1.??????(Gas Vaporization)

1
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2
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?????????????????????????,???????????????????,????
???????????????????????????
1.??????(Gas Vaporization) 2.???????(Chemical
Vapor Deposition, CVD) 3.???????(Chemical Vapor
Condensation, CVC) 4.???(Sputter)
3
??????
????????????(?????)??????????????,?????????,????(?
?????????????) ???????? ????1963??Ryozi
Uyeda????????,????????? ?????????????????????? 20?
?80???,Gleiter??????,???????????????????,?????????
????????(polycrystal)(? ???)????????
4
?????????????,???????????0.1kPa??????,??????(?2
kPa)????? ??(inert gas)(He?Ar,????99.9996)?
??????(?????CaF2?NaCl?FeF??????????????????????)??
???,?????????????????????????,???????????????? ?,?
?????,??????????(77K)?
??????,??????????????????????????????,????????????
?????????? ????,???????????? ??,??????????,???????
?????,???????????????????????,??????????????,?????
????????,?????????? ????????????
5
?????????????????,???????????????,????????,???????
????
????,????????(???????????)????,?????????????,?????
??????,????? ??lnPV(PV????????)?
??1-2??,??????????,??????????,??? ??,?????????????
???????
????????????????????? ????? ????,??????
???????
6
???????
???????(Chemical Vapor Deposition,??CVD)??????????
???????????,????????????? ??,????????????,????????
?????? ????????????????????,?????????????????????
???????????????? ?? ?????????????????????????????
? ????????????? ?????????????????????????????? ??
????????????????????? ?20??80???,CVD?????????????
?????? ???
7
????????????
(1)????? ?????(gas phase decomposition)??????????
?(single component thermal decomposition)?????????
??????????????????????????,???????????????????????
??????????????????????????,????????? ????
?????????????????????????????????????????,?Fe(CO)5
?SiH4?Si(NH)2?(CH3)4Si?Si(OH)4?,???????????
8
(2)????? ?????(vapor synthesis)??????????????????
??,????????????????????,??????????????????????????
????,??????????,??????????? ???
??????????????
9
????????????,???????????????????,????????????????,
???????????????????,?????????????????????????,????
????????????l-2???????????????????? (equilibrium
constant)?
10
???????
???????????????????????,??????????????????????????
??,???? ???????? ????????????????????,???????????
??????????????(CVD)????,?????????????????????????
,???????????,????????????CVD??????????????????????
??,????????,???? ???? ?????????,1994?W.
Chang??????????????????????????,??CVC?(chemical
vapor condensation, CVC),???????????SiC?Si3N4?ZrO2
?TiO2????????
11
??????????????????????????????????????????????????
????????????? ????????????? ??????????????????,??
???????,?????????,?????(??1-37),???11001400?C,???
? ????1001000Pa?????? ?????,???????,?????????,??
???????????????, ???????????????
12
???
???(sputter)???????????????????????????????????,??
??????,?????????????????,???????????????,??????? ?
?????????????????????? ????????,????(?)??????????
????????????,??????,??????????????,?? ????????????
?????????????? ??????????????? ????? ????(?)????
?????(??,????) ????????????? ?????????? ??????????
?????????????? ?????????
13
??1-39???,??????(Al????????????)?????Ar?(40250Pa)
?,???????????? ???,????????? ????????????????????
????,????????????? ??? ??,???????????????????????
??????Ag????,?????520nm???????? ??????????????
14
?????????
??????_???
15
?????????
??????????????????????????,??????????????,????????
????? ?,??????????,???????????? ???????? 1.??? 2.?
?? 3.??? 4.??????(????) 5.??????? 6.??-???
16
???
????????????????,??????(?OH-?C2O42-?CO32-?)?,?????
????????,????????????????????????,????????????????
,??????? ????????????
????
????????????????,??????????? ?????(coprecipitation
)? ??????????(single phase coprecipitation)?????
???(mixtured coprecipitation)?
17
(1)????? ????????????????,???????(single-phase
coprecipitation),????????(chemical compound
precipitation)? ????????????????????????????????,
??,?????????????????????????? ?,??????????????????
BaTiO(C2O4)2.4H2O ? BaTiO3 BaSn(C2O4)2.1/2H2O ?
BaSnO3 CaZrO(C2O4)2.H2O ? CaZrO3 LaFe(CN)6.5H2O ?
LaFeO3
?????????????????????????,??,??????????,??????????
????
18
(2)?????? ???????????,????????? ?ZrOCl2.8H2O?Y2O3?
?????ZrO2-Y2O3?????????Y2O3???????YCl3,???ZrOCl2.
8H2O?Y2O3????????????,???? NH4OH???Zr(OH)4?Y(OH)3
?????????,?????
?????????????????????ZrO2(Y2O3)?????
??????????????,?????????????????,?????????????pH??
??????,Zr?Y?Mg?Ca???????????,?pH??????,??????????
?pH?????,??2-2???
??????????,??????????????????????????????,????????
???????????????????,????????????
19
???
????????(hydrate)????,????????????????????????????
??????????????????????,????????????,??????????????
???????????????????????????????????,???????????,??
???????????????????????,?????????? ???????????????
?
??????
??????????????????,??????????????,????????????????
???????????,???????????????????????,??????????????
??,??????????,????????????????????????????2-3?????
???????????????,??????????????????pH????,????????2
0nm ????????
20
???????
?????????????(organometallic alcoholate)??????????
???,?????????????????????????? ??????????? 1.????
??????????,?????????,??????????? 2.???????????????
???
?????????????BaTiO3????? ??BaTiO3????????Ba?Ti???
?Ba?????Ba?????????,Ti????NH3??????????????,?????,
??? ???,?????? NH4Cl????? ????????????????,??BaTi
l1????????????,???2???????????????????,?????????
??????????????BaTiO3?? ????,????????? 2-4?
21
?????????????,??????????????????????,?????????????
???????????,???????????????????????X?????(X-ray
diffraction)?????(differential scanning
calorimeter, DSC)??????????????? ????? ?2-5???????
????????X???????????,X???? ???????????? ??????????
??????? ????,?????????? ??????????????????????????
?,???????????????????,??? ?????????????
22
??????,?????,????,?????????????????????? ????????
??0.011mol/L????????BaTiO3,?????????????????2-6??
????,?????????????100?,???BaTiO3??? ??????????
???????l0nm,??????,???????l5nm??,???????????,?????
???????????????,????10100nm?????????,?????????? ?
?,?????????????????
??????????????????,????????????????????????,?BaTiO
3??,??SrTiO3?BaZrO3?NiFe2O4?CoFe2O4?MnFe2O4???????
?(Ba,Sr)TiO3?Sr(Ti,Zr)O3?(Mn,Zn)Fe2O4?????? ??????
??,?????????????????????
23
??????????? 1.??????????????????????,??????
????? 2?????????,?????????????????,?
????????? 3.???????????????????,??????-??
??,?????,????-?-???????,??????
???????? 4.??????,????????,??????????,??
?????,?????????????? 5.?????????????,?????????????
?? ????????????????????????????
???????????,?????????????????
??????????????,????????????
24
???
??????????????????????????????????????????????????
???????????????,???????????1?m??????????? ????????
??? ????????????????????? ??????(spray drying
method) ????????????????????????? ??????(spra
y hydrolysis method) ??????????? ??????(spra
y baking method) ???????????????????
25
?????
??????????????????????????????? ???????? ?2-7????
?????????????,????????????????????????,???????????
????? ???,????????????????
???????????????????????????????????1020?m,??????
???????? ?????????800l000?C?????????????????????
??????200nm??,??????????,????????,? ????????????
26
?????
???????????,??????????????????,????????????????,??
??????????????????,????????????????,??????????????
?????????????,????????????????????
?2-8??????????????????????????????????????????????
??????,??? ?????????????????
??????????????,??????????????????,? ?????????????,
????????????
27
?2-8?,?????(1)??????????(2)??,?????????(6),???????
??????5002000cm3/min,?????122155?C???? ???133.32
2Pa? ?????????????????(8)????????????????????????1
30?C????(9)??????,???????(10)?????? ??????25?C? ??
??????????????????????????????????(11)???????,????
???????,???????25?C????,??????300?C???????????,???
????????
28
?????
?2-11??????????????????????????????,?? ???????????
??? ?????????????????? ????????????,?????????????
??????????????????????,????????????,????????????,?
????????????????,?????????,????? ?????,??????????
????????,???????, ????????????????
29
??????(????)
?????(solvent-thermal reaction)?????????(????)????
????????????????(???)(hydro-thermal
method)????,???????????????
???
????(hydro-thermal method)????????,??????????????,
????,??????????? ????? ??????????
??M??????????
?????(hydro-thermal precipitation) ??
30
?????(hydro-thermal synthesis) ??
?????(hydro-thermal reduction) ??
?? M???????
?????(hydro-thermal decomposition) ??
?????(hydro-thermal crystallization) ??
31
???????????????????,??????? ????????????????????
????????30 nm???? ?????????????????25nm????
????? ?,????????????100MPa????523973K??
?Zr5Al3?????l00MPa?773973K???????????
1035nm???????????????-Al2O3?????? ???????????SnO
2???????????0.25mol/L ??????????,????????????
???,? 150?C??12??,?????????,??????,???
??????????????5nm???SnO2??????
32
????????????????????????????
?????????????,??????????????
????????????????????????????
?????????????? ??????????????????,?????????
????????????????,??????????? ???? ??Ti(OH)4????
??,???30mm??430mm????? ?,????????,????????,?????
??? ??(temperature gradient)??300?C???????8h,???
????,?????????,??????,?l00?C???
???25nm?TiO2????????????????????
?????????????,?????????????? ???????????????????
? ???????,?Ba(OH)2?8H2O?TiO2????,???
?BaTiO3????????170 nm?
33
???????
???????(vaporization solvent-thermal
decomposition)????????????????????????????,???????
????,???????????????????? ?????????,??????????????
????? ?????????????????,??????(freeze-dying
method)????????????????????,??????????????????????
??,????????????????????,?????????,??????? ?,??????
?????????????? ????????? ??????,?????????????? ??
???????? ????????
34
??-???
??-????(sol-gel method)?????????????????? ???????,
?????????????????????? ????????????????,??????????
????????????,???????????????????????,?????????????
???,??????????????????????-??????????????,?????? ?
??????????????
??????? ????? ??(????????)???????????,???????
???????? ????-?????,???????,???????????,????
????????????? ????? ??????0.1 ?m?
35
?????????????????? ???????????????????????,???
?,????? ????????????,?????????,?????????? ??
?????? ?????????????,???????,????????? ?????
?,??????? ??????? ????????,????????? ?????????????
?????,???????????,???? ?????? ??????????
36
??-??????
??????-????????????????????,???????-?????????????
???????????????????????? ????2-15???
??-?????????????????????,????????? ????????,??????
??? ?20??80??????????-?????????????????????,?????
?-???????,??????????????? ??????,?????????????????
?????
37
????-????????????????????????????????,????????????
??????,??????????????,????????????????????????????
??????,??????,?????????????????????,????,?????????
???????,??? ????????????,? ??????????(???)?????
????????????,?????M(OH)n??,???????????????????????
????????,???????(?????),????????,?????????????????
????SnO2????????????-??????????20gSnCl2???250ml??
??,??0.5??,?1????,2????,?????5?,???60?C? ????????,
??100?C????SnO2?????
38
?????????
??????_???
39
?????????
?????????????????????????????,??????????????????,?
??????????,?????????????????????,????????????????,
?????????????? ??????,?????????? ?????????????????
??,????????????????????????????????(?)??????????,?
?(??)???????,??????????,?????????????????,????,??(
??)??????,????????,???????????,???????????????????
????????????? ????????,??????????
40
?????????????????,???????????????????(size
reduction process)?????????? ???(?????)??????(bu
ild up process)???? ??????????? ?????(?????????
????) ?????(???) ?????????? ?????(thermal
decomposition)(???????) ??????(solid-state
reaction)(???????) ??????(electrical
discharge)(??????????)
41
????
?????(thermal decomposition reaction)???????,?????
????????????????????????????,??? ????(S?????G????)

?(1)?????,?(3)????,????????,?(2)??(1)?????????????
??????,??????????????????? ?????????????????(1)???
?
?3-1?????????????????????????????, ???????? ??????
(M2C2O4)????,? ?Li??Na??????? ??????????(MC2O4),??
BeCC2O4.3H2O(24.8g/100g?)? ????????
42
???????
????????????????????,?????????????????????????????
?? ?????????????????
??I
??II
?IA??IIA?(?Be?Mg?)?IIIA???????????????????II(IA???
????MO,???MO?MCO3???)??,??????????????I?????,?????
?????,?? ??I???,??????,??????????I????
??????K1?K2?
43
????,CO?CO2??,?????????????????
???????
??K1?K2?K3?K4????????
???????????
??????(4)?K3?K4???????????G3??G4,??G3gt?G4???????K3
ltK4??????(4)K3ltK4,?????????????,??(4)??????G3?????
????????????G4????????,Cu?Co?Pb?Ni????????????,Zn?
Cr?Mn?Al????????? ????????
44
???????????????3-2?,??,??????????,????II??????????
,??????????????????????????,???II???????????,?????
???????????????????????????,????????????????????,?
???????????????????????????1/41/2??? ???
??????????????
????????????,?????????,???????,?????????????
45
??????????????????????????????????????????????,???
??????1.???????2.????????????,???????????????????
?????,????????????????????,?????? ?????????? ?????
????,???IV???????IIA?IIB?IVB??????MIIMIVO3????????
?????????,???????????MIV???MII????????????,?30?C??
????,?????????????,?????MIIMIVO(C2O4)2.nH2O???????
?????????,???BaTiO3????????,?500700?C????????????
??BaTiO3?? ????(Sr?Ba)TiO3??????????
46
?????
??????(solid-state thermal decomposition)?????????
??,?????????,???????????????????????????????????,?
??????????,???????????????? ?,???????????,????????
??3-1? ????????????,??????????,???????????,???????
?????????,????????????????????????,????1100?C????,
??????????12?m???????????????????????,???????? ??
?????
????????????????,??????????,?????????????????????,
?????????????????????????? ?(?????????????)???????
(???????????)???? ??,????????,???????????????????
,????????,????????????????????????????????????????
??,????????????????,???????,????? ?????,??????????
?,????????????????
47
?????
??????????????????,??????,??3-2?????-??????,???? ?
??? ????????,????????,?b???????????????,???????,??
?????,???????????????? ?? ????????????????????????
(electrical spark discharge),???????????,??10-710
-5s,?????(voltage gradient)???,?105106V/cm,??????
,?106109A/cm2,?????????????????????????,?????????
???, ??????????? ?????????,???????????????????????
?????????????????????,?????????????,??????????????
???,????? ?????,????????????????
48
????????????,?3-3????????????????????????,???????,
????????????????????????????20cm,???120cm,??????,?
? ?1015 mm? ??????24kV??????1200?/s??????????????
???,??????????????????????????????????????????????
??????????????,????????OH???Al??????Al(OH)3???????
??????,??????24?????????????????????0.61?m?Al2O3?
?????????????,??????? ??Al2O3???
49
???
?????,??????????????????????????(Ball
milling)?????????????????????????????,? ?????????
??????????????????????????,???????????????????????
???????????????????,?????????????????,??????(nanoc
rystal)????(noncrystal)????(pseudocrystal)?????,??
???????? ????????,??????????????????
?????????????3-4???????50?m??????????????????,????
?????????????????????????????,????????????510,???
???????????????3-4? ????????????? ????????????????
??????,???????????????,????????,??????????????????
????????????,??????????,????????????,?????????????
???????,??????????????,? ???100200?C?
50
??????????????,?????????????????????????????????,?
??????????,????????????????????????(????)???(????)
?????,??????????????????????????????,?????????????
????,????????????????????????????????????,????????
?12??,??????????3?10-4?????????????????(30????)
,??????? 10???? ????????????????,????????????,??,
????????????????????????1988?,??????Shingu????????
?????Al-Fe??????,??????????????????????,???????? ?
?????????????
51
?????????????????,??????????????? ????,???????????
??? ??????????????????????????????,???????????????
???????(??-??-???????),???????????????????????????
??? ??????????,???????????????? ?????????????,????
??????????????????,?????,???????????????????,?????
????????????,????????????103104?????????????,????
????????????????,???????????????,?????????????????
??????,????????,????????????????, ??????,????????,
???????????????
52
?????????????????????,???????????????????,????????
???????????????,????????????????????????????,?????
???,???????,??????????????????????,???????????????
???????????,??????????,??,??????????????????????(M
echanical Alloying,???MA),???????????,????? ?,????
???????? ???????????(Mechanical
milling?Mechanical grinding,??MM?MG)??????????????
,?????????????,??????????????,????????,??????? ???
??? ????????????????????????????????? ????????????
????????????? ?????????????????????????????,??????
????????,?????????????????????????????????????????
??????,???????????????????????????????????????????
????????????????????????????? ????????
53
?????(??????????)?????
??????????????????????? ????????????,????????????
???????? ???????,?????????,??????????????????
???????? ????????????????????????? ??????????????
??????????,?????????, ???????????????,????????
?,????????? ?,??????? ??????????????Ar?N2????
?????????????12(??)??????(??????),???
??????????
54
???????????????????????????????????,??????????????
??????????????????????????????????????,?????????,?
??????????????????????,?????????,?????????????????
??????????????,????????? ???????,?????????? ??,???
?????????????????????????????,?????????,??????????
???????????? ????,?????????????????????? ?????????
????????????? ??????,????????????????? ?????????
?????,?????????????????? ??????????????????,??????
???????X?? ?????????????????
55
?????????????
????????????bcc??(?Cr?Mo?W?Fe?)?hcp??(?Zr?Hf?Ru)??
?????????,?????fcc?????(?Cu)???????????3-3????bcc?
??hcp????????????????????????????,??????,?????????
??????????????????(?Fe?),??????????????? ???????