A neutron powder diffraction study of Fe and Ni distributions in synthetic pentlandite and violarite using 60Ni isotope

Texte intégral

(1)Open Archive Toulouse Archive Ouverte (OATAO) OATAO is an open access repository that collects the work of Toulouse researchers and makes it freely available over the web where possible.. This is an author-deposited version published in: http://oatao.univ-toulouse.fr/ Eprints ID: 3852. To link to this article: DOI: 10.2138/am.2006.2144 URL: http://dx.doi.org/10.2138/am.2006.2144. To cite this version: Tenailleau, Christophe and Etschmann, Barbara and Ibberson, Richard M. and Pring, Allan ( 2006) A neutron powder diffraction study of Fe and Ni distributions in synthetic pentlandite and violarite using 60Ni isotope. American Mineralogist , vol. 91 (n° 8-9). pp. 1442-1447. ISSN 0003-004X. Any correspondence concerning this service should be sent to the repository administrator: staff-oatao@inp-toulouse.fr.

(2)

(3)

(4)

(5)

(6)

(7)

(8)

(9)

(10)

(11)

(12)

(13) !" #$%#& & ''& ()(* + + &$ #, () # ,- ++&$(.. '' %/)(0(1 ". *

(14) <

(15) 5

(16) G < !

(17) , G 5

(18) G 2000 G . B5B5 3 :

(19) G

(20) F

(21)

(22) (

(23) *

(24) D

(25) D>"" 0M> H? 4 *

(26) @

(27)

(28) @

(29) H

(30) G !

(31) , G 5

(32) G 2002 G . +$ (

(33)

(34)

(35)

(36)

(37) À

(38) .

(39)

(40)

(41)

(42)

(43) $0!

(44) .

(45)

(46)

(47) 3)-! ).5- "208 (

(48) "

(49)

(50) ! ;3

(51) !.

(52) 2%. 9

(53)

(54) )$" 9

(55)

(56) . "0"0%2" 7 G

(57) .

(58) "20 8( ! ;3

(59)

(60) . 24. 9 !

(61) )-. 9 ! . 0."9

(62)

(63)

(64) 3;!

(65) . 5

(66) 3! .5) 400 8(

(67)

(68) !

(69)

(70) . 3 !

(71) B

(72)

(73) 1

(74)

(75) 400 8(

(76) ".

(77)

(78) ! ;3.

(79)

(80) '

(81)

(82)

(83) 1

(84)

(85)

(86)

(87)

(88) N"%4 8( ,

(89)

(90) . 3.O ! .O

(91) 3.O

(92) ! 4O . 2 3 !

(93)

(94)

(95)

(96) $0!

(97)

(98)

(99)

(100) .

(101)

(102)

(103) À .

(104)

(105) À

(106) .

(107)

(108) .

(109)

(110)

(111)

(112)

(113)

(114) .

(115)

(116)

(117)

(118) À

(119)

(120)

(121) PVV ! . "#$%& ' ( "#%)& * ++

(122) ,

(123) "#-.&. / .00) !

(124) 1

(125)

(126)

(127) .20 °(

(128) .

(129)

(130)

(131)

(132) 3 !

(133) .

(134)

(135) , "#-# . , "#-#

(136)

(137) . ! )2%3))(

(138) 004 5- D 6 "002" 7

(139) D 6 "0"0-. 7

(140) .20 8(

(141)

(142) . 02$9 : "#%2

(143) 1

(144) 0229

(145)

(146)

(147) ! 1 . , "#-#

(148)

(149) .

(150) """ 8( / . .00)

(151) "20

(152) .00. 8(

(153)

(154) 2

(155)

(156)

(157)

(158) 1. E A F

(159)

(160) (:B5<G,1H<: $20- /!5B (1 $ I

(161) < J 1")020 (G/! ( 3 K /1 A L

(162)

(163) . 3;!

(164)

(165) . <= >1 1

(166)

(167)

(168)

(169)

(170) . 3

(171)

(172)

(173)

(174)

(175) . ?

(176) "#%0& , !+ "#-)&. , "#-# . '

(177)

(178)

(179)

(180)

(181)

(182) .

(183)

(184)

(185)

(186)

(187)

(188) .

(189)

(190) ! "#%)& < 3 "#%)&. @ .00.& , .00$ '

(191)

(192) . 3 !

(193)

(194) . FFS

(195) 5

(196) ,

(197) .

(198)

(199) A.

(200)

(201)

(202)

(203) 5 1

(204)

(205)

(206) .

(207)

(208) 3;!

(209) B

(210)

(211)

(212) .

(213)

(214) 5 .

(215)

(216)

(217) . B 3 !

(218)

(219) C

(220) . ";-

(221)

(222) FFS 5 3 " .

(223)

(224) C

(225)

(226) . ";-

(227) 3 " ,

(228)

(229)

(230)

(231)

(232) 3 !.

(233)

(234) D

(235) B.

(236)

(237)

(238)

(239) .

(240) b (a). c (b). /& )- 5

(241)

(242)

(243) <5$

(244) <5) . .

(245) B .

(246)

(247)

(248) .

(249)

(250)

(251) G .

(252)

(253) À

(254)

(255) 3

(256) 1

(257)

(258) <=

(259)

(260) . ,

(261) "#%%

(262) 3.O .

(263)

(264)

(265) +

(266)

(267) .

(268)

(269) +

(270) 1

(271) À

(272) .

(273) ,

(274)

(275) 1

(276) À

(277) .

(278) ! 4O

(279) Q 3.O

(280) .

(281)

(282) ' . ( "#-2

(283)

(284) 3

(285) .

(286)

(287)

(288)

(289) 3

(290) 1 3

(291)

(292) .004 .

(293)

(294)

(295)

(296)

(297) .

(298)

(299)

(300) (( .5) ,

(301) .

(302) 3

(303)

(304)

(305)

(306) .

(307)

(308) 3.O 34O ,

(309)

(310)

(311) .

(312)

(313)

(314)

(315) .

(316)

(317) >1 ,

(318) 1

(319) 3 !

(320)

(321) .

(322)

(323) >1 0#2. "04 × "0N".

(324) 3;!

(325) .

(326)

(327) $0!

(328) 0.- × "0N".

(329)

(330) 3. &4%&,& ' ,&#$ $5#&$$ 5

(331)

(332)

(333)

(334)

(335)

(336)

(337)

(338) 3 " . ###O9 G ! " ##O9 G

(339) $0!

(340)

(341) .

(342) ##$09 B

(343) Á 5 ####O9 G .

(344) R"0N.

(345) ,

(346)

(347) .

(348)

(349) . $0!

(350)

(351)

(352)

(353) ! (

(354)

(355) 42 . +

(356)

(357)

(358) 5 .

(359)

(360) ! $0!

(361) . ,

(362)

(363)

(364)

(365)

(366)

(367) . / .00)

(368) À PVV

(369)

(370)

(371)

(372) 30-! 0.5. ,

(373) "0 .

(374)

(375) 400 8(

(376) 200 -00 8(

(377)

(378) ".

(379) . , +

(380) 15

(381)

(382) )20. 8( ,

(383)

(384)

(385) .

(386)

(387)

(388)

(389) PVV. , ""00 8(

(390) .

(391)

(392)

(393) #00 8(

(394) %.

(395)

(396)

(397) ,

(398)

(399) 1

(400)

(401) 02 + M

(402) .

(403) #00 8(

(404)

(405)

(406) "0 , . .00 8(

(407) .

(408) , .

(409)

(410)

(411) F P

(412)

(413) . 1

(414)

(415) + $00 8(.

(416) .)

(417)

(418)

(419)

(420) "20 8(

(421)

(422)

(423) .

(424) G . 1 . '

(425)

(426) 1

(427)

(428) ,

(429) "#%% .

(430)

(431) À 1 PVV . (

(432)

(433)

(434) 3! .54

(435)

(436)

(437)

(438) 400 8( . 200 %00 8( . 8(;

(439) ".

(440)

(441) +.

(442) 5 ,

(443)

(444) "000 8(

(445) .

(446) .

(447)

(448)

(449) #00 8(

(450) , .

(451)

(452) .

(453)

(454) 3! .54

(455) 3! .5) 5 À .

(456) 4 400 8(

(457) .

(458)

(459) $$ , 1

(460)

(461)

(462)

(463) P:* B5B5 H? .

(464)

(465) A I " #08. I .

(466) S5

(467) ,

(468)

(469) . 4P

(470) T B

(471) "##.

(472) U ,

(473) . .θ

(474) "$0N"%$8 I " -0N"008 I . .-N4.8 I 4 . Ω

(475) 0)" 0%0 00" ΔG;G

(476)

(477)

(478) R) V "0N) . V "0N4 . . V "0. , 1

(479) 1Á

(480) 42N".0 .

(481)

(482)

(483)

(484) G1

(485) 0%.N.)# 7 *

(486) +.

(487)

(488)

(489) À

(490)

(491) . 'GW(D:

(492) ,

(493) .

(494) G +

(495)

(496) 11

(497)

(498)

(499)

(500) , ! 1 $0! 1

(501)

(502)

(503) . "20 8(

(504)

(505)

(506)

(507) . ) $

(508)

(509)

(510) , .

(511) " 8(;

(512)

(513) ..2 8(

(514) .

(515) 400 8( 3

(516)

(517) $0! .

(518) .

(519) "20 8( 1

(520)

(521)

(522) P:*. B5B5

(523) $

(524) . ,

(525) ! 1 $0!

(526)

(527) . )

(528)

(529)

(530)

(531)

(532)

(533) P

(534)

(535)

(536) . %28

(537) %2

(538) 400 8(

(539) . 8(; .

(540)

(541) +

(542)

(543) 3

(544)

(545) .

(546)

(547)

(548)

(549)

(550)

(551) .

(552) ".

(553)

(554)

(555)

(556)

(557)

(558) N%4 N"%4 8(

(559) $

(560) . 1 .2 ..2 400 8( ,. "

(561)

(562) . , . ,

(563)

(564)

(565)

(566)

(567) 1

(568)

(569) À À .

(570)

(571)

(572)

(573)

(574) . / .00)

(575)

(576) . °C. $ À

(577) 8

(578) , + @5G5

(579) 1

(580)

(581) , +

(582)

(583) . À

(584)

(585)

(586)

(587) À

(588)

(589)

(590) . 3

(591) À

(592)

(593)

(594) . 1 1

(595) 1'

(596)

(597) À

(598)

(599) . . 000"

(600) À ,

(601) -. (

(602) ,D3

(603) À

(604)

(605) . B1 ( " " " À .

(606) 5

(607)

(608)

(609)

(610)

(611)

(612) .

(613)

(614) À

(615)

(616)

(617) .

(618) 3$4PPF

(619)

(620)

(621)

(622) .

(623)

(624)

(625) .

(626)

(627) <%25- B

(628)

(629)

(630) 5

(631) .

(632)

(633) 3 !

(634) 4.I .)H . N N

(635) 3P4P 4.H

(636)

(637) 3G4P. À G

(638) À À .

(639) À 3;!

(640)

(641) , 3;!.

(642)

(643)

(644) À À . '

(645)

(646)

(647)

(648) À

(649)

(650).

(651)

(652)

(653)

(654) . 1. 1.5. 2. 1.5. 2. °C. &$'$ $ $$ ,& ' $+ %&' & ,

(655)

(656) .

(657) $0! 1 .2 400 8(

(658) 3 . *1

(659) "

(660)

(661)

(662) G1 .

(663)

(664) À . ,

(665)

(666)

(667) 1

(668) Á

(669)

(670)

(671) . ! G

(672)

(673)

(674)

(675) . PVV;

(676) À , .002

(677) .

(678)

(679)

(680)

(681) (

(682)

(683)

(684) . 1. (Å) /& .- D

(685) .

(686)

(687)

(688) 1

(689) 1Á

(690)

(691)

(692) . $0 ! 1

(693) .2 8( 400 8(

(694) .

(695) " I . A

(696)

(697)

(698)

(699) @

(700)

(701) 1

(702) 1À . 5 5 χ. A 0")$# 0"-") 2422 0".#" 0")#-. .4-. .2 400 8( TABLE 2. Positional and displacement parameters of 60Ni-pentlandite. TABLE 1.. Unit-cell parameters and compositions of 60Ni-pentlandite at various temperatures. T (°C) Formula wt% a (Å) %60Ni(O) %60Ni(T) 34(1) 10.1075(1) 57(2) 46(2) 25* Fe4.8Ni4.2S8 34(1) 10.2045(1) 50(2) 47(2) 225 Fe4.8Ni4.2S8 34(1) 10.2349(1) 50(2) 46(2) 300 Fe4.8Ni4.2S8 Fe4.6Ni4.4S8 35(1) 10.1296(1) 52(2) 48(2) 25† Notes: Estimated standard deviations are given in brackets. T stands for tetrahedra and O for octahedra. * Composition and unit-cell parameters for the co-existing pyrrhotite are Fe6.6Ni0.9S8, a =3.4471(1) and c =5.7517(1) Å. † After an additional 2 months annealing at 150 °C.. T (°C) x(M) in 32f Uiso(M) × 102 (Å2) x(S) in 24e Uiso(S) × 102 (Å2) 25 0.1274 0.53 0.2590 0.38 225 0.1280 1.10 0.2624 0.53 300 0.1276 1.61 0.2600 0.99 0.1273 0.95 0.2601 0.81 25* Notes: M represents the metal. Since those parameters were fixed during the final cycles of refinement (for M distribution) errors are not given here. – x(M) = y(M) = z(M) ~ 0.125 : 32f Wyckoff position (Tetrahedral site) for Fm 3 m space group x(M) = y(M) = z(M) = 0.5 : 4f (Octahedral site) y(S1) = z(S1) = 0 : 24e x(S2) = 0.25 and y(S2) = z(S2) = 0 : 8c * After an additional 2 months annealing at 150 °C..

(703)

(704) , .

(705)

(706) .

(707)

(708) : "#%4 , "#-# . ,

(709)

(710) .

(711)

(712) & .

(713)

(714) .

(715) ! 3 ,

(716)

(717)

(718) .

(719)

(720)

(721) "20 °( , " . B

(722)

(723)

(724) . À , 4 ,

(725)

(726)

(727) 1

(728)

(729) .

(730) <15

(731)

(732) .

(733)

(734)

(735)

(736)

(737) 1 3

(738)

(739) <151<

(740)

(741) 51<15 . , <15 .

(742)

(743) .)). 7

(744)

(745)

(746) . $0 ! 1

(747)

(748)

(749) .

(750) <D 15 R.4% 7 : . "#%4 ,

(751) .

(752)

(753)

(754)

(755)

(756)

(757) !

(758)

(759) . : "#%2

(760)

(761)

(762) ,1 !+ "#-) , "#-#

(763) . 3.O

(764)

(765)

(766) ,

(767)

(768) . $0! 1

(769) 3.O .

(770) 0%- 7

(771)

(772) 0$" 7

(773)

(774) 3.O 5

(775) . "#%$ ! .O

(776)

(777)

(778) 0$#. 7

(779) ! 4O

(780) 0$0. 02$ 7 5

(781) "#%$ G

(782)

(783) . 3.O

(784) ! .O

(785)

(786)

(787)

(788) . <D 15 T

(789) R..$ 7 : . "#%4 U , <, 15

(790)

(791) $0! 11

(792)

(793) 3.O

(794) .

(795)

(796)

(797) <, 1<,

(798) .

(799) À

(800) D

(801)

(802) .

(803) 3;!

(804) .

(805)

(806) . "20 8(

(807) .

(808) À

(809) / . .00) B .

(810)

(811) 2

(812) "20 8(.

(813)

(814)

(815)

(816)

(817) .

(818)

(819)

(820) "

(821) ,

(822)

(823) . &

(824)

(825)

(826) .

(827)

(828)

(829) ! ;3

(830) . B

(831)

(832)

(833)

(834) . TABLE 3.. Thermal variations of distances (Å) and angles (degrees) in 60 Ni-pentlandite. T (°C) 25 225 300 25* 2.575 2.613 2.612 2.579 [M(T)-M(T)]e [M(O)-S] 2.436 2.425 2.456 2.430 2.255 2.301 2.291 2.266 [M(T)-S]1 2.147 2.156 2.170 2.152 [M(T)-S]2 <M(O)-S-M(T)> 126.2 126.6 126.3 126.4 69.6 69.2 69.5 69.4 <M(T)-S-M(T)>e1 107.7 106.9 107.5 107.2 <M(T)-S-M(T)>e2 109.471 109.471 109.471 109.471 <M(T)-S-M(T)>c 110.3 110.7 110.5 110.6 <S-M(T)-S>1 108.6 108.2 108.5 108.3 <S-M(T)-S>2 Notes: M represents the metal (Fe or Ni). T stands for tetrahedra and O for octahedra. C and E indicate corner-shared or edge-shared tetrahedra, respectively (see Fig. 1). Since atomic parameters were fixed during the final cycles of refinement (for M distribution) errors are not given here. * After an additional 2 months annealing at 150 °C..

(835) : "#%2 , "#-#.

(836)

(837)

(838)

(839) !

(840) 3.O

(841) .

(842)

(843)

(844) (

(845)

(846)

(847) .

(848)

(849)

(850) .

(851) .

(852)

(853)

(854)

(855)

(856) . $0! 1 "00 8(.

(857)

(858)

(859)

(860) , "#-#.

(861)

(862)

(863) . ,

(864)

(865) ,

(866)

(867)

(868) .2 ..2 8(. À

(869)

(870)

(871) . 3 4 ,

(872)

(873)

(874)

(875)

(876) . + , )

(877)

(878)

(879)

(880)

(881) . , 2 G

(882)

(883) .

(884) %$" 9

(885)

(886) 1

(887) PVV

(888) R"2 9 .

(889)

(890)

(891) PVV , . G R."0 "-$ "$" 7

(892)

(893) .

(894)

(895) À . ,

(896)

(897)

(898)

(899) $0! 1

(900)

(901)

(902) .

(903) 3! .5) À :À

(904)

(905) .

(906) 3 !

(907)

(908)

(909) .

(910) !

(911) .

(912) 3 ! .

(913)

(914) ,

(915)

(916) . 3.O! 4O D! 4O ,5) P .

(917) 400 8(

(918)

(919)

(920) 3 !

(921) .

(922) ,

(923)

(924)

(925) . $0 ! 1

(926) , $ ,

(927) . <1< R4) 7

(928)

(929) ,

(930). TABLE 4.. Thermal variations of composition and structural parameters of 60Ni-violarite. T (°C) Formula wt%violarite a (Å) %60Ni(O) %60Ni(T) wt%mss wt%pyrite 25* Fe0.95Ni2.05S4 76(1) 9.4424(1) 54(2) 97(1) 7(1) 17(1) 97(1) 8(1) 18(1) 75 Fe1.04Ni1.96S4 74(1) 9.4452(1) 50(3) 98(1) 8(1) 8(1) 150 Fe0.84Ni2.16S4 84(1) 9.4612(1) 59(3) 97(1) 8(1) 15(1) 225 Fe1.00Ni2.00S4 77(1) 9.4709(1) 52(3) 99(3) 7(1) 14(1) 300 Fe0.83Ni2.17S4 79(1) 9.4847(2) 59(6) 93(1) 7(1) 17(1) 25 Fe1.14Ni1.86S4 76(1) 9.4498(1) 47(2) 93(1) 9(1) 19(1) –73 Fe1.19Ni1.81S4 72(1) 9.4318(1) 44(2) 92(1) 9(1) 19(1) –173 Fe1.19Ni1.81S4 72(1) 9.4211(1) 44(2) Note: Errors are noted in parentheses. – * mss [P63/mmc: a =3.4118(2) and c = 5.3715(4) Å] and pyrite [Pa 3: a = 5.4237(3) Å] with shared Fe/60Ni occupancy on M site.. TABLE 5.. Thermal variation of atom positions and displacement parameters in 60Ni-violarite. T (°C) Uiso(M) × 102 (Å2) x(S) in 32e Uiso(S) × 102 (Å2) 25 0.05(4) 0.2578(2) 0.43(9) 75 0.06(5) 0.2572(3) 0.35(14) 150 0.01(10) 0.2583(3) 0.25(15) 225 0.32(10) 0.2573(3) 0.33(15) 300 0.45(22) 0.2586(6) 1.01(34) 25 0.67(8) 0.2581(2) 0.43(12) –73 0.11(5) 0.2573(2) 0.15(9) –173 0.03(5) 0.2582(2) 0.16(6) Note: Estimated standard deviations are given in parentheses. – x(M) = y(M) = z(M) = 0.125 : 8a Wyckoff position (Tetrahedral site) for Fd3 m space group x(M) = y(M) = z(M) = 0.5 : 4f (Octahedral site) x(S) = y(S) = z(S) ~ 0.25 : 32e.

(931) TABLE 6. Thermal variations of distances (Å) and angles (degrees) in 60Ni-violarite T (°C) 25 75 150 225 300 [M(O)-S] 2.289(1) 2.295(2) 2.289(2) 2.301(2) 2.2935(3) [M(T)-S] 2.172(3) 2.163(4) 2.185(4) 2.170(4) 2.195(10) <M(O)-S-M(O)> 93.6(1) 93.4(1) 93.9(1) 93.4(1) 94.0(3) <M(O)-S-M(T)> 122.6(1) 122.8(1) 122.5(1) 122.8(1) 122.4(2) 86.2(1) 86.5(1) 86.0(1) 86.5(1) 85.9(3) <S-M(O)-S>1 93.7(1) 93.5(1) 94.0(1) 93.5(1) 94.1(1) <S-M(O)-S>2 <S-M(T)-S> 109.471(1) 109.471(1) 109.471(1) 109.471(1) 109.471(2) Notes: Where M replaces the metal (Fe or Ni). T stands for tetrahedra and O for octahedra (see Fig. 1). Errors are given in parentheses.. °C. 1. 2. 1.5 °C. 25 2.288(2) 2.179(3) 93.8(1) 122.5(1) 86.1(1) 93.9(1) 109.471(1).

(932)

(933) .

(934) .

(935)

(936) &

(937) 1

(938)

(939)

(940)

(941)

(942) . ,

(943)

(944)

(945)

(946) .

(947)

(948)

(949)

(950) .

(951)

(952) N"%48( G

(953)

(954)

(955) .

(956)

(957) 5

(958) . . '

(959)

(960) À .

(961)

(962)

(963)

(964)

(965) &

(966) .

(967)

(968)

(969) D

(970) . 1

(971) & <1<. .$ 7 ,

(972) <1<

(973)

(974)

(975) .

(976) <1< R4) 7 B

(977) . +

(978)

(979)

(980) .

(981)

(982) D

(983) .

(984)

(985) .

(986)

(987)

(988) . 29'&/,&$ Q 5 <

(989) P Q

(990) .

(991)

(992) B5B5 ,

(993)

(994)

(995)

(996)

(997)

(998) .

(999)