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KDP

01.04.07 ­

-

· 2008 ·


.. ( )

: :

- , .. - .. , .. ,

:



24 2008 ., 1530 .501.002.01. . .. : 119991, -1, , , , , . . . .. . 20 2008 .

501.002.01, -

..


I.

1.1. (KH2PO4, - KDP) -, . KDP , , . , . . , , KDP , . , , . KDP . KDP , , : , , .. , . KDP , - , , . KDP KDP, , . KDP , KDP , . , . , . 1990-2000- , , . 3


, , , KDP , KDP; KDP, . , . 1.2. , -, KDP. -, , KDP. - - , . : · KDP, , () . · KDP . , , . · ; KDP. 1.3. KDP. , . ­ : · KDP Cr3+ · KDP 4[Ru2OCl10] (potassium m-oxo-bis [pentachlororuthenate[IV]] monohydrate)*. · KDP ( ): Amaranth, Chicago Sky Blue, Xylenol Orange

*

- , ­ « ».

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. 10-4 .% (100700 ppm). 1.4. : · ­ , , , KDP. · KDP, KDP. · KDP. · , , . · , KDP KDP . · KDP. · . 1.5. - KDP , . , , , , . , , , , , , . KDP, KDP , , , .

5


1.6. , . , . .. .. . (). 1.7. :
· Third international seminar on ferroelastics physics (ISPF-3). Voronezh (Russia), 11-14 September 2000. · 10-th International Meeting on Ferroelectricity (IMF-10), Madrid (Spain), 3-7 September 2001 · 16- , , 17-21 2002. · 7-th International Symposium on Ferroic Domains and Mesoscopic Structures (ISFD-7), Giens (France), 15-19 September 2002. · NATO Advanced Research Workshop on the Disordered Ferroelectrics (DIFE-2003), Kiev(Ukraine), 29 May-2 June 2003 · 10-th European Meeting on Ferroelectricity (EMF-2003), Cambridge (United Kingdom), 3-8 August 2003. · 4-th international seminar on ferroelastics physics (ISPF-4), Voronezh (Russia), 15-18 September 2003. · «-2004» ( «»). , , 2004. · 10- (-2004), -, 23-27 2004. · 8-th Russia-CIS-Baltic-Japan Symposium on Ferroelectricity, Tsukuba (Japan), 15-19 May 2006. · 3-th East-European Meeting on Ferroelectrics Physics, Lviv (Ukraine), 4-7 September 2006.

1.8. . 9 , 11 ( ­ 20 ).

1.9. , , . ­ 161 ., 123 ., 6 . 158 .

6


II.
. ,

2.1. , KDP. 1.1 KDP. KDP ­ , , , , [1-2]. OH...H ( R 2.50 A ) , = 0,3-0.4 A (.1). , , , 122 , , [3]. , , , , . 1. - KDP. , . ­ , [3]. , . , , . ( ) ­
. 2. KDP: () (b) [4].

, . 7


1.2 KDP. KDP , , . KDP , , (100) (010) [4]. , , 1 . 25 A ( ­10), ( ) - 50-100 A. 80-100 (1-2 ). KDP , , , , . , (. 2.) , , , , . , KDP , [5]. , , , . , KDP, , , . , , , [5]. , . , . , , KDP . , KDP, , . KDP . (), () . . 8


1.3 KDP , . , KDP. KDP : ( , .. «») , ( , TF). , [6-7]. , . FERRO , , - :



MONO





FERRO

DOM - = MONO + DOM .

, , , , [4]. : DOM MONO . , , . , . . , , [5,8]. [5], , , . ( ), , , , ­ . 9


. TF , , , ( ) . ­ . , KDP. , . , , . - . , , ( ), , , . , KDP, . , , , C «» . . , KDP . KDP ­ . KDP, .

--- · --· -- · -- · -- · ---

10


2.2. , KDP, . KDP M3+ ( Fe3+, Al3+, Cr3+ ) - , [9]. , . , , , [10]. - K+, + H2PO4-. 3+ , . - , , (. 3) *. KDP , . , -, , ­ «» : , , SO3-. - (, ), , , , , [11]. , , - , .

. 3. KDP ( ): Chicago Sky Blue, , , Sunset Yellow, Amaranth, {101}. [010], [11].
­ , , .
*

11


. 4. , KDP.

. 5. KDP ( ): r3+, Chicago Sky Blue, Xylenol Orange.

12


2.3. , . 4 , KDP. 1, . 5. , , .

KDP ( ) KDP ( ) KDP + Cr3+ KDP + 4[Ru2OCl10] KDP + Xylenol Orange KDP + Amaranth KDP + Chicago Sky Blue

. KDP-0 KDP-1,2,3

/





C0, ppm

1, ppm

2, ppm

A B,, D D



KDP+Cr KDP+R KDP+XO KDP+A KDP+CSB

Prism Prism Prism Pyramid Pyramid

9-10-12 \ 7-7-10 8-8-6 5-5-6

5 100 700 345
300400

3-35 \ 5.5

0-3 \ 1.4



100 0-5 100 0-5

« « « « « «

1. » - (a-b-c), » ­ , 0» - ( - ) 1» - 2» - «» » ­ , «/» - /

. B. C. D. .

, ( ..) , ( ..) , ( .., .) , ( ., .) , ( .., ..)

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2.4. . KDP, . KDP, . . , KDP , , (.6). , , - ( Fe3+, Al3+ Cr3+), [12]. KDP (.6). , KDP . .

. 6. KDP, (KDP-1), (KDP-0).

­ , . , , . -, , , , , , . 14


, , , , , ( , , , , , ). , , , , , , , «» KDP . C , . --------------------------------------------------------------- ---------- , KDP ­ , . ­ , , , ; ; KDP. r3+ : , . , , . ­ : , , , [12]. . TF . , . , , , . , , . ( ) ­ .

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K4[Ru2Cl10O], , . KH2PO4 (KDP), , {100} , {101} (.7). , , 0.38±0.05 , (.8). , , KDP, .

.7. KDP c .

. 8. KDP c .

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- KDP ( Amaranth, Chicago Sky Blue Xylenol Orange), . - ­ , - . KDP . , , ( 104 KDP), KDP. . 9 KDP+Amarnth. , , KD, . , , ( 2 .9). , . , . ,
. 9. () () KDP - Amaranth. - ' .

, , . «» 17


[13-14], . Amaranth KDP. , KDP, , - , .

. 10. . KDP Chicago Sky Blue ().

. 11. KDP Amaranth CSB. : 10 mHz - 1 MHz. - , 0 = 1 = 1
RC

,

- , R,C - ( â 10-1).

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KDP, , , ; . , , KDP C (.10). , . , . - , , . «» «» ­ ; , ­ , . , , 10 mHz ­ 1 MHz 30-80 ° . - (Cole-Cole) . . 0 (T ) - (T ) . (KDP-1(Pyr) KDP+(Pyr) KDP+CSB(Pyr) , «» - , (.11). . , (KDP+A, CSB (Pyr)), 1-2 . KDP , , .



DC

=

A( 0 ) W exp - A T kT







WA, 2. 19


WA , - , , ­ . , , , . , . KDP-0a KDP-1(Pyramid) KDP-1(Prism) KDP+A (Pyramid) KDP+A (Prism) KDP+CSB (Pyramid) WA, 0,44 0,43 0,65 0,52 0,77 0,65 KDP+R (Pyramid) KDP+R (Prism) KDP+XO (Pyramid) KDP+XO (Prism) WA, 0,67 0,70 0,65 0,73

2. KDP.

KDP. , , , , , - . , , , - . , , , , , , , . . , , . -, . , , - , , . , , . , , KDP, 20


, , . , , , ­ . , ­ - «» . , , , , .

--------------------------------------------------------------- --------- 3 . , , C . , . --------------------------------------------------------------- ---------
: «»: 1. «» ­ ; . C ­ (ppm). ­ ( C ), TF -



max DOM

- C ( ). - ( 110 ),
max

RT - (293 ). - - -. Hyst. ­ C

tg tg

max

- ( TF ).

( C 121). --------------------------------------------------------------- ------------------

--- · --· -- · -- · -- · ---

21



max
3


10
DOM max

C, ppm , 10
KDP ,%


,


TF,
RT -3

tg
,

tg
, - 103

Hyst., %

KDP-0 0,12 0,55

0,55

KDP-1

<1 15 3
\

KDP-2
\

86 88,5 79,1 90 85
\ \ \

1
\



KDP-3 82,1 0,48

Pyramid Pyramid Prism Pyramid Prism Pyramid Prism

121,68 121,70 121,66 121,7 121,6 121,68 121,64

5,5 4,8 3,4 3,8 4,1 3,7 3,6

97 14 53 85 62 32 41

2 85 4 3 2 10 187

3,7 5,0 3,9 3,2 3,2 3,1 3,1

1

KDP

Pyramid

KDP+Cr

Prism
\ \

2 32 29 4

KDP+R

Pyramid Prism

121,68 121,54 121,52 121,62 121,64 121,26

3,5 2,8 3,5 3,0 3,2 4,5

89 75 79 89 36 12

87,6 79,0 79,7 80,5 81 <77

0,70 0,66 0,68 0,84 0,22 -

9 21 35 33 5 70
\ \

3,2 3,0 3,4 3,1 3,3 3,1

<1 1 <1 <1 3 31
\

KDP+XO

KDP - \ Pyramid 1,4 121,7 2,9 84 93 \ Prism 5,5 121,6 2,4 68 88

KDP+CSB

KDP+A

Pyramid Prism Pyramid Prism

100 0-5 100 0-5

121,82 121,62 121,64 121,74

4,4 5,7 4,0 5,3

13 44 25 94

80,0 79 83,2 89,1

0,08 0,76 0,19 1,04

45 54 17 2

3,1 2,9 4,5 3,4 4,0 3,8

2 16 5 16 1

3. ( ­ . .)

22


III.
· 1. , , («» ), . KDP , , . · 2. , KDP ­ {101} {100} - , ( Fe3+, Al3+ Cr3+), . .
(Cr3+) : , . - , .
· 3. KDP ­

· 4. , K4[Ru2Cl10O] ( ) , . , , , 0.38±0.05 . · 5. Chicago Sky Blue Amaranth, , . , , KD, - . , , , . · 6. KDP (KDP+Amaranth,CSB ) C , . .
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· 7. 10 mHz ­ 1 MHz, . , , , . · 8. KDP. , , . , , ­ . · 9. , KDP: , , . , , , . « » KDP .
4.1
[1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] .., .., .. KH2PO4. : , 1981 .. . . . . 1992. Koval S., Kohanoff J., Lasave J. et.al. First-principals study of ferroelectricity and isotope effects in H-bonded KH2PO4 crystals. PRB, v.71, p.184102 (2005) Bornarel J. Domains in KH2PO4. Ferroelectrics, v.71, p.255 (1987) .. , . , 2000 Kamysheva L.N., Drozhdin S.N. The peculiarities of the KDP group crystals connected with the domain structure dynamics. Ferroelectrics, v.71, p.281 (1987) Nakamura E. Anomalous Dielectric Behavior of KDP type Crystals in the Ferroelectric Phase. Ferroelectrics, v.135, p.237 (1992) .., .., .. . , . ., .57, .128 (1993) Rashkovich L.N. KDP-family Single Crystals. Adam Hilger, Bristol, 1991 Zaitseva N., Carman L. Rapid Growth of KDP-type Crystals Progress in Crystal. Growth and Characterization of Materials, v.43, p.1-118 (2001) Kahr B., Gurney R.W. Dyeing Crystals. Chemical Reviews, v.101, p.893 (2002)

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[12]

[13]

[14]

.., .., .., .. , - KDP, . , .46, .1072 (2001) .., .., .., . KDP. , . 37, .1003 (1992) .., .., .. . KDP . , .39, .914 (1994)

4.2.
a) ·1 .., .., .., .., . « KH2PO4(KDP)». , .43, .2179-2182 (2001) Strukov B.A., Shnaidshtein I.V., Pavlovskaya T.V., Grabovsky S.V., Uesu Y., Fukunaga M. «Phase transitions and dielectric relaxation in dyeing KDP» Ferroelectrics, v.267, p.329-334 (2002) .., .., .. « KDP, » , .48, .357-361 (2003) .., .., .. « KDP» , .45, .518-522 (2003) Grabovsky S.V., Shnaidshtein I.V. and Strukov B.A. «Temperature hysteresis of the domain contribution to the dielectric constant of doped KDP crystals» Ferroelectrics, v.290, p.91-96 (2003) .., .., .., .. « » , .4, .8-18 (2003) .., .., .. « K4[Ru2Cl10O] KDP» . . ., 2, c.55-57 (2004) Grabovsky S.V., Shnaidshtein I.V., Strukov B.A., Jang S.-H. and Kahr B. «Effect of the complex inorganic impurity K4[Ru2Cl10O] on dielectric properties and phase transition of KDP crystal» Ferroelectrics, v.298, p.103-106 (2004) Strukov B.A., Shnaidshtein I.V., Grabovsky S.V. «Phase transitions in KDP crystals with the complex organic and inorganic impurities». Condensed Matter Physics, v.10, p.111-118 (2007)

·2

·3

·4

·5

·6

·7

·8

·9

25


) 1 Strukov B.A., Shnaidshtein I.V., Pavlovskaya T.V., Grabovsky S.V. and Carman L. «Caloric and dielectric properties of dyeing KDP crystals». Abstracts of the third international seminar on ferroelastics physics (ISPF-3). Voronezh (Russia), 11-14 September 2000, p.30 (2000) Strukov B.A., Shnaidshtein I.V., Pavlovskaya T.V., Grabovsky S.V., Uesu Y., Fukunaga M. «Phase transitions and dielectric relaxation in dyeing KDP» Abstracts of the 10-th International Meeting on Ferroelectricity (IMF-10), Madrid (Spain), 3-7 September 2001, p.21 (2001) .., .., .. « KDP» 16- , , 17-21 2002, .37 (2002) Grabovsky S.V., Shnaidshtein I.V., Strukov B.A., Carman L. «Global-type temperature hysteresis of dielectric constant in ferroelectric phase of dye doped KDP crystals» Abstract book of 7-th International Symposium on Ferroic Domains and Mesoscopic Structures (ISFD-7), Giens (France), 15-19 September 2002, p. A3PO4. Strukov B.A., Grabovsky S.V., Shnaidshtein I.V. «Effect of nonisomorphic organic and inorganic impurities on the phase transition and dielectric properties of KDP crystals» Abstracts of NATO Advanced Research Workshop on the Disordered Ferroelectrics (DIFE-2003), Kiev(Ukraine), 29May-2June 2003, p.64. (2003) Grabovsky S.V., Shnaidshtein S.V., Strukov B.A., Jang S.-H., Kahr B. «Influence of complex impurities on dielectric properties of KDP crystal» Abstracts of 10-th European Meeting on Ferroelectricity (EMF-2003), Cambridge (United Kingdom), 3-8 August 2003. Journal of Conference, v. 8, p.141 (2003) Grabovsky S.V., Shnaidshtein I.V., Strukov B.A. «Dielectric properties of KDP crystals obtained by rapid growth method» Abstracts of the 4-th international seminar on ferroelastics physics (ISPF-4), Voronezh (Russia), 15-18 September 2003, p.115 (2003) .. « KH2PO4 (KDP)» «-2004» ( «»). , , 2004. c.281-282 (2004). .., .., .., ., ., .., . « KDP, » 10- (-2004), -, 23-27 2004, c.89-90 (2004). Shnaidshtein I.V., Grabovsky S.V. «Influence of the complex molecular impurities on the ferroelectric phase transition in KDP crystals» Abstracts of the 8-th Russia-CIS-Baltic-Japan Symposium on Ferroelectricity, Tsukuba (Japan), 15-19 May 2006, p.117 (2006). Strukov B.A., Shnaidshtein I.V., Grabovsky S.V. «Phase transitions in KDP crystals with the complex organic and inorganic impurities» Abstracts of the 8-th Ukrainian-Polish and 3-th East-European Meeting on Ferroelectrics Physics, Lviv (Ukraine), 4-7 September 2006, p. 40 (2006).

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