花岗岩硅烷偶联剂水泥浆界面层的形成机理 (1)
- 1. 21 2 ¶ Æ ¾ ¨ Vol.21 No.2
2007 4 Å CHINESE JOURNAL OF MATERIALS RESEARCH April 2 0 0 7
/ ÍÅ / Ì ÀÊ·» ¸ Ä ∗
Ý Þ¼ © «º Ù ¼ß ÚÜ
Û
Õ Ñ Ï ± ÂËÍ Ç ÖÛ Ú¤¢ À ºÕ Ê¢ ÅÎ Î ± ¨
( 515063)
(SCA) , (FTIR) ÃXÒ
(XPS) ¼
SCA ¤ . , SCA Ç, Ä
ªªÇ ± ± ½ ¡Ò½ º ¤ Óä߳ ÖÓ Û± Ç
¹ ËÖª²¥·
. /SCA/ , SCA
À¼
¿Â ×°
.
± ± ½ ÖË
, , , /SCA/ ,
TU528 1005-3093(2007)02-0140-05
Forming mechanism of granite/silane coupling agent/cement
paste interface
LI Yili LU Xiaohua FENG Yulong XIONG Guangjing∗∗
(Department of Civil Engineering, Shantou University, Shantou 515063)
* Supported by National Natural Science Foundation of China No.50278050.
Manuscript received June 19, 2006; in revised form August 30, 2006.
** To whom correspondence should be addressed, Tel:(0754)2902989, E–mail:gjxiong@stu.edu.cn
ABSTRACT The mechanisms that the bond strength between aggregates and cement paste could
be significantly increased by modifying the aggregate surfaces with silane coupling agent (SCA) were
analysed. The formation and the influencing factors of granite/SCA interface were investigated using
spectrophotometry, contact angle measurement, FTIR and XPS. The results revealed that strong bonds,
including chemical bonds, formed on the modified granite surfaces. The interface transition zone (ITZ)
benefits from the existence of the uncondensed silanetriols and the distributed organofunctional network.
KEY WORDS inorganic non–metallic materials, concrete, silane coupling agent, granite/SCA/cement
paste interfacial layer, bond mechanism
Æ É
40%[1] ; C50 Ø Ý²
Æ
¶ m3 , Ã Ø
¾¸ ,
15 ¨ Â Ø.
ß (SCA) « ¯ Ì
« ¯´
د Ô »
£
90% ²
»× Ú¾¸
[3,4]
.
[2]
. ƾ £,
«
»Ú µ
É
0.35),
û¨£ Û ß. Û ¼ [8] É
KH–570 SCA Ë
»¶Å Ø«
È « ¯ («
«
« Þ «¦, Ò µ« Ï « ¯ (« 0.25) £ÂÉ
»·´Ï Ï Â ÕÏ , Ô » × ÒÓ Í£±² 25.9%  44.7%; ³
Ì
[5∼7]
. « ¯´
É« ¯Ùµ¡§«ßÑÆÝ ÁÌ¿Â , ÑÉ
« « ¯Ñ Å ¯ ,
£ » , ɱ SCA
KH–570 SCA Ë
Ū Ø« « ¯/
/« ¯
È « ¯,
», É
»ÂÆÝ «
²§Õ «¦ Ø, Ê § » ·´ ¯/ »±² 121.4%  51.2%[9]. ÃØ
ª ¤ » Ø Ý [10∼13]
SCA ,
* Æ ªÓ² 50278050 ÐÆ. SCA ÊÔ Â Ô Ñ ¦, É Ã ß
20066 Æ 19 Ê ´; 2006 8 Æ 30 Ê £ ´. « ¶Å Ø É ²ÃØ ß« ² [14] .
Ç È: ¢ ¸, ¢ SCA ºÑ ÔÜÂÊÔÜ, ÔÜ Ô
- 2. 2 Ì´ : ° / ¬ ° ¼ ß ÕÊ
/ 141
Å, ÊÔÜ ÊÔ Å, Ê . « É Ã (à 20 £) 60 £ 120 £ µÎ 100 mL
Š« ¯×ÚÊÔÌ, SCA Ø 1% SCA Ë Ù, ¦¾ 20 min À , É
À , Æƾ /SCA/« ¯ ÔÃØ Ê (Æ C1 É Ã 24 h ). Éß
¾½
» Þ ÔÉ. ¸ º ¡ 8 Ñ« (ßµ ´× 1 μL), ¸
£ OCA 20 Þ¹ ¨ ¹Ô ¹Ô
³Ç¶
1
, À 16 µ¨ ¼ .
1.1 À ƨ 20 g ³ ©§Â¦
Ó § ߸ ( 80 mm Ì (FTIR) Ó , ¼ « 4 ( 1),
× 25 mm × 2.5 mm) Â
0.3 mm), SCA (KH–570)(« Õ
CCH3 COO(CH2 )3 Si(OCH3 )3 , ¨¥
ƨ ( Ø
¦
CH2 ¨
γ– ¢Ò
ß D0 , ß D1 D2 D3, « É
à (à 20 £) 60 £ 120 £ µÎ 100 mL Ø
1% SCA Ë ¦¾ 20 min, ¹±Ä¦ Ö
Ò Ò ¢ Ò , ¨¸Õ¦Ú RSiX3 , É 60 £Ê 0.5 h Ñ Ë, Nicolet Nexus 870 FTIR
Ù R £« ÔÒ , X « Ò ), Ê«± (´ MCT–B ¥¹ ) ¹ß½ .
Ä ( ¨Å), 36% ± («ÎÅ), Ñ«, SCA Ë
Ðκإ ¨« µÆØ
(× «¨ 0.1%  1%)[10,13,15] .
, ºÑ¹ Å SCA Ë
VG Multilab 2000 X
½
Ð
.
¦
¹Ô
¢
¸ ¥ ¦
1.2 ¨ , ÄÔ¶ ¨
Ë Ø °ÔɱºÃض«
,
ƨ ²Ú Å Ø. ¼ 5 ß« ( 1).
Ó ¹
SCA Å
(UV–vis)
¦
1),
Ú
Å
Á ¨ »±º ½
. Æ À ߸
20 mm×25 mm×2.5 mm.
4À(
»Ð
ß
À 250 mL Ø 0.1%( Ø ²Ñ±Ï « Ø E0 , À ß E1 E2 E3 , « É Ã (Ã
¥¹) SCA Ë , « 5 , ¶¡Î 5 g 20 £) £
60 120 £ µÎ 100 mL Ø 1%
ƨ, « É Ã (à 20 £) 40 60 90  120 SCA Ë ¦¾ 20 min, À ±Ä 1 h, É
£ ¦¾ 20 min, Ö Ö A0 A1 A2 A3 à 24 h , ³ XPS ¹ß. ¸ Ô Æ¨
 A4 ¶ 50 mL  ¾ Æ; Æ 5 ÆÊ ß D1 D2 D3 º ¨£, Ô ß F1 F2 F3 ,
(101–0 ÝÐÇ¿ Ë ) « © 50 mL ± ȳ XPS ¹ß. ³ ´¹ß SCA É
Ä/« (´× 95 : 5) Ù, Ó Ç «Ô (JS–3A Ý Å Ç Ø, Æ §°¹¹ß F1 F2 Á
ÔÑÈÃÇ « ) « À 20 min, ÈÉ Ö ºÈ« ©Î±Ä/« (´× 1 : 1) Ë ÙÓ
(SHE–3 « « ( Ö )) Ö B0 Ç «Ô à « À 10 h, ¹±Ä Ö, É
B1 2 3 Â B4 ¶ 50 mL. Æ A
B B
« ÈÜ (80–2 ÝÐÖÈÜÔ), À » ,
– ¨«
ÂB Ö
Ø Agilent 8453 ¹ É λ=226
¥ 60 £Ê , Èɳ XPS ¹ß (
Æ F11 F21 Á º« ©Î±Ä/« (´× 1 : 1)
Ë Ù¹ 100 £ « À 10 h, ¹±Ä Ö, É
F11 21 ); È
F
nm Á ( ) Ø. 60 £Ê , ³ XPS ¹ß ( F12 22 ). Ó ²
F
À¯À ߸ ( 1) ³ Ï Ó , Æ MgKα X Â, ² C1s( Å 284.6 eV)
ß C0 , Æ À ( ß C1 C2 C3 ) × Å .
² 1 SCA ° °
Table 1 Grouping of the test specimens
¬
Method
Unmodified SCA modification reaction temperature/ ¤
granite r.t. (∼20) 40 60 90 120
UV–vis A0 B0 A1 B1 A2 B2 A3 B3 A4 B4
Wettability C0 C1 C2 C3
FTIR–ATR D0 D1 D2 D3
XPS E0 E1 E2 E3
F1 F2 F3
F11 F21
F12 F22
- 3. ¶ Æ ¾ ¨
ÔÈ
142 21
¾2 Å ß ´ Ì ½
Ô ±Éº ÏÓ µÒ
,
2
É 2950 1455(CH3), 2840(CH2), 1720(C ¨
2.1 SCA O), 1640(C ¨ C), 1160(C—O), 1090 Â 1010 cm−1
Ö
¾ ·
£ÁÉÃØ ²Ø߬
¹ß
1
SCA Ö
UV–vis
.
A B
,
(Si—O). ¾ 3
D0 ß , D1 2 3
ƨ¦ Ì
1720 1455
.
1160 Â
¯ Ø
D D
A Ø߬ ÜË Ù , SCA 1086 cm−1 ¤ SCA , £É±º
Ä º
߬
.
; £ÃØ ² Ö
£ ÃØIJ
£ ÃØIJ .
,
±
,
,
,
,
, B
SCA ÃØ , SCA
£
Ú SCA É 1090 cm Á Ñ °¨¨Ñ Ö,
−1
·Á Û ¨© Si—O—Si . Ú É Ì
Þ Ç Å.
Ä/«Ë À SCA Ä , ܲ ¨  ¨ Ó, É Ã SCA Þ ¨
©ÞÕ Å ±³ À SCA Ä . A Ö © Å, ÏÉ ² Á
Ü
£: ¹
²ªÜÞÕ
µ± SCA Ë
¹ÔÍ ×: Ź²ÃÁÉ ´ß Ù
Ø ,
µ« SCA; B Ö ¯ SCA, Û Si—O—Si .
2 ¨, SCA «
ß« ¨
SCA, Ú Ä/« SCA ç .
Æ£, ɲ澶« Þ ¨ Â
¨©. ÊÚ SCA ÄÜÞÕ Å, Ð
SCA Ä , Ï ÆÄ . »È, ¹
ß±ºÃض« ¹ SCA «
,Ü Å SCA
. ß C0 1 2 Â C3
C C « 84.0◦
86.4◦ 92.9◦ Â 93.8◦. £, SCA Ô ÃØÄ
², « Ä , Æ£
.Ü
Ï , È Ò§ .
£
Ï ( « ) ¦¾ÃØ ² ߬
ÃØ ², SCA Ï¡, ÔÒ R 2 Æ Í ¿
Fig.2 FTIR spectrum of pure SCA
1 × ¡ Ú SCA
A B ÄÙ 3 ° ¯© Í ¿
Fig.1 Relationship between relative SCA contents Fig.3 FTIR–ATR spectra of granite powders before
and temperatures and after modification by SCA solution
² 2 SCA ¬
Table 2 Elementary binding energy before and after modification by SCA solution/eV
Æ
E0 E1 E2 E3 F1 F11 F12 F2 F21 F22 F3
Si2p 102.62 102.81 102.80 102.92 102.81 102.82 102.74 102.93 102.80 102.80 102.85
O1s 532.04 532.06 532.14 532.08 532.13 532.0 532.08 532.13 532.0 532.0 532.08
- 4. 2 Ì´ : ° / /¬ ° ¼ ß ÕÊ 143
 ,
Si—OH © ¡
 à 0.3 eV. ƣ,
Si—O—Si ©, Ó Ã
¥ «¦, §Õ Û « , Ï Û
Ø; ¡Ú « Ò º« « ¯ Ç
SCA Ü
¢»  צ ,
Þ ¨©. ¸
Si
O C
¦ ¦ ¨©. »È¦¾ÃØÂÑ£ ÔÚ
À Ý » .
Ë É¶Ö ¼ º
± , C
Si2p ÁÉ
¦
µ¨ 1 : 2.25 : 0.63, Si
¨Ï¡Ã 3 ; Ñ£
¨Â , C µ¨ ,
O µ¨
¦ ±
à 2.2
SCA
/SCA/
« , ±ÚÃز ,
. ×±Ï « ¯ . Ú° ƾ £,
¾4 ß E0  E1 XPS Å ¾. É Ã /SCA/« ¯ » Šز
ß E0, ß E1 É C1s 288.6 eV Þ SCA Â [8,9,14]
. ¸ ÆÓ «
Ò . ¬Ã¹ Ñ£
( Î /SCA/« ¯ Þ ÔÉ: (1)
)ß º Ò . Ó Ò SCA « Ò «Þ Si—O—
SCA £ ¨ © , ÜÔÉ ²Ã Si ©; (2)SCA È Ò £ ² « Ì,
Ø Ñ£ ±Á. ¦¾ÃØIJ Ñ£Ä , ÌÄ , R Ò Ä ,
É C1s 288.6 eV Ò Â Si2p Á SCA Ù È ÒÄ , «
¨Â Ó, SCA ÄÉ Þ Ä¾; (3)SCA È Ò º« « Ù
¨©Å. ¨©Þ ÔÉ : KH–570 ÉÄ«Ë Ù
« ¦¾ Ä, ÄÙ Si–OH ©±ÈÔ,
¨ Ò «Þ « ¦
Ò «Þ Si—O—Si ©; (4) À
« ²,
«« ¦© ¦
«
, Ô
¯Ù«
Si—O—Si ©, ¨ ´£ Ò Å »«¦, ÒÔ« « ÙÉ
Þ ´ . É ²ÃØ
[9,10]
Ñ£ µ±, Î £ Ì ¥ Â ·´ [9] , Ê
³ SCA Ù ¢ µ« « , ºÑ¡ » Ø. «
Ò £Â Ò £ «, Ê É « ¾ Õ, «¦ Æ, £Þ«
Þ £«», Ô «
· Ú, ÜÔÉÝö« , SCA º
.
Si ¥ O ¥ Si ¨©; ɦ¾ÃØ
² £«Ò R ÏÉ
«¦, £
» ½Ò , Æ [9]
·´É
Ó
, Ê Ô
¥
;
Ñ SCA « Ø , ´£ Ò Å (5) Ì SCA ¦¾ Ø (Ñ£ Ã
± Â, È Si ¥ OH , ɲ澶« Ø ²), Í SCA È Ò§ , « ¯ ¨
À « . £, É ¦¾ÃØ © Å § . « Ô« ²
² ¢Ú « Ò£« R Ò £Þ«
½.
« ¯ Å ªÝ·¹, Ú£«Ò §Õ
ºÑÏÉ «Â£«Ò º
½
¥«¦Ñ Ø
, ¹³É
ÕÏ¡, Šئ . ÊË ¨ß
« , Ò
Þ Ï
·´Ï ,
« ¯ « ¾ , Ê Ù [14]
.
Æ [10, 16–19] £, Ò
Ca Al ÅÌ « ©. Æ£, À À
Ø , ¶ È ÒÏÉ, Ü
SCA Ø §ÌÅÜ ÃØÂÑ£.
È
,
3
ÉÝò SCA
1.
« ¯ » / ½, /« ¯
»ÏÉ SCA Ó ¨© Å,
» Å ØÂ » ÓØ Ð ±².
4 C1s Ñ §Æ
Fig.4 C1s electronic bonding energy
2. SCA Ø À
ÏÉ À Å Ä Ò£ޫ² ÔÒ .
SCA ¾ÉÝà Ø ݦ¾Ñ£ ¶«
Ú
- 5. 144 ¶ Æ ¾ ¨ 21
³
´Á
. 11 Yang Rui, Liu Yujuan, Wang Kunhua, Yujian, Charac-
terization of surface interaction of inorganic fillers with
silane coupling agents, Journal of Analytical and Applied
Pyrolysis, 70, 413(2003)
1 YAN Peiyu, XING Feng, Investigation into the Materi- 12 M.E.Connell, W.M.Cross, T.G.Snyder, R.M.Winter,
als of Structure Engineering Following the Principle of J.J.Kellar, Direct monitoring of silane/epoxy interphase
Sustainable Development, in: The Strategic Development chemistry, Composites Part A, 29A, 495(1998)
Seminar of Architecture, Environment and Civil Engineer- 13 Akihiko Kondo, Takafumi Urabe, Kohiji Yoshinaga, Ad-
ª
ing, N.S.F.C., 2004, (12), 178–179
³ , , ¬ ¦¢ ÀÎ ¾» · ¯¿,
sorption activity and conformation of–amylase on various
(
¢ ¼ ¬» ª ¢ د , Æ ªÓ²
ultrafine silica particles modified with polymer silane cou-
Á , 2004, (12)p.178 ¦ 179
pling agents, Colloids and Surfaces A: Physicochemical
and Engineering Aspects, 109, 129(1996)
2 ZHAO Xiaolong, BA Hengjing, Preparation technology of 14 LI Yili, XIONG Guangjing, LI Yiqiang, Influence of
high duribility concrete with ordinary strength, Architec- temperature and immersing period on splitting tensile
ture Technology, 35(1), 26(2004) strength of granite/silane coupling agent /cement paste in-
( ÓÓ, ©Éº, ¿¹ Ú³ ¡ µÕÞ¦, Þ terface, Building Technique Development, 33(1), 34(2006)
¦, 35(1), 26(2004)) ͵ , ¢ ¸, ͸ , ÅÚö²Ò¤ ± / /
(
3 P.K.Mehta, P.J.M.Monteiro, Concrete Microstructure, ± ½·Æ Ú , Þ¦ ¢, 33(1), 34(2006))
15 XU Yi, TANG Shouyuan, TENG Yi, ZHANG Xiaofeng,
Properties, and Materials, 3rd ed. (New York, McGraw
Hydrolysis and condensation of silane agent for metal-
Hill, 2006) p.41∼46
lic surface treatmen, Journal of Chongqing University,
4 B.Dannys, B.Gerard, G.Jacques, Contribution to the For-
25(10), 72(2002)
mation mechanism of the transition zone between rock–
¤ º, ¡ , ¸, Ô , ²¥ ÂË
(
,Þ ªª , 25(10), 72(2002))
cement pastes, Concrete and Cement Research, 23(3),
335(1993)
16 HUANG Congyun, LONG Shizong, Action mechanism
5 J.C.MASO, The bond between aggregates and hydrated of coupling agent and polymer in sulphoaluminate–MDF
cement pastes, in: Proceedings of 7th International cement, Chinese Journal of Materials Research, 8(2),
Congress on the Chemistry of Cement ,Vol. 3 (Paris, Edi- 158(1994)
tions Septima, 1980), p.VII–1/3–VII–1/15 ( ËÇ, ÓÙ , KH Ã ÇÍ PVA ÊÐÔ ¦
6 R.Zimbelman, Contribution of cement–aggregate bond, MDF Û , ÖË · ¯¿ª , 8(2), 158(1994))
Cement and Concrete Research, 15(5), 801(1985) 17 ZENG Zhiqiang, XIAO Xiaoyue, GUI Zhilun, LI Longtu,
7 J.C.MASO, B.Bourdette, Interfacial transition zone in Surface grafting of coupling agents on the Al2 O3 –SiO2 –
concrete, Advanced Cement Based Materials, 2(1), TiO2 membranes, Chinese Journal of Materials Research,
13(2), 125(1999)
Ö , ÒÖÆ, ØÙ, ÍÓ , Al O –SiO –TiO ¯§
30(1995)
( 2 3 2 2
8 MA Yiping, Study on increasing of interfacial bond
strength between cement paste and aggregate, Journal of
¡– §¿, · ¯¿ª , 13(2), 125(1999))
18 Y.W.Leong, M.B.Abu Bakar, Z.A.Mohd Ishak, A.Ariffin,
Building Materials, 2(1), 29(1999)
Ü ½, ²³ Ц٠±
( Ú ¯¿, · ª Effects of filler treatments on the mechanical, flow, ther-
mal, and morphological properties of talc and calcium car-
, 2(1), 29(1999))
bonate filled polypropylene hybrid composites, Journal of
9 Xiong Guangjing, Luo Baiyun, Wu Xiang, Li Gengying, Applied Polymer Science, 98, 413(2005)
Chen Liqiang, Influence of silane coupling agent on quality 19 LIU Tiejun, OU Jinping, LI Jiahe, Effects of silane–
of interfacial transition zone between concrete substrate treated silica fume on damping property of cement mor-
and repair materials, Cement & Concrete Composites, 28, tar, Journal of the Chinese Ceramic Society, 31(11),
97(2006) 1125(2003)
10 E.P.Plueddemann, Silane Coupling Agent, 1st ed. (New Ò·
( , ´», Í Ã, ¡
York, Plenum Press, 1982) p.19, p.49∼52, p.128∼130 , ª , 31(11), 1125(2003))