Effective Use of Mesoporous Silica Filler

DOI:10.1002/ejic.201301615

Effective Use of Mesoporous Silica Filler:Comparative Study on Thermal Stability and Transparency of Silicone Rubbers Loaded with Various Kinds of Silica Particles Norihiro Suzuki,[a]Yuichiro Kamachi,[b]Kimiko Takai,[b] Shosuke Kiba,[c]Yoshio Sakka,[d]Nobuyoshi Miyamoto,[e]and Yusuke Yamauchi*[b,f,g]

Keywords:Silicone/Mesoporous materials/Nanoparticles/Silicone rubber/Polymers

Four types of silica fillers(nonporous silica particles,mesopo-rous silica particles,silica gels with micropores,and fumed silica particles)have been used as inorganic filler materials for silicone rubber.To determine their effectiveness as filler materials,a systematic study on the thermal strength and transparency of the obtained silica/silicone composites was conducted.The mesoporous silica/silicone composite shows the lowest thermal expansion and higher transparency than 1.Introduction

Owing to the siloxane bond(Si–O–Si)backbone being stronger than the C–C bond backbone of other organic rubbers,silicone rubber can withstand severe conditions such as high temperature,UV irradiation,and ozone expo-sure,whereas other organic rubber cannot bear these condi-tions.In addition,silicone rubber is chemically stable and has a high biocompatibility.Therefore,silicone rubber has been widely used in various fields,from the aerospace in-dustry to the medical research field.Among the various characteristics of silicone rubber,we have focused on its transparency and flexibility with a view to its application in electrical devices such as light-emitting diode(LED)covers, [a]International Center for Y oung Scientists(ICYS),National

Institute for Materials Science(NIMS),

1-2-1Sengen,Tsukuba,Ibaraki305-0047,Japan

[b]World Premier International(WPI)Research Center for

Materials Nanoarchitectonics(MANA),National Institute for Materials Science(NIMS),

1-1Namiki,Tsukuba,Ibaraki305-0044,Japan

E-mail:Yamauchi.Yusuke@nims.go.jp

https://www.wendangku.net/doc/387756238.html,

[c]Toyota Tsusho Corporation,

2-3-13Konan,Minato,Tokyo108-8208,Japan

[d]Materials Processing Unit,National Institute for Materials

Science,

1-2-1Sengen,Tsukuba,Ibaraki305-0047,Japan

[e]Department of Life,Environment and Materials Science,

Fukuoka Institute of Technology,

3-30-1,Wajiro-Higashi,Higashi-ku,Fukuoka811-0295,Japan [f]Faculty of Science and Engineering,Waseda University,

3-4-1Okubo,Shinjuku,Tokyo169-8555,Japan

[g]Precursory Research for Embryonic Science and Technology

(PRESTO),Japan Science and

Technology Agency(JST),

2-1Hirosawa,Wako,Saitama351-0198,Japan the other composites.The thermal strength and transparency of silica gel/silicone composite is quite similar to those of nonporous silica/silicone composite.Fumed silica/silicone composite is highly transparent(indeed,its transparency is the same as pristine silicone),but the thermal strength is at the same level as nonporous silica/silicone composite.These results clarify that mesoporous silica particles are the most promising filler materials for silicone rubber.

light guide films,and optical fibers.Because of the recent trend toward miniaturization and multifunctionalization in the electrical device field,the demand for application in working conditions is growing.Therefore,we have to study the use of silicone rubber at higher temperatures than ever.

In general,nanotubes and nanosheets have been used as inorganic fillers.This is a common way to enhance the strength of polymers.Indeed,several studies have been re-ported on the enhancement of the mechanical strength[1–4] and the reduction of thermal expansion[5–8]of polymers by the loading of inorganic fillers.However,the inorganic fil-lers tend to decrease the transparency of polymers owing to light scattering.To achieve both enhanced thermal strength and high transparency,new types of inorganic filler materi-als are desirable.

In our previous papers,we demonstrated that the loading of mesoporous silica particles effectively reduces the coeffi-cient of linear thermal expansion(CTE)of epoxy poly-mer[9–14]and silicone rubber.[15,16]Mesoporous silica,which has a very large number of nanopores and extremely large pore volumes,can be synthesized through the spontaneous self-assembly of surfactants.[17–23]When mesoporous silica particles are used as inorganic fillers of polymers,large amounts of polymers are confined inside the mesopores. The confined polymers do not contribute to the CTE at all, because the thermal expansion of the confined polymers is strongly suppressed by the robust silica framework.In addition,relative to silicone rubbers loaded with nonporous silica,silicone rubbers loaded with mesoporous silica show greater transparency.[15,16]

Although several previous studies have clarified the supe-riority of mesoporous silica particles over nonporous silica particles as inorganic filler materials,a comparative study with other silica particles has been never reported.A de-tailed systematic study is necessary to further emphasize the effectiveness of mesoporous silica particles as inorganic filler materials for silicone rubber.In this study,we have synthesized silica/silicone composites loaded with four types of silica particles (nonporous silica particles,mesopo-rous silica particles,silica gels with micropores,and fumed silica particles)and compared their thermal strength and transparency.On the basis of our systematic comparison,mesoporous silica particles are considered to be the best for filler materials for silicone rubbers.

2.Results and Discussion

In this study,we used four types of silica filler.Hereafter,we describe each silica filler as NS (nonporous silica par-ticles),TMPS (FSM-16-type mesoporous silica particles),SG (silica gel powders),and FS (fumed silica particles).Sil-ica fillers were pretreated under vacuum at 60°C to remove the adsorbed water.Pretreated fillers and silicone rubber were mixed with a vacuum mixer at room temperature until a bubble-free mixture was obtained.The obtained mixture was then heated under vacuum.First,the mixture was kept at 40°C for around 20h,then gradually heated to 150°C,and finally held at 150°C for 30min.The detailed amount of each component is listed in Table 1.Hereafter,silica/sili-cone composites are described as X_Y wt.-%,in which “X”indicates the doped filler (NS,TMPS,SG,and FS)and “Y”indicates the weight-percent of fillers.

Prior to the fabrication of silica/silicone composites,we characterized the starting filler materials.SEM images of fillers are shown in Figure 1.NS are perfect spheres with diameters of 0.5–2μm (Figure 1,a).TMPS have a similar diameter of that of NS,although TMPS has a more dis-torted shape (Figure 1,b).SG are slightly bigger than NS and TMPS (Figure 1,c);in contrast,FS are much smaller.The diameter of FS is estimated to be several tens of nano-meters (Figure 1,d).

Table 1.Sample preparation and physical data of silica/silicone composites with various amounts and types of doped silica filler.The dead pore ratios were calculated by Equations (1)and (2).The relative ratios of silicone inside and outside the pores were estimated by means of Equations (3)and (4),respectively.The weight ratios of the silicone (located outside the pores)in the composites were calculated by using Equation (5).Sample

Amount [g]Density Pore volume of

Dead pore Relative ratio of Weight ratio of CTE fillers ratio silicone [wt.-%]outside silicone

Silica

Silicone [g cm –3][cm 3g –1]

[vol.-%]Inside Outside [wt.-%]

[?10–6°C –1]

pores pores Silicone rubber 0.007.00 1.074––––100269NS_5wt.-%0.35 6.65 1.101––––95262NS_10wt.-%0.70 6.30 1.126––––90255TMPS_5wt.-%0.35 6.65 1.095 1.0088.5 5.095.090.2249TMPS_10wt.-%0.70 6.30 1.130 1.0098.911.888.279.4237SG_5wt.-%0.35 6.65 1.0930.3861.3 1.3398.793.7264SG_10wt.-%0.70 6.30 1.1190.3874.5 3.4296.686.9253FS_5wt.-%0.35 6.65 1.095––––95263FS_10wt.-%

0.70

6.30

1.121

–

–

–

–

90

253

Figure 1.SEM images of (a)NS,(b)TMPS,(c)SG,and (d)FS.

The porous structure of fillers was examined by low-an-gle X-ray diffraction measurements,TEM observations,and N 2adsorption–desorption isotherms.The low-angle X-ray diffraction profile of TMPS had several peaks assignable to (10),(11),and (20)diffractions of a well-ordered 2D hexag-onal structure (Figure 2).On the basis of the d 10value (5.0nm),the pore–pore distance was estimated to be 5.8nm.Hexagonally packed

mesopores within TMPS were

Figure 2.Low-angle X-ray diffraction profile and TEM image (in-set)of TMPS.

also confirmed by TEM (see inset in Figure 2).In contrast,no peaks appeared for the other fillers,thus showing that the porous structure inside the fillers is random (or there are no mesopores,especially in NS).

The N 2adsorption–desorption isotherms of each filler are summarized in Figure 3.In NS,a type-III isotherm typ-ical of the nonporous materials was obtained (Figure 3,a).TMPS showed a type-IV isotherm with a capillary conden-sation step at P /P 0=0.5,which is typical of mesoporous materials (Figure 3,b).On the basis of the pore-size distri-bution calculated by means of the Barrett–Joyner–Halenda (BJH)method,the uniform mesopore (mean diameter 3.9nm)was confirmed (see inset in Figure 3,b).The Bru-nauer–Emmett–Teller (BET)surface area and total pore volume was estimated to be 800m 2g –1and 1.00cm 3g –1,respectively.SG had a type-I isotherm and showed the exis-tence of uniform micropores (Figure 3,c).To analyze this isotherm,the t -plot method was used and the total surface area and micropore volume were calculated to be 650m 2g –1and 0.38cm 3g –1,respectively.As shown in the inset,uni-form micropore sizes were confirmed from the pore-size distribution calculated by means of the MP method.The mean micropore diameter was 1.2nm.The isotherm of FS was similar to that of NS,although a rapid increase in vol-ume was observed at a high relative pressure region (P /P 0?0.95)(Figure 3,d).

After the preparation of silica/silicone composites,their thermal stability was investigated with a thermal mechani-cal analysis (TMA)chart.Figure 4summarizes the ob-tained length-normalized TMA charts of silica/silicone composites.Similar to our previous studies on silica/silicone composites,[14–16]the glass-transition points did not appear in the TMA charts because the glass-transition temperature of silicone rubber is much lower (from –125to –120°C)than the temperature region in

this measurement.[24–26]The

Figure 3.N 2adsorption–desorption isotherm of (a)NS,(b)TMPS,(c)SG,and (d)FS.For porous silica fillers (TMPS and SG),the pore-size distribution is also included as an inset.

CTE values were determined from a slope of the TMA chart,and the CTE value of silicone rubber itself was 269?10–6°C –1.As the amount of the loaded fillers was increased,the CTE values monotonically decreased regard-less of the type of fillers (see also Table 1),although the degree of reduction differed among the fillers.After the loading of TMPS,the CTE value decreased more efficiently,which had always occurred in our previous studies.[15,16]In contrast,the CTE value of SG_Y wt.-%and FS_Y wt.-%was nearly the same as NS_Y wt.-%.For NS_Y wt.-%and FS_Y wt.-%,both the loaded silica particles are nonporous.Therefore,only an interface interaction between the silica particles and silicone rubber should be effective.Because FS has a much larger BET surface area (310m 2g –1)than NS (2m 2g –1),the interface interaction in FS_Y wt.-%is thought to be much larger than NS_Y wt.-%when the loaded amounts of particles are the same.Thus,we expect that the CTE value of FS_Y wt.-%is

lower than that of

Figure 4.Length-normalized thermal mechanical analysis (TMA)charts of composites with (a)5wt.-%silica fillers (X_5wt.-%)and (b)10wt.-%silica fillers (X_10wt.-%).Values of ΔL and L 0are the displacement of length and the original specimen length,respectively.The estimated CTE values are also noted.

NS_Y wt.-%.However,it should be noted that there was no significant difference in the CTE values between them.This result indicates that an interface interaction between the silica surface and silicone rubber is not essential for re-duction of CTE.

For TMPS_Y wt.-%or SG_Y wt.-%,as in our previous studies,the “dead pore ratio”was calculated by the follow-ing equations to quantitatively estimate the pore filling in the porous filler-doped composites [Equations (1)

and

(2)].[9–16]

(1)

(2)

in which x is the additive amount ratio of porous fillers,and ρ,ρsilicone ,and ρsilica are the density of the composites,silicone (1.07g cm –3),and silica (2.18g cm –3),respectively,and V 0is the total pore volume of fillers.When all pores are fully filled with silicone rubber,the dead pore ratio becomes 100vol.-%,whereas it is 0vol.-%if all pores remain.Table 1lists the estimated dead pore ratio of each composite.The dead pore ratio of TMPS_Y wt.-%was nearly 90vol.-%or higher,thus indicating that most of the mesopores were filled with silicone rubber.In contrast,the dead pore ratio of SG_Y wt.-%was much lower.As mentioned above,the pore size of SG was very small (around 1.2nm,which is in the micropore region),therefore silicone rubber has diffi-culty penetrating these micropores.Consequently,a large amount of air remained inside the micropores,thereby re-sulting in the lower dead pore ratio.

Then,we calculated the weight ratio of silicone outside pores by Equations (3),(4),and (5).V 0is the pore volume of fillers,x is the additive amount ratio of porous fillers,and ρsilicone is the density of silicone rubber (1.07g cm –3),respectively.The calculated outside polymer amounts of each composite are summarized in Table 1and their relationship to CTE is shown in Figure 5.As seen in our previous works,the CTE values of TMPS_Y wt.-%were in proportion to the weight

ratio of silicone

outside

(3)(4)

(5)

mesopores.It should be noted that the CTE values in TMPS_Y wt.-%were almost in the least-squares regression line for the data of NS_Y wt.-%.This fact strongly demon-strated that the thermal expansion behaviors of TMPS_Y wt.-%were governed by only the silicone rubbers outside filler particles.The expansion of silicone rubbers inside the pores was suppressed almost completely,thus indicating that the silicone rubbers confined physically inside the pores are thermally stable owing to the

robust silica frameworks.

Figure 5.Relationship between CTE and the weight ratios of sili-cone outside pores in the composites.The least-squares linear re-gression line for the data of NS_Y wt.-%(shown as a dotted line)is also noted.In the cases of NS_Y wt.-%and FS_Y wt.-%,all the silicone is present outside the particles,because NS and FS have no porosity.

The CTE values of SG_Y wt.-%were nearby in the re-gression line.Thus,similar to TMPS_Y wt.-%,thermal ex-pansion of the silicone rubber confined inside the micro-pores was suppressed.Because of the larger pore volume of TMPS (1.00cm 3g –1)and the higher dead pore ratio (around 90vol.-%or higher)in the composites,the amount of physically confined silicone rubbers in TMPS_Y wt.-%was greater than that in SG_Y wt.-%.Consequently,TMPS_Y wt.-%showed lower CTE than SG_Y wt.-%when the weight ratio of doped fillers was the same.

The degree of transparency of silicone composites was examined with UV/Vis-NIR spectra.Figure 6shows the UV/Vis-NIR spectra of composites loaded with 10wt.-%fillers.The silicone rubber itself was highly transparent (transmittance was nearly 90%)over the whole range be-

tween 350and 850nm,and loading of FS did not affect the transparency.In contrast,loading of other fillers (NS,TMPS,and SG)caused a reduction in the transparency.TMPS_10wt.-%showed higher transmittance than NS_10wt.-%as shown in our previous works,whereas SG_10wt.-%had a similar

transmittance of NS_10wt.-%.

Figure https://www.wendangku.net/doc/387756238.html,parison of UV/Vis-NIR spectra for several silica/sili-cone composites.

The difference in transparency between NS_10wt.-%and FS_10wt.-%is explained by the degree of light scat-tering.When light scattering caused by dispersed spherical particles occurs in the obtained silica/silicone composites,transmittance is described

as in Equation (6)

(6)

in which x is the optical path length,V p is the particle vol-ume fraction,r is the particle radius,λis the light wave-length,and n p and n m are the refractive indices of the par-ticles and matrices,respectively.[27]In this UV/Vis-NIR measurement,because the film thickness of each composite was set to be 50μm,the optical path length (x )is treatable as a constant.The particle volume fraction (V p )is calcu-

lated as Equation (7)

(7)

in which ρand ρsilica are densities of the composite and silica (2.18g cm –1),respectively,and x is the additive amount ratio [wt.-%]of silica in the composite (in this study,x =10).This value is almost the same,because the density of both composites is quite similar.Therefore,only particle size (r )should be considered.Because FS is much smaller than NS and I /I 0is proportional to the cube of the particle size,light scattering occurs far less in FS_10wt.-%,thus leading to much higher transparency.

In the case of TMPS_10wt.-%and SG_10wt.-%,we as-sumed that Equation (6)is suitable even though TMPS and SG are not perfectly spherical particles and introduced an

apparent filler consisting of a silica framework,silicone rubber confined inside mesopores,and air remaining inside mesopores (a detailed explanation is given below).A vol-ume fraction of an apparent filler (V p )can be

calculated by Equation (8)

(8)

in which ρand ρsilica are densities of the composite and silica (2.18g cm –1),x is the additive amount ratio [wt.-%]of silica in the composite (in this study,x =10),and V 0is the pore volume of the original silica particles per weight.Because the particle size (r )of TMPS and SG is not dra-matically different from that of NS (Figure 1),the values of V p and [(n p /n m )–1]should be important for the difference in transparency among TMPS_10wt.-%,SG_10wt.-%,and NS_10wt.-%[Equation (6)].Because of the high porosity of TMPS and SG,the volume fraction of loaded filler (V p )in TMPS_10wt.-%and SG_10wt.-%is larger than that in NS_10wt.-%[Equation (8)].Particularly for TMPS,be-cause of the silicone that filled the mesopores,the average refractive index of filler (n p )became close to that of the silicone matrix (n m ).Therefore,[(n p /n m )–1)]in TMPS_10wt.-%is supposed to be smaller than that in NS_10wt.-%.Indeed,when we calculated the value of V p ?[(n p /n m )–1]in both composites by equations we have previously reported,[14]it was 0.016for TMPS_10wt.-%,which was smaller than the value for NS_10wt.-%(0.018).In contrast,SG_10wt.-%did not show better trans-parency than NS_10wt.-%.This is probably because of the considerable amount of air that remained inside the micro-pores.If we assume that the silicone rubbers cannot be in-troduced into the inner part of SG particles (i.e.,only the pores close to the pore entrance are filled with the silicone rubbers),a silica/air core and silica/silicone shell would be formed in each particle.The refractive index of air (1.00)is much smaller than that of silica (1.46)and silicone (1.41).Therefore,the average refractive index of SG filler (n p )be-came much different from that of silicone matrix (n m ).For that reason,even though the porous SG particles are doped,the clear enhancement of transparency that was ob-served in NS_10wt.-%did not occur in SG_10wt.-%.

3.Conclusion

We examined the ability of four types of silica particles to function as inorganic fillers for silicone rubber from the viewpoint of their thermal strength and optical trans-parency.Relative to NS,FS retained the transparency of silicone rubber owing to its much smaller size.However,in terms of thermal strength,FS had no advantage,regardless of its much larger surface area.This is because interface interaction is not a dominant factor in determining the CTE of silica/silicone composites.For TMPS,by confining silicone rubber in the mesopores almost completely,both

suppression of CTE and improvement of transparency were achieved at the same time.In contrast,the composite loaded with SG showed inferior properties to that loaded with TMPS.This is because,owing to its smaller pore dia-meter,confinement of silicone rubber in the micropores of SG was not sufficient and large amounts of air remained inside the micropores.These results confirm that mesopo-rous silica particles like TMPS have a greater potential as inorganic filler material for silicone rubber.By using meso-porous silica nanoparticles,the transparency of such com-posites will be dramatically improved in the future. Experimental Section

Materials:Silicone rubber(X-32-3095)was acquired from Shin-Etsu Chemical Co.,Ltd.Nonporous silica particles(Admafine SO-C6)were obtained from Admatech Co.Ltd.FSM-16-type mesopo-rous silica particles(TMPS-4)were purchased from Taiyo Kagaku Co.,Ltd.Silica gel beads were acquired from Toyota Kako Co., Ltd.Because the silica gel beads were too large to be used as fillers, the silica gel beads were first crushed by applying high pressure, and then ground by mortar to make much smaller powders.Hydro-philic fumed silica particles(Aerosil380PE)were obtained from Nippon Aerosil Co.,Ltd.

Preparation of Filler/Silicone Composites:Silica fillers were pre-treated under vacuum at60°C to remove the adsorbed water.Pre-treated fillers and silicone rubber were mixed with a THINKY vac-uum mixer AR V-310at room temperature until the fillers were well dispersed.A bubble-free mixture was obtained.The obtained mix-ture was heated under vacuum.First,the mixture was kept at40°C for around20h,then gradually heated to150°C,and finally held at150°C for30min.The detailed amount of each component is listed in Table1.

Characterization:SEM images of silica fillers were observed with an SU-8000(Hitachi)instrument.TEM images were taken with a JEM-2100F(JEOL)instrument.Low-angle X-ray diffraction mea-surements were conducted with a RINT2000/PC(Cu-Kα)(Rigaku) instrument.The N2adsorption–desorption measurement of each filler was measured with a BELSORP-mini II(BEL Japan)instru-ment at77K.Prior to the measurement,a pretreatment of the particles was conducted under vacuum at80°C for24h with a BELPREP-vac II(BEL Japan)instrument.The specific gravity of synthesized filler/silicone composites was determined by means of the Archimedean method.Thermal mechanical analysis(TMA) data of the composites were collected with a TMA-60analyzer (Shimadzu).Prior to the measurement,rectangular specimens (10mm?4.5mm?4.5mm)were prepared from the fabricated composites.The temperature was increased at a rate of5°C min–1 during the measurement.The obtained TMA charts were normal-ized by original specimen length(10mm).The transparency of the composites was examined by the UV/Vis-NIR spectrum measured with a V-570spectrophotometer(JASCO).The thickness of each composite was fixed to50μm.

Acknowledgments

The authors gratefully acknowledge the suggestions and advice of Dr.T.Kotani.

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Received:December21,2013

Published Online:May7,2014

初中语文古文赏析曹操《短歌行》赏析(林庚)

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The way常见用法

The way 的用法 Ⅰ常见用法： 1)the way+ that 2)the way + in which（最为正式的用法） 3)the way + 省略（最为自然的用法） 举例：I like the way in which he talks. I like the way that he talks. I like the way he talks. Ⅱ习惯用法： 在当代美国英语中，the way用作为副词的对格，“the way+ 从句”实际上相当于一个状语从句来修饰整个句子。 1)The way =as I am talking to you just the way I’d talk to my own child. He did not do it the way his friends did. Most fruits are naturally sweet and we can eat them just the way they are—all we have to do is to clean and peel them. 2）The way= according to the way/ judging from the way The way you answer the question, you are an excellent student. The way most people look at you, you’d think trash man is a monster. 3）The way =how/ how much No one can imagine the way he missed her. 4）The way =because

The use of force

孩子。 Does your throat hurt you? Added the mother to the child. 女孩的表情没有任何变化，而她的目光却一直没有从我的脸上移开。 But the little girl’s expression didn’t change nor did she move her eyes from my face. 你看过她的嗓子了吗？ Have you looked? 我想看，孩子的母亲说，但看不见。 I tried to, said the mother but II couldn’t see. 这个月碰巧她上学的那个学校已经有好几例白喉病。虽然到目前为止没有人说出这件事，但很显然，我们心里都想到了。 As it happens we had been having a number of cases of diphtheria in the school to which this child went during that month and we were all, quite apparently, thinking of that, though no one had as yet spoken of the thing. 好了，我说，我们先看看嗓子吧。 Well, I said, suppose we take a look at the throat first. 我以医生特有的职业方式微笑着，叫着孩子的名字。我说，来吧，玛蒂尔达，张开嘴，让我看一下你的嗓子。 I smiled in my best professional manner and asking for the child’s first name I said, come on, Mathilda, open your mouth and let’s take a look at your throat.没有任何反应。 Nothing doing. 哦，来吧，我劝道，张大你的嘴，让我看看。看，我说着把两只手伸开，我的手里没有东西，张大嘴，让我看看。 Aw, come on, I coaxed, just open your mouth wide and let me take a look. Look, I said opening both hands wide, I haven’t anything in my hands. Just open up and let me see.

高中语文文言文曹操《短歌行(对酒当歌)》原文、翻译、赏析

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翅，哪里才有它们栖身之 所？ 可依？ 高山不辞土石才见巍 峨，大海不弃涓流才见壮阔。（比喻用人要“唯才是举”，多多益善。）山不厌高，水不厌深。 只有像周公那样礼待贤 才（周公见到贤才，吐出口 中正在咀嚼的食物，马上接 待。《史记》载周公自谓： “一沐三握发，一饭三吐哺， 犹恐失天下之贤。”），才 能使天下人心都归向我。 周公吐哺，天 赏析 曹操是汉末杰出的政治家、军事家和文学家，他雅好诗章，好作乐府歌辞，今存诗22首，全是乐府诗。曹操的乐府诗多描写他本人的政治主张和统一天下的雄心壮志。如他的《短歌行》，充分表达了诗人求贤若渴以及统一天下的壮志。 《短歌行》是政治性很强的诗作，主要是为曹操当时所实行的政治路线和政策策略服务的，但是作者将政治内容和意义完全熔铸在浓郁的抒情意境之中，全诗充分发挥了诗歌创作的特长，准确而巧妙地运用了比兴手法，寓理于情，以情感人。诗歌无论在思想内容还是在艺术上都取得了极高的成就，语言质朴，立意深远，气势充沛。这首带有建安时代"志深比长""梗概多气"的时代特色的《短歌行》，读后不觉思接千载，荡气回肠，受到强烈的感染。 对酒当歌，人生几何？ 譬如朝露，去日苦多。 慨当以慷，幽思难忘。 何以解忧，唯有杜康。 青青子衿，悠悠我心。 但为君故，沈吟至今。 呦呦鹿鸣，食野之苹。 我有嘉宾，鼓瑟吹笙。 明明如月，何时可掇？ 忧从中来，不可断绝。 越陌度阡，枉用相存。 契阔谈，心念旧恩。 月明星稀，乌鹊南飞， 绕树三匝，何枝可依？ 山不厌高，海不厌深， 周公吐哺，天下归心。 《短歌行》是汉乐府的旧题，属于《相和歌?平调曲》。这就是说它本来是一个乐曲的名称，这种乐曲怎么唱法，现在当然是不知道了。但乐府《相和歌?平调曲》中除了《短歌行》还有《长歌行》，唐代吴兢《乐府古题要解》引证古诗“长歌正激烈”，魏文帝曹丕《燕歌行》“短歌微吟不能长”和晋代傅玄《艳歌行》“咄来长歌续短歌”等句，认为“长歌”、“短

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外国文学名著鉴赏期末论文院—系：数学学院 科目：外国文学名著鉴赏（期末论文）班级： 08级数学与应用数学A班 姓名：沈铁 学号： 200805050149 上课时段：周五晚十、十一节课

奋斗了，才有出路 ——读《鲁宾逊漂游记》有感小说《鲁宾逊漂游记》一直深受人们的喜爱。读完这篇小说，使我对人生应该有自己的一个奋斗历程而受益匪浅。当一个人已经处于绝境的时候，还能够满怀信心的去面对和挑战生活，实在是一种可贵的精神。他使我认识到，人无论何时何地，不管遇到多大的困难，都不能被困难所吓倒，我们要勇敢的面对困难，克服困难，始终保持一种积极向上、乐观的心态去面对。在当今社会只有努力去奋斗，才会有自己的出路！ 其实现在的很多人都是那些遇到困难就退缩，不敢勇敢的去面对它。不仅如此，现在很多人都是独生子女，很多家长视子女为掌上明珠，不要说是冒险了，就连小小的家务活也不让孩子做，天天总是说：“我的小宝贝啊，你读好书就行了，其它的爸爸妈妈做就可以了。”读书固然重要，但生活中的小事也不能忽略。想一想，在荒无人烟的孤岛上，如果你连家务活都不会做，你能在那里生存吗？读完这部著作后，我不禁反问自己：“如果我像书中的鲁宾逊那样在大海遭到风暴，我能向他那样与风暴搏斗，最后逃离荒岛得救吗？恐怕我早已经被大海所淹没；如果我漂流到孤岛，能活几天？我又能干些什么？我会劈柴吗？会打猎做饭吗？我连洗洗自己的衣服还笨手笨脚的。”我们应该学习鲁宾逊这种不怕困难的精神，无论何时何地都有坚持地活下去，哪怕只有一线希望也要坚持到底，决不能放弃！我们要像鲁宾

逊那样有志气、有毅力、爱劳动，凭自己的双手创造财富，创造奇迹，取得最后的胜利。这样的例子在我们的生活中屡见不鲜。 《史记》的作者司马迁含冤入狱，可它依然在狱中完成《史记》一书，他之所以能完成此书，靠的也是他心中那顽强的毅力，永不放弃的不断努力的精神。著名作家爱迪生从小就生活在一个贫困的家庭中，可是他从小就表现出了科学方面的天赋。长大后爱迪生着力于电灯的发明与研究，他经过了九百多次的失败，可它依然没有放弃，不断努力，最后终于在第一千次实验中取得了成功。 鲁宾逊在岛上生活了二十八年，他面对了各种各样的困难和挫折，克服了许多常人无法想象的困难，自己动手，丰衣足食，以惊人的毅力，顽强的活了下来。他自从大船失事后，找了一些木材，在岛上盖了一间房屋，为防止野兽，还在房子周围打了木桩，来到荒岛，面对着的首要的就是吃的问题，船上的东西吃完以后，鲁宾逊开始打猎，有时可能会饿肚子，一是他决定播种，几年后他终于可以吃到自己的劳动成果，其实学习也是这样，也有这样一个循序渐进的过程，现在的社会，竞争无处不在，我们要懂得只有付出才会有收获，要勇于付出，在战胜困难的同时不断取得好成绩。要知道只有付出，才会有收获。鲁宾逊在失败后总结教训，终于成果；磨粮食没有石磨，他就用木头代替；没有筛子，就用围巾。鲁宾逊在荒岛上解决了自己的生存难题，面对人生挫折，鲁宾逊的所作所为充分显示了他坚毅的性格和顽强的精神。同样我们在学习上也可以做一些创新，养成一种创新精神，把鲁宾逊在荒岛，不畏艰险，不怕失败挫折，艰苦奋斗的精

The way的用法及其含义(二)

The way的用法及其含义（二） 二、the way在句中的语法作用 the way在句中可以作主语、宾语或表语： 1.作主语 The way you are doing it is completely crazy.你这个干法简直发疯。 The way she puts on that accent really irritates me. 她故意操那种口音的样子实在令我恼火。The way she behaved towards him was utterly ruthless. 她对待他真是无情至极。 Words are important, but the way a person stands, folds his or her arms or moves his or her hands can also give us information about his or her feelings. 言语固然重要,但人的站姿,抱臂的方式和手势也回告诉我们他(她)的情感。 2.作宾语 I hate the way she stared at me.我讨厌她盯我看的样子。 We like the way that her hair hangs down.我们喜欢她的头发笔直地垂下来。 You could tell she was foreign by the way she was dressed. 从她的穿著就可以看出她是外国人。 She could not hide her amusement at the way he was dancing. 她见他跳舞的姿势，忍俊不禁。 3.作表语 This is the way the accident happened.这就是事故如何发生的。 Believe it or not, that's the way it is. 信不信由你, 反正事情就是这样。 That's the way I look at it, too. 我也是这么想。 That was the way minority nationalities were treated in old China. 那就是少数民族在旧中

曹操《短歌行》其二翻译及赏析

曹操《短歌行》其二翻译及赏析 引导语：曹操(155—220)，字孟德，小名阿瞒，《短歌行 二首》 是曹操以乐府古题创作的两首诗， 第一首诗表达了作者求贤若渴的心 态，第二首诗主要是曹操向内外臣僚及天下表明心迹。 短歌行 其二 曹操 周西伯昌，怀此圣德。 三分天下，而有其二。 修奉贡献，臣节不隆。 崇侯谗之，是以拘系。 后见赦原，赐之斧钺，得使征伐。 为仲尼所称，达及德行， 犹奉事殷，论叙其美。 齐桓之功，为霸之首。 九合诸侯，一匡天下。 一匡天下，不以兵车。 正而不谲，其德传称。 孔子所叹，并称夷吾，民受其恩。 赐与庙胙，命无下拜。 小白不敢尔，天威在颜咫尺。 晋文亦霸，躬奉天王。 受赐圭瓒，钜鬯彤弓， 卢弓矢千，虎贲三百人。 威服诸侯，师之所尊。 八方闻之，名亚齐桓。 翻译 姬昌受封为西伯，具有神智和美德。殷朝土地为三份，他有其中两分。 整治贡品来进奉，不失臣子的职责。只因为崇侯进谗言，而受冤拘禁。 后因为送礼而赦免， 受赐斧钺征伐的权利。 他被孔丘称赞， 品德高尚地位显。 始终臣服殷朝帝王，美名后世流传遍。齐桓公拥周建立功业，存亡继绝为霸 首。

聚合诸侯捍卫中原，匡正天下功业千秋。号令诸侯以匡周室，主要靠的不是 武力。 行为磊落不欺诈，美德流传于身后。孔子赞美齐桓公，也称赞管仲。 百姓深受恩惠，天子赐肉与桓公，命其无拜来接受。桓公称小白不敢，天子 威严就在咫尺前。 晋文公继承来称霸，亲身尊奉周天王。周天子赏赐丰厚，仪式隆重。 接受玉器和美酒，弓矢武士三百名。晋文公声望镇诸侯，从其风者受尊重。 威名八方全传遍，名声仅次于齐桓公。佯称周王巡狩，招其天子到河阳，因 此大众议论纷纷。 赏析 《短歌行》 (“周西伯昌”)主要是曹操向内外臣僚及天下表明心 迹，当他翦灭群凶之际，功高震主之时，正所谓“君子终日乾乾，夕惕若 厉”者，但东吴孙权却瞅准时机竟上表大说天命而称臣，意在促曹操代汉 而使其失去“挟天子以令诸侯”之号召， 故曹操机敏地认识到“ 是儿欲据吾著炉上郁!”故曹操运筹谋略而赋此《短歌行 ·周西伯 昌》。 西伯姬昌在纣朝三分天下有其二的大好形势下， 犹能奉事殷纣， 故孔子盛称 “周之德， 其可谓至德也已矣。 ”但纣王亲信崇侯虎仍不免在纣王前 还要谗毁文王，并拘系于羑里。曹操举此史实，意在表明自己正在克心效法先圣 西伯姬昌，并肯定他的所作所为，谨慎惕惧，向来无愧于献帝之所赏。 并大谈西伯姬昌、齐桓公、晋文公皆曾受命“专使征伐”。而当 今天下时势与当年的西伯、齐桓、晋文之际颇相类似，天子如命他“专使 征伐”以讨不臣，乃英明之举。但他亦效西伯之德，重齐桓之功，戒晋文 之诈。然故作谦恭之辞耳，又谁知岂无更讨封赏之意乎 ?不然建安十八年(公元 213 年)五月献帝下诏曰《册魏公九锡文》，其文曰“朕闻先王并建明德， 胙之以土，分之以民，崇其宠章，备其礼物，所以藩卫王室、左右厥世也。其在 周成，管、蔡不静，惩难念功，乃使邵康公赐齐太公履，东至于海，西至于河， 南至于穆陵，北至于无棣，五侯九伯，实得征之。 世祚太师，以表东海。爰及襄王，亦有楚人不供王职，又命晋文登为侯伯， 锡以二辂、虎贲、斧钺、禾巨 鬯、弓矢，大启南阳，世作盟主。故周室之不坏， 系二国是赖。”又“今以冀州之河东、河内、魏郡、赵国、中山、常 山，巨鹿、安平、甘陵、平原凡十郡，封君为魏公。锡君玄土，苴以白茅，爰契 尔龟。”又“加君九锡，其敬听朕命。” 观汉献帝下诏《册魏公九锡文》全篇，尽叙其功，以为其功高于伊、周，而 其奖却低于齐、晋，故赐爵赐土，又加九锡，奖励空前。但曹操被奖愈高，心内 愈忧。故曹操在曾早在五十六岁写的《让县自明本志令》中谓“或者人见 孤强盛， 又性不信天命之事， 恐私心相评， 言有不逊之志， 妄相忖度， 每用耿耿。

2008年浙师大《外国文学名著鉴赏》期末考试答案

（一）文学常识 一、古希腊罗马 1．（1）宙斯(罗马神话称为朱庇特)，希腊神话中最高的天神，掌管雷电云雨，是人和神的主宰。 （2）阿波罗，希腊神话中宙斯的儿子，主管光明、青春、音乐、诗歌等，常以手持弓箭的少年形象出现。 （3）雅典那，希腊神话中的智慧女神，雅典城邦的保护神。 （4）潘多拉，希腊神话中的第一个女人，貌美性诈。私自打开了宙斯送她的一只盒子，里面装的疾病、疯狂、罪恶、嫉妒等祸患，一齐飞出，只有希望留在盒底，人间因此充满灾难。“潘多拉的盒子”成为“祸灾的来源”的同义语。 （5）普罗米修斯，希腊神话中造福人间的神。盗取天火带到人间，并传授给人类多种手艺，触怒宙斯，被锁在高加索山崖，受神鹰啄食，是一个反抗强暴、不惜为人类牺牲一切的英雄。 （6）斯芬克司，希腊神话中的狮身女怪。常叫过路行人猜谜，猜不出即将行人杀害；后因谜底被俄底浦斯道破，即自杀。后常喻“谜”一样的人物。与埃及狮身人面像同名。 2．荷马，古希腊盲诗人。主要作品有《伊利亚特》和《奥德赛》，被称为荷马史诗。《伊利亚特》叙述十年特洛伊战争。《奥德赛》写特洛伊战争结束后，希腊英雄奥德赛历险回乡的故事。马克思称赞它“显示出永久的魅力”。 3．埃斯库罗斯，古希腊悲剧之父，代表作《被缚的普罗米修斯》。6．阿里斯托芬，古希腊“喜剧之父”代表作《阿卡奈人》。 4．索福克勒斯，古希腊重要悲剧作家，代表作《俄狄浦斯王》。5．欧里庇得斯，古希腊重要悲剧作家，代表作《美狄亚》。 二、中世纪文学 但丁，意大利人，伟大诗人，文艺复兴的先驱。恩格斯称他是“中世纪的最后一位诗人，同时又是新时代的最初一位诗人”。主要作品有叙事长诗《神曲》，由地狱、炼狱、天堂三部分组成。《神曲》以幻想形式，写但丁迷路，被人导引神游三界。在地狱中见到贪官污吏等受着惩罚，在净界中见到贪色贪财等较轻罪人，在天堂里见到殉道者等高贵的灵魂。 三、文艺复兴时期 1．薄迦丘意大利人短篇小说家，著有《十日谈》拉伯雷，法国人，著《巨人传》塞万提斯，西班牙人,著《堂?吉诃德》。 2．莎士比亚，16-17世纪文艺复兴时期英国伟大的剧作家和诗人，主要作品有四大悲剧——《哈姆雷特》、《奥赛罗》《麦克白》、《李尔王》，另有悲剧《罗密欧与朱丽叶》等，喜剧有《威尼斯商人》《第十二夜》《皆大欢喜》等，历史剧有《理查二世》、《亨利四世》等。马克思称之为“人类最伟大的戏剧天才”。 四、17世纪古典主义 9．笛福，17-18世纪英国著名小说家，被誉为“英国和欧洲小说之父”，主要作品《鲁滨逊漂流记》，是英国第一部现实主义长篇小说。10．弥尔顿，17世纪英国诗人，代表作：长诗《失乐园》，《失乐园》，表现了资产阶级清教徒的革命理想和英雄气概。 25．拉伯雷，16世纪法国作家，代表作：长篇小说《巨人传》。 26．莫里哀，法国17世纪古典主义文学最重要的作家，法国古典主义喜剧的创建者，主要作品为《伪君子》《悭吝人》（主人公叫阿巴公）等喜剧。 五、18世纪启蒙运动 1）歌德，德国文学最高成就的代表者。主要作品有书信体小说《少年维特之烦恼》，诗剧《浮士德》。 11．斯威夫特，18世纪英国作家，代表作：《格列佛游记》，以荒诞的情节讽刺了英国现实。 12．亨利·菲尔丁，18世纪英国作家，代表作：《汤姆·琼斯》。 六、19世纪浪漫主义 （1拜伦， 19世纪初期英国伟大的浪漫主义诗人，代表作为诗体小说《唐璜》通过青年贵族唐璜的种种经历，抨击欧洲反动的封建势力。《恰尔德。哈洛尔游记》 （2雨果，伟大作家，欧洲19世纪浪漫主义文学最卓越的代表。主要作品有长篇小说《巴黎圣母院》、《悲惨世界》、《笑面人》、《九三年》等。《悲惨世界》写的是失业短工冉阿让因偷吃一片面包被抓进监狱，后改名换姓，当上企业主和市长，但终不能摆脱迫害的故事。《巴黎圣母院》 弃儿伽西莫多，在一个偶然的场合被副主教克洛德.孚罗洛收养为义子，长大后有让他当上了巴黎圣母院的敲钟人。他虽然十分丑陋而且有多种残疾，心灵却异常高尚纯洁。 长年流浪街头的波希米亚姑娘拉.爱斯梅拉达，能歌善舞，天真貌美而心地淳厚。青年贫诗人尔比埃尔.甘果瓦偶然同她相遇，并在一个更偶然的场合成了她名义上的丈夫。很有名望的副教主本来一向专心于"圣职"，忽然有一天欣赏到波希米亚姑娘的歌舞，忧千方百计要把她据为己有，对她进行了种种威胁甚至陷害，同时还为此不惜玩弄卑鄙手段，去欺骗利用他的义子伽西莫多和学生甘果瓦。眼看无论如何也实现不了占有爱斯梅拉达的罪恶企图，最后竟亲手把那可爱的少女送上了绞刑架。 另一方面，伽西莫多私下也爱慕着波希米亚姑娘。她遭到陷害，被伽西莫多巧计救出，在圣母院一间密室里避难，敲钟人用十分纯朴和真诚的感情去安慰她，保护她。当她再次处于危急中时，敲钟人为了援助她，表现出非凡的英勇和机智。而当他无意中发现自己的"义父"和"恩人"远望着高挂在绞刑架上的波希米亚姑娘而发出恶魔般的狞笑时，伽西莫多立即对那个伪善者下了最后的判决，亲手把克洛德.孚罗洛从高耸入云的钟塔上推下，使他摔的粉身碎骨。 （3司汤达，批判现实主义作家。代表作《红与黑》，写的是不满封建制度的平民青年于连，千方百计向上爬，最终被送上断头台的故事。“红”是将军服色，指“入军界”的道路；“黑”是主教服色，指当神父、主教的道路。 14．雪莱，19世纪积极浪漫主义诗人，欧洲文学史上最早歌颂空想社会主义的诗人之一，主要作品为诗剧《解放了的普罗米修斯》，抒情诗《西风颂》等。 15．托马斯·哈代，19世纪英国作家，代表作：长篇小说《德伯家的苔丝》。 16．萨克雷，19世纪英国作家，代表作：《名利场》 17．盖斯凯尔夫人，19世纪英国作家，代表作：《玛丽·巴顿》。 18．夏洛蒂?勃朗特，19世纪英国女作家，代表作：长篇小说《简?爱》19艾米丽?勃朗特，19世纪英国女作家，夏洛蒂?勃朗特之妹，代表作：长篇小说《呼啸山庄》。 20．狄更斯，19世纪英国批判现实主义文学的重要代表，主要作品为长篇小说《大卫?科波菲尔》、《艰难时世》《双城记》《雾都孤儿》。21．柯南道尔，19世纪英国著名侦探小说家，代表作品侦探小说集《福尔摩斯探案》是世界上最著名的侦探小说。 七、19世纪现实主义 1、巴尔扎克，19世纪上半叶法国和欧洲批判现实主义文学的杰出代表。主要作品有《人间喜剧》，包括《高老头》、《欧也妮·葛朗台》、《贝姨》、《邦斯舅舅》等。《人间喜剧》是世界文学中规模最宏伟的创作之一，也是人类思维劳动最辉煌的成果之一。马克思称其“提供了一部法国社会特别是巴黎上流社会的卓越的现实主义历史”。

(完整版)the的用法

定冠词the的用法： 定冠词the与指示代词this ,that同源,有“那(这)个”的意思,但较弱,可以和一个名词连用,来表示某个或某些特定的人或东西. (1)特指双方都明白的人或物 Take the medicine.把药吃了. (2)上文提到过的人或事 He bought a house.他买了幢房子. I've been to the house.我去过那幢房子. (3)指世界上独一无二的事物 the sun ,the sky ,the moon, the earth (4)单数名词连用表示一类事物 the dollar 美元 the fox 狐狸 或与形容词或分词连用,表示一类人 the rich 富人 the living 生者 (5)用在序数词和形容词最高级,及形容词等前面 Where do you live?你住在哪? I live on the second floor.我住在二楼. That's the very thing I've been looking for.那正是我要找的东西. (6)与复数名词连用,指整个群体 They are the teachers of this school.(指全体教师) They are teachers of this school.(指部分教师) (7)表示所有,相当于物主代词,用在表示身体部位的名词前 She caught me by the arm.她抓住了我的手臂. (8)用在某些有普通名词构成的国家名称,机关团体,阶级等专有名词前 the People's Republic of China 中华人民共和国 the United States 美国 (9)用在表示乐器的名词前 She plays the piano.她会弹钢琴. (10)用在姓氏的复数名词之前,表示一家人 the Greens 格林一家人(或格林夫妇) (11)用在惯用语中 in the day, in the morning... the day before yesterday, the next morning... in the sky... in the dark... in the end... on the whole, by the way...

The use of force

The use of force 大意: Mathilda had been ill for three days. Her mother had given her some medicine, but it didn’t do any good. So they had to ask the doctor to come. There had been a number of cases of diphtheria in Mathilda School and two of them had been dead. When the doctor arrived at Olson’s home, he wanted to examine Mathilda throat first. But no matter how he coaxed, She wouldn’t open her mouth. So the doctor had to get the tongue depressor into her mouth. But Mathilda reduced it to splinters. In orde r to protect Mathilda herself and other children, the doctor had to make sure whether she had diphtheria or not, so that he could treat her in time. Letting Mathilda‘s father hold her wrists he tried his best to open her mouth and found she really had diphtheria. This story made us can think such a question that something in life can’t only depend on self-willingness. Under some circumstances, certain force seems necessary. 对医生的评价:After the doctor arrived at the girl’s home, he wanted to see her throat. As there had been a number of cases of diphtheria in the school to which the girl went during that month, the doctor also thought that of the girl. So he smiled to the girl and asked her to open her mouth and let him have a look at her throat. No matter how the doctor coaxed, the girl shut her mouth firmly. Thinking that the girl might have diphtheria and possibly die of it, the doctor decided to use force to open her mouth. He had seen at least two children lying dead in bed of neglect in such cases. He felt that he must get a diagnosis now. So he grasped the girl’s head with his left hand and tried to get the wooden tongue depressor between her teeth. But when the doctor got the wooden spatula behind her last teeth. She gripped the blade between her molars and reduced it to splinters. In the final unreasoning assault the doctor outer powered the girl. He forced the heavy silver spoon back of her teeth and down her throat till she gagged. Her both tonsils were covered with membrane. From that the doctor had done, I thought he was a responsible person. In order to save the lives of the patients, especially those children who did not know how to co-operate with the doctor, he had to take some measure. Otherwise a good or suitable time of treatment would be missed. The doctor appears to be compassionate and keen to human behavior, characteristic of a good doctor, though he is also undeniably blunt and slightly prejudiced. 思想: Though there are reasons often justifiable, what compels the use of force against others isn't simply altruism alone. The overall theme of the story revolves around power and submission and the doctor's unnerved feeling following the forceful encounter. 作者如何写的: The story is narrated in first person by a doctor, who is answering a house visit to see a sick girl. Williams uses interior monologue as a "stream-of-consciousness" tool reflects the narrator's experience of dialogue and gives insight into the character and his appraisal of the situations he encounters. The story is written without the use of quotation marks, and the dialogue is not distinguished from the narrator's comments. The story is rendered from the subjective point of view of the doctor, and explores his subdued enjoyment of forcefully subduing the stubborn child in an attempt to acquire the throat sample.

外国名著赏析论文

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