地质系．矿物学．地质出版社，1985
10．北京大学地质学岩矿教研室．光性矿物学．地质出版社，1979
11．winklr,H.G.F著，邵克忠译．晶体构造和晶体性质．北京科学出版社，1960
12．高振敏．成因矿物学．武汉：中国地质大学出版社，1990
13．朱明华．仪器分析．北京：高等教育出版社，1993
14．罗献林等．中外奇石．北京科学技术出版社，1998
15．陈贤容．电子白旋共振实验技术．科学出版社，1986
16．李明琴等．黔西南某冰洲石矿床矿物学特征研究．贵州地质，1999(3)233-236
17．曹俊臣．贵州天然黄色冰洲石的水热褪色极其染色机制研究．地质地球化学，1982(5)：48-55
18．吴瑞华等．天然宝石的改善及鉴定方法．地质出版社，1994。
19．A.C.马尔福宁[苏]．矿物物理学导论．地质出版社，1984
20．A.C.马尔福宁[苏]．矿物的谱学、发光和辐射中心．科学出版社，1984
21．裘祖文．电子自旋共振波谱．科学出版社，1980
22．吴瑞华．与大治铁矿矿桨成矿有关的CaMgSi_(m06-kmg3)(AeSi_3O_(10))F_2-NaAeSi_3O_8—FeO四元系液相不混溶性的实验研究．硕士论文，1983
23. Nassau K . Gemstone enhancement. Butte worth .stonehamma, 1984 K.przibram and J.E .caffyn Irradiation colors and luminescence. pergaman press, 1962
24. Bill H.calas. Color center: associated rare-earth ions and the origin of Coloration in natural fluorites, physics and chemistry of minerals, 1978, vol 3:pp 37-75
26. Cohen A.J. Optical studies of biaxial related color centers in smoky quartz, American mineraogist., 1986,vol 71 :pp589-598
27． James H,Schlman . Color centers in solids. International series of monographs on solid state physics ,1962,vol 2
28． Gittus.J . Irradiation effects in crystalline solids. Applied Science pub, London, 1978
29． Medlin W.I. . Trapping center in thermo luminescent calcite. phys.Rev..196, v.136:p1779-1779
30． Feofilov,p.p. . Absorption and luminescence of bivalent ions of rare-earth elements in natural and synthetics fluorite crystals. Opt.stektr. 1956(1) :pp992-999
31． Hayes,w.ed. . Crystals with the fluorite structure; electronic, vibration and Defect properties. Oxford: oxford university press, 1974
2．地质辞典(四)．地质出版社．1986
3．张相训．桂西下甲方解石脉水晶矿床特征及成因初步研究．广西地质，1990(3)：19-30
4．税哲夫等编著．碳酸盐岩中冰洲石成矿模式及经济技术开发研究．贵阳：贵州科技出版社，1999
5．[英]B.Henderson著，范印哲译．晶体缺陷．高等教育出版社，1984
6．R.C.伯恩斯著，任党、郭其悌译．晶体场理论的矿物学应用．科学出版社，1970
7．[苏]基耶夫连科、[苏]安得鲁先科．冰洲石矿床的普查与勘探．中国工业出版社，1962
8．邓世荣．水晶和冰洲石．建筑工程出版社，1958
9．西北大学地质系．矿物学．地质出版社，1985
10．北京大学地质学岩矿教研室．光性矿物学．地质出版社，1979
11．winklr,H.G.F著，邵克忠译．晶体构造和晶体性质．北京科学出版社，1960
12．高振敏．成因矿物学．武汉：中国地质大学出版社，1990
13．朱明华．仪器分析．北京：高等教育出版社，1993
14．罗献林等．中外奇石．北京科学技术出版社，1998
15．陈贤容．电子白旋共振实验技术．科学出版社，1986
16．李明琴等．黔西南某冰洲石矿床矿物学特征研究．贵州地质，1999(3)233-236
17．曹俊臣．贵州天然黄色冰洲石的水热褪色极其染色机制研究．地质地球化学，1982(5)：48-55
18．吴瑞华等．天然宝石的改善及鉴定方法．地质出版社，1994。
19．A.C.马尔福宁[苏]．矿物物理学导论．地质出版社，1984
20．A.C.马尔福宁[苏]．矿物的谱学、发光和辐射中心．科学出版社，1984
21．裘祖文．电子自旋共振波谱．科学出版社，1980
22．吴瑞华．与大治铁矿矿桨成矿有关的CaMgSi_(m06-kmg3)(AeSi_3O_(10))F_2-NaAeSi_3O_8—FeO四元系液相不混溶性的实验研究．硕士论文，1983
23. Nassau K . Gemstone enhancement. Butte worth .stonehamma, 1984 K.przibram and J.E .caffyn Irradiation colors and luminescence. pergaman press, 1962
24. Bill H.calas. Color center: associated rare-earth ions and the origin of Coloration in natural fluorites, physics and chemistry of minerals, 1978, vol 3:pp 37-75
26. Cohen A.J. Optical studies of biaxial related color centers in smoky quartz, American mineraogist., 1986,vol 71 :pp589-598
27． James H,Schlman . Color centers in solids. International series of monographs on solid state physics ,1962,vol 2
28． Gittus.J . Irradiation effects in crystalline solids. Applied Science pub, London, 1978
29． Medlin W.I. . Trapping center in thermo luminescent calcite. phys.Rev..196, v.136:p1779-1779
30． Feofilov,p.p. . Absorption and luminescence of bivalent ions of rare-earth elements in natural and synthetics fluorite crystals. Opt.stektr. 1956(1) :pp992-999
31． Hayes,w.ed. . Crystals with the fluorite structure; electronic, vibration and Defect properties. Oxford: oxford university press, 1974