Äîêóìåíò âçÿò èç êýøà ïîèñêîâîé ìàøèíû. Àäðåñ îðèãèíàëüíîãî äîêóìåíòà : http://www.chem.msu.ru/rus/journals/jvho/2006-3/131.pdf
Äàòà èçìåíåíèÿ: Mon Oct 2 16:24:36 2006
Äàòà èíäåêñèðîâàíèÿ: Sat Dec 22 13:53:35 2007
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133


: B Dhaeh\ < E A[Zjkdbc


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NH CH
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0,8 0,6 0,4 0,2

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134


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Al2O3 + MgO Al2O3 + TiO2 + MgO Al2O3 + TiO2 + Y2O3

50 40 50 60 40 50 50

95 94 90 94 90,5 95 95

20--22 20--22 20--22 20--22 15--18 22--25 22--25

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1,8 1,8 2,0 0,5 1,2 0,8--1,4 0,5--1,0

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** Al2O3 + MgO+ TiO2 Al2O3 + MgO+ TiO2



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135


: B Dhaeh\ < E A[Zjkdbc


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1. Evropian Chemical News. 13-19.10.1997. 2. www.the-innovation-group.com. Chem. Profiles. Aniline.htm. 3. Hudlicky M. Reduction in Organic Chemistry, Chichester Ellis Horwood, 1984, 309 p. 4. GbdheZ_\ XL Ydm[khg :F :gbebg. F Obfby 5.

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