CHAPTER SEVEN

1
CHAPTER SEVEN

• MECHANOCHEMISTRY OF PULVERIZING

2
7.1 Summary of mechanochemistry of pulverizing

• ??????????????????????????????????????
• ???????????????????????????,???????(Mechanochemis
  try)?

3
??????????????19??90???
1893?,Lea???HgCl2??????Cl2??,??????????HgCl2??????
20??60??, Peter????????????????????????
?????????????????????????????
?20??80???,?????????????,?????????????????????
??,????????????????????????????????????????????
??
4
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5
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6
(No Transcript)
7
reactions induced by mechanochemistry
CaO TiO2 CaTiO3 SrO TiO2 SrTiO3 SrO
MnO2 SrMnO3 La2O3 Mn2O3 SrO MnO2
La1-xSrxMnO3 Bi2O3 V2O5 2BiVO4 Bi2O3 Sb2O5
2BiSbO4 Ca(OH)2 Al(OH)3 Ca3Al2(OH)12 Sr(OH)2
Al(OH)3 Sr3Al2(OH)12
8
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9
7.2 Mechanochemistry effects of pulverizing and
mechanism

• ????????????????(?????????????)???,???????????
• ???????????????????????????????????????????????
  

???????????????????? (1)????????????????????????
??????????????????????? (2)?????????????????????
????????????????? (3)?????????OH????????????????
??????????????????????
10
7.2.1 Comminution equilibrium
Fig.7-1 Dependence of particle size and specific
area upon comminution time
11
???? ?????????????????????????
????????? (1)???? ????????????????(van der
waals ????????)??????????????????,????????????????
?,????????,?????????????????????? (2)????????????
?????????????????????????????????????????????????
?????????,?????????
12
??????? ???????????????????????? ??????,?????
???????? ????????????????????????,?????????????
?? ?????????????????????????????,???????????????
???,???????????????
????,???????,???????????,???????????????????????
????????????? ??,?????????????,?????????????????
??????????????????
13
Fig.7-2 Relation between primary particle
and secondary particle
Fig.7-3 Theory comminution
equilibrium
14
??????????????,?????????,??????????????????????
???
Fig.7-4 Dependence of specific surface area
on grinding time
15
Fig.7-5 Ratios of mean particle diameters of
Al2O3 powder with different primary
diameters by wet and dry grinding
?0.6µm?3.9µm?22µm
16
7.2.2 Change of crystal structure

• 7.2.2.1 Lattice distortion
• ????????????????,????????,?????????????,?XRD??????
  ????????????????
• ?????????,??????,??????????,???????????????,?????,
  ???????,XRD????????????????

17
Fifg. 7-6 XRD patterns of mixture of ZnO and
Fe2O3 powder ground for different times
a0hb10hc20hd40h
18
The thickness of non-crystal layer and its mass
fraction

• ?????????????????????????????????????d,??????d,???
  ????????Yam?
• 
  (7-1)

???????????????????(???????)?
?????????SiO2?,????
2.60g/cm3?2.20g/cm3?
19
Fig.7-7 Relation of non-crystal layer and
particle size of quartz
20
?????,???????,???????????
?????,??????????????,????????????????????????????,
?????,?????????? ?????????????????????????????
??????????????
???????????7-8????????????,???????,?????????,???
??????,????????????????????????????
21
Fig.7-8 Distribution molds of activation sites
(a) Distribution in surface layer
(b) Distribution partially
(c) Uniform distribution wholly
22
??,??????????????????,????A????????????????(10-
510-7s),???????,?B????????
23
7.2.2.2 ????(Transformation)

• ????TiO2(????,???????,??3.9,????5.56.0)??????????
  ??????(????,??????,??4.24.3,?????6)?
• 300????PbO,??????,???PbO(????)????????,????PbO(???
  ?)?????
• 2CaOSiO2?Fe2O3???????????????
• ß?2CaOSiO2 ? ??2CaOSiO2
• ??Fe2O3 ? a?Fe2O3
• ????????????????,???????????????,?????350K???24h,?
  ?????????????

24
????????(???2.7,?????3)??????????????????????????(
???2.94,?????3.54)??????????450????????????.
25
???????????????? ??????????,????????????,?????
????????????????????? ?????????,???????????????
,???????????????????(??????)?????????????????????
?????????????????????????
26
7.2.2.3 Chemical changes resulted from the
mechanochemistry effect

• (1)????(Dehydration effect)
• ??????????,???????????100?,??????3/2H2O????????XRD
  ????,??15min?????????
• ?????,???495605??8451058??????560min?TG?DTA?IR?
  ?????,?????????,??????????,???????,??????????

27
???OH?????,?Ca(OH)2?Mg(OH),?OH?????,???????????,?
??? ?????SiO2?,?????????Ca(OH)2???SiO2??14h?,CH?X
RD???????,?????????Mg(OH)2?SiO2?????60min?,Mg(OH)
2?XRD????DTA???????,????????????
???????????????? ???????????????,????????,???
??????????????????????????????,??Mg(OH)2?SiO2?????
??????? SiO2??????Mg(OH)2?SiO2???????
28
(2)????(Solid phase reaction)

• ??????,???????????????????????????????????????
  ?????????????????????????????????????,???????
  (in situ reaction) ?
• ????????????????????,????????????????????????????
  ???????

29
1) ?????(Mechanical AlloyingMA)

• ????????????????????????????????????????
• ?MA??????????????????
• ?Al??????????????,??550??????,???Al/Al4C3??????,??
  ?????????????????????????????????????
• MA????AlMg???SiC?????AlCu???????????????????

30

• ????Al?Ti?????????????Al3Ti???AlTi????,??????????
  ??????????????
• ???MA???SmFeTi????????????60kOe
• ?MA?????????????,?Fe2B?TiSi2?TiB2?NiSi?WC?SiC??

???????? ???????????(SHS)??
??????????,????????
31
??????,???????????-??-???,????????????????????
?,????????????????????,?????????????????
?MA?????????????? ?????MA??,?????????????
?????????????/???????????????,???????????,????????
?????,??????????,???????????????/??????????????,??
???CuO?????????????,??????????????????????????????
???????????????
32
?????????????? ?????????????,???????????????
?? ?????????????????????????????????????,??????
?? ???????????????????? ????????????????????,
???????????????????????(?515nm),?????????????????
?????? ???????????????????????????
??????????????????????????,???????????????????????
????????MA?????????????????,??????????????????????
???? ??????????????????????????
33
2)????(Decomposition reaction)

• NaBrO3???????????
• NaBrO3 ? NaBr O2
• ?????????????
• 2NaBrO3 ? Na2O O2 Br2
• ???? MeCO3? MeO CO2(Me???????)??????????,????
  ????????????????????????????????,???????????

34
3)???? (Compounding reaction)

• ??????????????????????????????
• ???? 2CaO SiO2 ? ß?2CaOSiO2
• BaO TiO2 ? BaTiO3
• MgO SiO2 ? MgSiO3
• ???? ?
• ????????????????????
• ???? NiS H2O ? NiO H2S

35
4)????(Substitution reaction)

• ???Mg?CuO???????????,??????
• Mg CuO ? MgO Cu
• 5)????
• ??CaCO3?SiO2?????????,??????
• CaCO3 SiO2 ? CaOSiO2 CO2
• ???????,????????????????????????????????????????
  ????????
• ??????,??????????????????????

36
7.2.2.4 Mechanism of mechanochemistry reaction

• (1)????????(Friction plasma zone)
• ?????????
• ??????,????1300K??,???????????????????????,?????
  ??????,?????????,????????,???????
• ??????????,?????10-810-7s.
• ????????????7-14???

??,???????,??????????????,????????,??????????
?????????????
37
??????
????
??????
????
Fig.7-13 Scheme of energy change of activated
solid
Fig.7-12 Mold of friction plasma zone
38
Fig. 7-14 Scheme of mechanochemistry
reaction 1?????2???????3????????? 4????????
??
39
(2)????????(Thermodynamics of active state)

• ?????????????,???????????????
• ?????????????????????????,??????????????????
• ????????,????????????????????????????,??????????
  ???????,??????????????????????,???????????????????
  ?????,??????,???????????????????????????
• ??????,????????,???????????????,???????????

40
(3)??????(Proton action mould)
OH-??
??
Mg(OH)2
TiO2
H2O
MgO?TiO2?? ??MgTiO3
Fig . 7-15 The mechanochemistry reaction
mechanism of formation of MgTiO3 from Mg(OH)2and
TiO2
41
7.3 Applications of mechanochemistry

• 7.3.1 Mechanochemistry modification of powder
• ?????????????????????????????,????????????,??????
  ????
• ??????????????????.
• ????????????????????????????????,????????
• ?????,?????????????????????????????,??????????????
  ?
• ???????????????????????,???????
• ?????????????????,????????,?????????

42
??????????????????????????????????
1)????????????????????????????????????,??????,???
?,??????????????????,??????,????????????????????,?
????????????????????????????????? ??????????
1)????????????????????????,??????????????????,??
???? 2)???????????????????????????????????????
??????????????????? ?
43
7.3.1.1 ????????? (Surface modification )

• ?????????????????(phA)???????????,?5h??????,??????
  ????phA?????????phA??????????????????,????????????
  ?????
• ?????????????n??????????????,???Al2O3????????????
  ??????????,??????????????????????????????????????
• ????(PP)??????????,??????????NP7.5???????KRPS???PP
  ??????

44
??????????????????????????????????????
??????????????????,???????????,????????,?????????
????????????????,??????????????????,??????,??
????????????????????????????????????
45
7.3.1.2 ?????? (Modification by grain-grain
inclusion)

• ????????????????(????????)????(????)????????????
  ????????
• NHSO???????????????????????????,??????????(PMMA)(
  0.4µm)?????12(5.0µm)????(5.0µm)????
  SiO2(0.6µm)??????(212µm)??????????????

46
??????????? (1)???????????? (2)??????????????
????? (3)???????????? (4)????????,??????????? (
5)?????????????????
????????????????????????????????????????????,?
????????????????????????????????????????,?????????
???????????????,??????????????,???????????????????
?????????????????? ?
47
7.3.1.3 ?????????(Grafting modification)

• ???????????????,?????????????????????????????????
  ??,?????????????????????????
• ???????????????????????????????????????????,??????
  ??????????
• ?????????????,???????????????,???????????????????
  ,??????????????

48
?????????? (1)??? ???????????????????,?????,??
??????????,?????????,?????????????????????????????
??????,?????,?????? (2)?????????
???????????,?????????????????????????,????????????
???????,???????????????,?? 1)???????,????????,??
??????????????,????????? 2)???????????,????????,
????????????????
49
3)??????????????????????? 4)????????????,????
?????????????
(3)????????????? ??????,???,????????????????????
?????,??????????????,??????????????????????,?????
?????? ??,???????????????
50
7.3.2 ???????????????? ????? (Preparing
nano-metal, non-crystal metals and alloys by
mechanochemistry method)

• ????????????????
• ??MA(Mechanical Alloying)?????????????????????????
  ???
• MA???20??60????INCO?Benjamin??????????????????????
  ??????
• ???????,?????????????????????????????????????,????
  ????????????????????????????,???????????????,?????
  ???????,???????????

51

• ??20??80????,MA??????????????1981?,Yermakov???Y
  Co3?Y2Co3?YCo5??????????????????????????,Koch???MA
  ?????Ni60Nb40?????????????MA????????????
• ??,MA????????????????,?????????????,????????????
  ??,????????,???????? ?

52
7.3.2.1 MA?????????(Synthesis dispersing
strengthen alloys by MA)

• ?????????????????????????????,?????????????????Ni?
  ????
• ???AlMg??????????450MPa,????13,?????76Gpa,??????
  ??????910-6m
• ???Al/SiC(p)??????????AlMg???6061Al???2.43??2.82?
  
• ???????????????Cu??????MA??,?????????????????Cu???
  ,?????????????????Cu???,?CuMo?Cu/Al2O3?Cu/ZrO2??C
  u/ZrO2?????,ZrO2?????2050nm,??????100nm??????????
  ?????????????,????????????,????????

53
7.3.2.2 ??????? (Preparing materials with
meta-stable state )

• (1)??????? (noncrystalline state materials)
• ?????????????(Rapid SettingRS)????????,???????,??
  ????????????????,??????????,RS????????????????????
  ???,?????
• MA???????,?????????,??????????????????????

54
MA??????

• 1)?????????
• 2)?????????????????3)????????????????
• 4)?????????????????
• 5)????????????????,????????????????
• 6)???????????????????

55
(2)????????(Super-saturation solid solution)
??????????,????????????,???MA????????,??????????Fe
Cu?AgCu?????????,??????????MA?????????????
1)??????????????(????) 2)???????,??????,???????
?????,???????????????,XRD??????????????????,??????
??????????????
56
7.3.2.3 MA???????(Preparing nano-crystalline
materials by MA)

• 1988?,Shingu???????????????AlFe?????,????????????
  ?????????????,?????MA???????????,?????????????????
  ?????????????????????????

57
7.3.2.4 MA?????????(To prepare intermetallic
compounds by MA)

• NiAl?TiAl?FeAl?NbAl??????????,?????????????,??
  ?????????????,???????????,??????,????????????MA???
  ??????,????????,????????,?????????????,MA?????????
  ?????,??????????
• Dymek?MA????????NiAl??,???????????1380MPa,?????gt11
  .5????NiAl???????????400MPa,?????2.3?

58
MA????(??????????) (1)?????? (2)???????? (3)???
???????????,????????????????????????????? (4)????
??
59
7.3.3 ???????????? To prepare new materials by
mechanochemistry method

• 7.3.3.1 ??????(Nano-ceramics)
• Li???(Li0.5Fe2.5O4)???????????????????????,??????
  ??????
• ????????Li????,????1000???????????Li?????,??????Li
  ?????????
• ?Li2CO3?aFe2O3???,????130h?,???????30nm?Li0.5Fe2.
  5O4???,??????600???????,????????Li0.5Fe2.5O4?

60
?aFe2O3?ZnO?????,????????70h?,???????????????
aFe2O3(s) ZnO(s) ? ZnFe2O4(s)
???????,?????10nm??,??????800?????????
BaTiO3?????????????????????????
???????TiO2?BaCO3????????????,?????,??????
?????CaTiO3??????????????????????????,???????,???
?,???????
61
?Ba(OH)28H2O????TiO2?Ba/Ti1??,?????????3h???Ba
TiO3????700???3h??????BaTiO3????1200???1h?????????
?????94??BaO?TiO2???????,?????????????BaTiO3?????
??5h????BaTiO3,15h?????BaTiO3??????2030nm?
CaTiO3????????????????,??????????????????????TiO2?
CaO????????????????? ? ??? ? ????
????0.20.5h?,????????????25h?,TiO2?CaO????CaTiO3
?CaTiO3??????20nm ?
62
????????PZN(Pb(Zn1/3Nb2/3)O3)
??????????PbO?ZnO?Nb2O5?ZnNb2O6?PbO?????????????48
h,?????????????,???????????????
????20h,???????????PZN????,?????1015nm?
63
7.3.3.2 ?????? (To prepare functional
materials)

• (1)??????(Biology ceramics)
• ß????(ßTCP)???????????,??????,?????????????????
  ??
• ßTCP???????
• ??????????????????????????ßTCP,?????(1000?,24h),
  ?????
• ?????????????????ßTCP????????????
• ???????????????????,?????ßTCP???1h?,?700????1h,
  ßTCP????????0.38µm??????24.9m2/g?

64
(2)????????(FCM) MA/???????(MA/PS)??FSZ/TiAl?????
?????????,25FSZ/TiAl(FSZ?Fully Stablized
ZrO2)??????Hv1016? (3)??????(Super-conducting
materials) ?Cu?Ba?Yi??????????,??????????????,???
??????????????? (4)????????(Shape remembering
alloys) ?Ni??Ti??11??????MA??,??????????????,??
?????????,???????5?,?373K???????????gt300MPa,?????
????????
65
(5)??????(Magnetic materials) ?MA????NdFeB???????
????????1600kA/m,????????,???????????????????
?MA????SmFe?????,??ThMn12V?????SmFeV?????944kA/m?
?PuNi2???Se?Fe?Zr?????1184kA/m?Se?Fe?Ti???????512
0kA/m?
66
7.3.3.3 ????????(Nano-composite)

• ??Fe??????????(PTFE)?????,??????101??,???????????
  ?????/????????????HRTEM????,???????????,?????????8
  nm?
• ?Fe3O4?????????(PVC)???????,??a?Fe3O4/????????(??1
  0nm,????)?
• ?Ni?Al?Ti?C???Ni50Al50 10Ti50C50????????,??????
  ???????????NiAl?TiC????(NiAl????lt10nm).

67
?Ti??B4C?31??????????????30h?,?????TiB2/TiC???
????8nm?TiC????????????10020nm?TiB2??
????????????????????????????????????????,?????????
????,???????,???????????????????????????
68
7.3.3.4 ?????? (Storing hydrogen materials)

• ???????(SWNTs)??????????????????,??10min?Li???????
  ???SWNTs?Li1.7C6???Li2.7C6??????Li3.2C6???Li1.3C6
  ?SEM?Raman Spectrum?XRD????,?????????????????????
• ?????????TiFe?TiFe2?Ti, TiFe??????????TiFe2??????
  ????TiFeHx?TiH1.924?Fe?????
• ???????????NiSi????,?????????,????????????1180mAh/
  g?

69
?Mg?????????????????????Mg/C??????????0.067MPa?
H2???,Mg??????????????MgH2,?453K???15h?,Mg?????H/M
g???1.5? ??CoFe3Sb12???????????
CoFe3Sb12??????Sb?????????????,??????Li3Sb?CoFe3Sb
12???20mA/g?????????????396mAh/g?
???????????50????,?100mA/g??????,????????380mAh/g
,????????????
70
7.3.4 ??????????????????(Application of
mechanochemistry in production of cement and
concrete)

• 7.3.4.1 ????????????(Adding grinding aids to
  increasing fineness of cement)
• ???????,????????,????????????,????????,??????,????
  ????,?????????????????????
• ??????,?????????????????,??????,???????,??????????
  ????????
• 1930?Goddard?????????????????

71
?7-1 ??????????
72
???????? (1)???????????????,??????????,????????
????? (2)?????????????,?????????,???????????
(3)???????????????,????????,??????????
?????????? (1)??????(?????)????????,????????????,
?????????????? (2)?????????????????????,?????????
????????,????????? (3)???????,??????????????,????
??????????????????
73
7.3.4.2 ???????????? (Activation of clinker
compounds and mixing materials)

• ??1350????????????????170h???????????????????????
  ?????,??????????????,????????????????????????,???
  ?,????????,?????????????
• ??????????????????????,??????????????????,????????
  ?????????????????????????????????????????????

74
????????400m2/kg,??300m2/kg,??????6065?????425
??????????????400m2/kg,??350m2/kg?,??????60?????5
25R????? ???????????5h,?????1µm??,??????????????
????????????3d?7d?????4?? ???????????????????????
?,??????????????????????,?525???????????????70?4
25???????????45?425R??????
75
7.3.4.3 ??????? (Synthesis of silicate
compounds)

• ????Ca/Si????1.5???????????????????2h(????0.230.3
  )?????Ca/Si????0.53,????0.8?,??3h?????????
• ??????????????????????C2S???5h??873K??????C2S,????
  ??????
• ??1350?????????????????1h?30h,??30h???7d???????1h?
  14??
• ??????3CaOAl2O3CaSO4??Ca(OH)2????Al(OH)3????????
  ??120min,??AFt,?????773K????3CaOAl2O3CaSO4,?????
  ?????????????
• ????????,????800K??????????????????????????????

76
7.3.4.4 ???????????????? (Reutilization of waste
concrete by mechanochemistry activation)

• ??????????????????????,????????????,??????????
• ??????????????,???????????????????????,???????????
  ????????????
• ??????????????????????????????????????????????,???
  ???????????

• ??????????

77
???????? (1)????????,????????,??????,???????,???
?????????????? (2)????????????,??????????????????
,???????????????? (3)????????????????????? (4)??
???????????????? ?? (1)???????,?????,????????????
,?????????????????????? (2)????????????????,?????
?????? (3)?????????????????,??,??????????????????
?
78
7.4 ?????? (High energy ball milling technology)

• 7.4.1 ??????(Equipments of High energy ball
  milling )
• ?????????????
• 7.4.1.1 ?????? (Structure of planetary mill)
• ?????????????????????????

?????????????????????????????(????????)???
???????????????????,??????????
79
???
???
??
????
??????
Fig. 7-16 Schematic of structure of planetary mill
80
Differences between planetary mill and ordinary
ball mill (1)???? ??????,????????????????????????
(2)?????? ??????????????,???????????????????????
(3)?????? ??????????????,????????????????????(?
???)??????????(????)????????????????,??????????,
???????? ?????????????????????????
81
7.4.1.2 Work principle of planetary mill
Fig.7-17 Force analysis of grinding media

• ????????O1??,???????r???????????????O????R?????,?
  ??????R??r??R??????

82
???????m,?????r,?m???F? FGR Gr Gk
mLd?r/dr (7-2) ??,GRm?R2L??????????
Grm?r2r?????????? Gk2m?R?r?????????????????
mLd?r/dr??????????,?R???,?????
?????????????????????????????,????????????????????
????,??????????? ???????????????????(??)???????10
g20g??????,??????,????????????????????56????,??
???????????????

83
7.4.2 Factors effecting high energy ball milling
and mechanochemistry action

• ???????????????????????????????????
• (1)Performances of raw materials
• ??????????????????????????????????
• ?MO(M???????)??Si???????MOSi2???,?MO?Si?????????,?
  ?14h?,???????15min???????,?????aMOSi2,???Si??MO??
  ?,????????,????????aMOSi2?,??ßMOSi2

84
(2)Strength of ball milling ????????????????????
??????????????????????????????????
??????????????????????? ????,???????????,???????
? ?????,??????????,?????????????,??????????????
????????? ??????????????????????????????????????
??????,???????,????,???????????????????????,??????
???????
85
(3)Fnvironment of ball milling
??????,?????????????????????????????????,?????,???
??????100h???????????????,???????????????????,???
???????????????????????????????
??????????????????????,???????????,??????????????
????????????????????(??)???????????,?????????,????
??????????????????????????????????,?????????????

86
(4)Atmosphere of ball milling ?????MA????????????
???????????Ar?N2?,???????,?????MA??,????????,????
???????????? ??????????????????????NH3?N2????Si?,
??Si???NH3???????????????????Ar????,N2??????Si3N4?
?,?NH3??????Si3N4???N2?????,????Si3N4??,?NH3?????
???????Si3N4???? ???NH3?????,Si??????N2?????????
??,????????N????Si3N4????
87
(5)Sizes of grinding media and ball/material
ratio ?????????????????????,??lt10mm(????????????
????????)? ????1030?????????????,??????????????
?? ??????,?????????? ??????,??????????,????????
???,???????????????
88
(6)Ball milling time and temperature
????????????????? ???????,MA???????????????????,?
?????????????????????????????????????????
?????????,??????????????????? ??????????????????
????????,???????????,????????????????????????????,
????????,??????????????????,????????????350K?
89
?? ????????,???????????????????????????????????
??????,??????????????,????????????????????????????
??????????????????????????????????????????????????
??????????????????????????????????????????????????
???????,??????????????,???????????????????????????
???????????????????????????,??????????????????????
???
90
END
THANKS!
91
?7??????

• 1?????????????????????????????????
• 2??????????????????????
• 3??????????(????)
• 4???????????
• 5??????????(??????)?