�������� ���� �� ���� ��������� ������. ����� ������������� ��������� : http://cryst.geol.msu.ru/literature/kurs/2015_03_belik.pdf ���� ���������: Tue Apr 14 08:39:06 2015 ���� ��������������: Sat Apr 9 23:54:16 2016 ���������: IBM-866

� . ..�



.
: , .. : .-., c... .. : ... ..

2015



1. . 1.1 , . 1.2. . , 2. 2.1 . 2.1.1. : , - . 2.1.2. . 2.2. 21 27 44 45 15 11 5 3

2



, , . - - , , , - , , . � , , [BO4], [PO4] [BO3] � , . 250 . OH-. � , , . , , , � ( ) . , :

. : � - -

. � : , � , , ICSD.
3


. , , . - - , . ... .. . . . ... .. , ., . . . . .. .

4


1. . 1.1. ,
- V , . � , , � , , . 15, 30,97376 [1]. . � (V) � P2O5. . . - (H3PO4). : , [2].


34 2

3(4)2

4

34 2(4)3 (24)3

4


224

(24)2

- , : (NH4)3HPO4 � , (NH4)2HPO4 � NH4H2PO4 � . � , 0.08 � 0.09%. , . ( 0.07 /). , , . ( (Fe, Ni, Co)3P, ) ,
5


[PO4]3-. [ 3]. 200 , [2+, Fe2+, Fe3+, Al3+, (UO2)2+, Cu2+, Mn2+, Pb2+, Zn
2+

.], (OH-, Cl-, F-, O2-, CO32-)
4.

. aHPO

. - (a5(PO4)3X (X-F, Cl )). a5(PO4)3F, � [4]. . . , , . , .. , [3]. , � . Mn+2, Mn+3, Fe+2 Fe+3 . � , � , [5]. , Zr, Ti, Ni, TR. O
4 3�

,

, TR- . � Al, Fe, Mn, (, .), [5]. �

. , ( - ).
6


. , . , , . , . . [O4] [SiO4]4�. 1.
3�

.
�

: [SO4]2



. . , [O4]3� [SiO4]4� [SO4]2�. . , , . , Ca
2+

Na1+, Y TR (

). 2.





. , , 4 , , SiO2, . . [SiO4]4�, 3+ Th4+, U4+ Zr4+[2]. Si4+. , [4]3-- , , . , . [PO4] , , . ,
7


- Na2CaCu2(P2O7)2*10H2O.

[P2O7]4-:

Na2Ca(P2O7)�4H2O





� III . 5, 10.811. 4 /. , 100 ; � . ( 4,6 /), . . , . , ( 80) � , (, ) (, ). , -- . -, , , . 3 4, , . , -- . . . , [BO3]3 [B2O5]4, [B3O6]3 [B2O4]2 ..[2]. , , : , . ,

, , -, -, -, -, - . , � , Sr, TR, Be . , ,

, , � Mg, Ca, Na, K, Sr. .
8


. , , (, , ) ( ) [6]. . , [7]. , -, - . - [7]. , , , Cl, F, , , (, ), (, ). , , . :

(0 - 50�), (50 - 250�) (>250�C). , 8 .
-











(3)3

(25)4-,







.

50-250�

. , , , , , ,
9

- .


, , III , . , [3]3 [4]5, , [SiO4]4-[2]. , . [5].

10


2.2. . , .
, [PO4], [BO4] [BO3] � (, , ) . - - , .. P--O--B . , , , [PO4], [BO4] [BO3] , [MO4]-. , -: . Mg3(H2O)6[B2(OH)6(PO4)2] � , . , . 1870 , . , . . , , . 3 [9]. . 2, 2,05. 2V =6.3475 �, b=9.8027 �, c=6.2976 �; P . . : , , ; Z=1,

11


1961 . , A2 Am. , . [9] (.1), . Mg(2)-B-P (�T2M�, T-, -) (.1). 2 Mg(1) � T2M�M�T2M (.1). 2��2 b (. 1).

()

()

. 1. : 2M, xz (a); () Mn3(OH)2[B(OH)4][PO4] � (. 2) , , . , 1930 [10]. [11,12].

12


. 2. (, , John A. Jaszczak). - , . : a = 7.8231(9) , b = 15.1405(14) , = 6.6999(7) , Z=4, V=793.57(14) 3, Pbnm. [10]. n-, . . (.3). [B(OH4)]- Mn , (.3).

13


.3 : , (), xy (). . � 2 � � 2 ( ), {010}. � Na2Fe3(OH)2[PO4]2 [13].

14


3. . 2.1. . 2.1.1. : , - .
. , , , . , . , . , . . / , . . . - (, ) . - � , ( ), . - , � , . : , . , , [14]. , -

, -
15








,







,





, . - : 1250-1350� 1-5/ . , , . . , . - . , � ( ). � . - . - [14]. : (, ., 1980). . . , , , . . , -. : , . , ,
16


[14]. . � - -. , . ,



[15]. , , . � . - . : 1. ; 2. . . - , , . � , , , . � . . - . , , . - (lg S = -Q (T
m

� T)/4.58 T

m

T, S � , ..
m

; Q � ; T

�

; T �
17


; 4.58 � ) . 1. . , . 2. . , . 3. . 4. , . , . , , - B2O3, P2O5, Sb2O3, SiO2 , - . - � . [14]. , . . : , ( , (Pb, Sn, Zn, Cd, Sb, Ga, In, Tl, Bi )) ( , ) ( ) , , ( ) ( ) ( ) , , ) , , ) , ).

18


(), . , , 1 . uO (NH4)2HPO4 Rb2CO3 H3BO3 Cs2CO3 CsH2PO4 B2O3 MnCO3 Li2CO3 V2O5 1. ... .. .. .. .. .. .. . .. ... .

� � .12-1400..1� (.4) . �. , . 5. 3 7 3 (.6).

19


.4



.

.5 .

20


.6 , .

21


2.1.2. .
, , : . , . , . , , 3-5%, , . [16]. , . , , , . , � . , , . . , , (.7).

22


.7 , , [16]. � , BA + AC, 1: n = 2d sin , d � ; �- , ; �- ; n � . , , , , - . -1 (.8).

23


.8. [16]: 1 � ; 2 � (), ; 3 � ; 4 � . . , . . 0.2 � 0.4 . , , . 1 ( ) -2 . � 2 2 6 70. , . spectr.exe. (d), 2 (I). , , PDF. , , . , . , , , . . .

24


: 1. ; 2. ; 3. .

, . , , 0.05-0.3 . , -. ( ), . , , , . . . , [16]. , - . Xcalibur CCD-. , (, , ). ~ 0,05 � 0,1 . , , , . ( �). ( ). �CrystAlis�,
25


. ICSD .

26


2.2. .
13 , 2. 2. .
- ( ) ( , , .) ( ) a=13.403(19), V=2407, . I- == =90�, (Rb, Al, Cu, P)

8/4

Rb2CO3 CuO H3BO3 (NH4)2HPO Cs2CO3 CuO H3BO3 (NH4)2HPO CsH2PO4 CuO B2O3 (NH4)2HPO CsH2PO4 MnCO3 B2O3 (NH4)2HPO

1:1:1:2

20 750� 48 750� 64 300�

4

- - ,

A

8/5

1:1:1:2

20 750� 48 750� 64 300� 2 4 1 2 4 1 0 2 8 1 0 2 8 1 0 0 9 6 2 50� 950� 00� 4 �

-

-

4

10/1

1:1:2:6

B

4

10/2

1:1:2:6

4

9 6 2

50� 950� 00� 4 �

1., .

C

a=10.031(4) b=11.813(5) c=26.659(9) == =90� V=3159(2) (Cs, Al, P, Cu) a=10.033(4) b=11.824(5) c=26.687(8) == =90� V=3.180(12) � B (Cs, Mn, P, O (Al �)) a=12.270(11) b=8.964(9) c=17.816(16) = =90� =108.37(8) V=1860(4) (Al, P, O, Cs, Mn)

2., ( )

D

16/5

Cs2CO3 CuO B2O3 (NH4)2HPO

4:1:2:6

4

19 18 51 11

950� 950� 600� 24�



-

-

27


16/6

Rb2CO3 CuO B2O3 (NH4)2HPO

4:1:2:6

4

1 5 1

9 1 1 1

8

9 6 2

50� 950� 00� 4 �

: - , - -

-

-

20/1

Li2CO3 CuO (NH4)2HPO B2O3

1:2:6: 10
4

20 20 48 11

9 6 2

50� 950� 00� 4 �

. 1. , . 2.-

E

a=10.02(7) c=8.22(12) ==90�, =120� V=717(4) C- =6.896(9) b=8.122(6), =109.53 = =90� c=9.175(18) V=484(1) a=11.519(4) b=11.519(4) c=5.632(3) == =90� V=747.3(5) I-
17

-Cu2P2O7

20/2

Li2CO CuO V2O5 B2O3

3

1:2:6: 10

2 4 1

0 2 8 1

0

950� 950� 600� 24�

()

CuB2O

4



Cu2Al6B4O

=10.574(6) c=5.657(5) == =90� V=632.4(8)

C 21/3 Rb2CO CuO B2O3 V2O5
3

2:6:1: 16

8 900� 12 900� 35 650� 8 24�

- , ,

-

Cu2V2O MnV2O

7

21/4

Rb2CO3 MnCO3 B2O3 V2O5 Li2CO3 CuO (NH4)2HPO B2O3 Rb2CO3 CuO B2O3 (NH4)2HPO Rb2CO3 CuO B2O3 (NH4)2HPO

2:6:1:16

8 3 8

90 12 56 24

0 � 900� 50� �

7

a=6.731(9) b=8.739(11), = =90� =103.57(8) c=4.979(4) V=284.7(6)

25/1

1:1:6: 10
4

25/2

1:2:4:16

4

25/3

1:2:4:16

4

10 950� 10 950� 62 650� 17 24� 10 950� 10 950� 62 650� 1 7 2 4 � 10 950� 10 950� 62 650� 1 7 2 4 �

. - . . , - . , -

BPO

4

Cu2P2O BPO
4

7

BPO

4

-
28


8/4
Rb2CO3-CuO-H3BO3-(NH4)2HPO4 (Rb:Cu:B:P) 1:1:1:2 1 . - . . . Rb, Al, Cu, P ( Cs). : a=13.403(19), V=2407, , I . , , B , Rb2CO3-CuO-(NH4)2HPO4. ISCD . , , Al Cs.

8/5
Cs2CO3-CuO-H3BO3-(NH4)2HPO
4







8/4, - , .

10/1
sH2PO4-CuO-B2O3-(NH4)2HPO4 s:Cu:B:O=1:1:2:6 1 . B, , , 0.1 . . Cs, u, Al, P, O. , a=10.031(4), b=11.813(5), c=26.659(9) V=3159(2), . , .

29


10/2
sH2PO4-MnCO3-B2O3-(NH4)2HPO4 ( 10/1, , , ) 1:1:2:6 . ( ), , , , . : Cs, Mn, P, Al, O. , (a=10.033(4), b=11.824(5), c=26.687(8), V=3.180(12)) , , . . D, ,

. , , . s, Mn, P, Al, O. , 2. ISCD, , , .

.9 D, . .

30


16/5 16/6
8/4 8/5, �, , . Cs2CO3-CuO-H3BO3-(NH4)2HPO
4



Rb2CO3-CuO-H3BO3-(NH4)2HPO

4





4:1:2:6 (Cs/Rb:Cu-B-P), . - . - : - , , .

20/1
Li2CO3-CuO-(NH4)2HPO4-B2O3 (Li:Cu:P:B) 1:2:6:10 2 . ( ), , - . . , a=10.02(7), c=8.22(12) V=717(4), ==90�, =120�. , . , - .

: =6.896(9) b=8.122(6), =109.53 c=9.175(18) V=484(1), C , -Cu2P2O7(.10)

31


.10. -Cu2P2O7 xy.

. , (001), .

20/2
Li2CO3 � CuO - V2O5 - B2O3 1:2:6:10 2 . ( ), ( 0.5 ). : CuB2O4 (.12). a=11.519(4), b=11.519(4), c=5.632(3), V=747.3(5).

I ,

32


.11 CuB2O4 . .

.12 CuB2O4.

33


, [B3O6]. , . [B3O6]3-- (21 +22) : 1, 3 4 2. (2 24) , . (Cu1 Cu2) . Cu1 1, . Cu2 (2, 3 24) (41 23). Cu1, , Cu2 � . , - , (~10% ). . : =10.574(6), c=5.657(5), V=632.4(8). : Cu2Al6B4O17 LiAl7B4O17. , (Al2O3). Cu2Al6B4O17 [20] .13.

34


.13 Cu2Al6B4O17

.

u2Al6B4O17 , . , ( .11 ). , . - . "", - 2. . LiAl7B4O17. - .

21/3
Rb2CO3 � CuO - B2O3 - V2O5 2:6:1:16 , , 0.1 ). - (.14).
35


.14





,







. . Cu2V2O7 (.15, . 3), .

.15 , 21/3.
36


3. 21/3. 2Theta [�] d[A]


(A)

, Cu2V2O7

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

18.31 2 6 .3 6 2 8 .6 6 3 1 .8 9 3 2 .5 8 3 3 .4 3 3 3 .7 9 3 5 .2 8 3 6 .7 6 3 7 .0 5 3 7 .2 8 3 8 .1 8 4 1 .8 9 4 2 .4 7 4 2 .9 2 5 0 .3 8 5 0 .6 0 5 7 .9 8

5.6233 3.9227 3.6135 3.2560 3.1887 3.1104 3.0777 2.9517 2.8366 2.8155 2.7983 2.7350 2.5023 2.4811 2.4450 2.1017 2.0932 1.8455

467.95 244.00 193.56 1000.00 599.46 203.36 645.92 192.12 206.16 304.41 175.71 213.79 199.56 193.90 169.07 162.32 189.90 160.93

21/4
Rb2CO3- MnCO3 - V2O5 - B2O3 2:6:16:1 1 (.16 ).

37


.16. MnV2O7. . : a=6.731(9) b=8.739(11), =103.57(8) c=4.979(4) V=284.7(6). � MnV2O7, 17.

38


.17. MnV2O7 . MnO6-, MnO3 , V2O7- . MnO3 V2O7- , .

25/1
Li2CO3-CuO-(NH4)2HPO4-B2O3 (Li:Cu:P:B) 1:1:6:10 . - . (.18, .4) BPO4 Cu2P2O7.

39


.18. , 25/1. 4. 25/1.
1 2 3 4 5 6 7 8 9 10 11 12 2Theta [�] d [] , BPO4(A), Cu2P2O7 (B)

28.45 31.18 32.91 33.87 35.16 35.49 41.27 41.94 46.71 48.41 48.84 50.61

3.6406 3.3280 3.1575 3.0711 2.9612 2.9349 2.5381 2.4995 2.2562 2.1819 2.1637 2.0928

1000.00 24.68 96.27 40.29 74.29 51.51 34.85 28.45 268.71 10.25 7.33 12.14

, , ,
40


13 14 15 16 17 18 19 20 21 22

51.66 52.19 52.38 53.88 55.86 57.36 58.96 62.00 63.84 65.06 68.63 68.73 69.06 69.31

2.0529 2.0337 2.0266 1.9745 1.9096 1.8639 1.8176 1.7367 1.6917 1.6635 1.5867 1.5848 1.5774 1.5730

23.21 6.34 3.62 21.84 12.55 73.72 30.69 9.09 15.92 4.63 3.03 4.66 3.14 10.10

, , ,

23 24 25 26

25/2
Rb2CO3-CuO-H3BO3-(NH4)2HPO4 Rb:Cu:B:O=1:2:4:16 . - . BPO4 (.19, .5).

41


. 19. , 25/2. 5. 25/2.
1 2 3 4 5 6 2Theta [�] 2 8 .4 1 3 1 .2 3 3 3 .8 0 4 6 .6 8 5 7 .2 9 5 8 .9 7 d[A] 3.6457 3.3233 3.0773 2.2580 1.8660 1.8173 1000.00 2 7 .7 8 6 3 .8 8 225.97 6 6 .4 8 2 2 .9 3

25/3
Rb2CO3-MnCO3-H3BO3-(NH4)2HPO
4







Rb:Cu:B:O=1:2:4:16 , . BPO4. 10-20 2 (.20).
42


.20 , 25/3 . 6. 25/3
1 2 3 2Theta [�] 2 8 .4 3 46.72 57.33 d[A] 3.6431 2.2559 1.8649 1000.00 225.97 6 6 .4 8

, .

43


.
1. - - . 10 : 5 , -Cu2P2O7, CuB2O4, Cu2Al6B4O17, u2V2O7 MnV2O7, 5 , . 2. , . 3. , ( ) , . 4. , .

44


.
[1] .. // , � �, 1971 [2] .. // , � , 2007 [3] .. // , . , 2005. [4] .. // : () . [ ]// . - . .: 1977, . 24 [5] .. // , .2, , , 1994 [6] .. . : , 1976. [7] .. , .. , .. , .. , .. , .. // // ,2003 [8] Weilong Zhang, Wendan Cheng, Hao Zhang, Lei Geng, Yeyu Li, Chensheng Lin, Zhangzhen He // Inorganic Chemistry Article, 49, P.2550-2556 (2010) [9] P.K. Sen Gupta, George H. Swihart // American Mineralogist, V.76, P. 1400-1407 (1991) [10] Paul B. Moore, Subrata Ghose // American Mineralogist, V.56, P.1527-1538 (1971) [11] Moore P B , Ghose S , American Mineralogist , 56 (1971) p.1527-1538 [12] Huminicki, D.M.C.;Hawthorne, F.C. Canadian Mineralogist (2002), 40, 923-928 [13] Y. Olga, S. Ian, M. Werner, D. Olga // Zeitschrift f?r Kristallographie - Crystalline Materials. -- 2013. -- Vol. 228, no. 10. -- P. 509�519. [14] .. // -, , 1978 [15] .. , .. , .. , .. // , , , , 2010 [16] .. // . . , 2000.
45


[17] Olga V.Yakubovich, Ian M. Steele, Werner Massa, Olga V. Dimitrova // Crystal Structure Communications, P. 94-98 (2009) [18] .. , .. , // , , 1976 [19] .. , .. , .. , .. , .. , .. . . , . 3 . ."", (1980). [20] Ying Wang, Shilie Pan, Yunjing Shi // Chemistry European Journal, 18, P.12046-12051 (2012) [21] P. A. Plachinda and E. L. Belokoneva//Synthesis and Crystal Structure of Commensurate Polymorph of Ln4AlCu2B9O23 (LnLu,Ho) and Refinement of Cu2Al6B4O17 .1965-1970 (2008)

46