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Nanoemulsions with enhanced temperature stability using thermo-sensitive

Nanoemulsions with enhanced temperature stability using thermo-sensitive
Nanoemulsions with enhanced temperature stability using thermo-sensitive

Colloids and Surfaces A:Physicochem.Eng.Aspects 396 (2012) 115–121

Contents lists available at SciVerse ScienceDirect

Colloids and Surfaces A:Physicochemical and

Engineering

Aspects

j o u r n a l h o m e p a g e :w w w.e l s e v i e r.c o m /l o c a t e /c o l s u r f

a

Nanoemulsions with enhanced temperature stability using thermo-sensitive association of nonionic surfactant and amphiphilic polyelectrolytes

Johanna Galindo-Alvarez a ,Véronique Sadtler b ,Philippe Marchal b ,Patrick Perrin c ,Christophe Tribet c ,Emmanuelle Marie a ,Alain Durand a ,?

a

Laboratoire de Chimie Physique Macromoléculaire UMR 7568CNRS-Nancy University,ENSIC,1rue Grandville,BP 20451,F-54001Nancy cedex,France b

Laboratoire Réactions et Génie des Procédés UPR 3349CNRS-Nancy University,ENSIC,1rue Grandville,BP 20451,F-54001Nancy cedex,France c

Laboratoire de Physico-chimie des Polymères et des Milieux Dispersés,UMR 7615CNRS-ESPCI-UniversitéParis 6,75231Paris cedex,France

a r t i c l e

i n f o

Article history:

Received 1November 2011Received in revised form 11December 2011

Accepted 15December 2011

Available online 24 December 2011

Keywords:

Nonionic surfactants Amphiphilic polymers Nanoemulsions

Temperature sensitivity

a b s t r a c t

Aqueous mixtures containing a non-ionic surfactant (tetraethylene glycol monododecylether,C 12E 4),an amphiphilic polymer (poly(sodium acrylate)hydrophobically modi?ed with azobenzene groups ran-domly attached along the chains,HMPA)and 0.3M NaNO 3were studied regarding the associations between macromolecules and surfactant assemblies (micelles or lamellar phases)at various temper-atures (4–37?C).The effects of the thermo-induced transition of surfactant assemblies from micelles to lamellar phase on phase separation behavior were systematically investigated as a function of sur-factant and polymer concentration,polymer structure (amount of grafted hydrophobic groups)and temperature.Rheological properties of polymer-rich coacervates revealed thermo-thickening behav-ior,in accordance with phase separation behavior.Finally,bulk phenomena were applied to design nanoemulsions with improved temperature stability taking the opportunity of strengthening interfacial layers through thermo-thickening properties.

? 2011 Elsevier B.V. All rights reserved.

1.Introduction

Water-soluble polymers are widely used for controlling rhe-ology of aqueous formulations.In addition to the obtained level of viscosity and its response to applied stress,one of their inter-ests is that variables like pH or ionic strength can be used to control the level of viscosity or other ?ow characteristics [1,2].Temperature is a non invasive parameter that may be easy to use as stimulus on formulated systems either in the laboratory or at industrial scale for inducing variations of physical proper-ties like viscosity of ?uids or colloidal stability of dispersions [3].Thus,thermo-sensitive systems have been largely studied by both academics and industrialists for various applications.One par-ticular strategy followed for the formulation of thermo-sensitive aqueous systems was combining water-soluble amphiphilic poly-mers to poly(ethylene glycol)-based nonionic surfactants [4–7].The latter undergo transitions in self-association upon increasing tem-perature while the amphiphilic polymer,through its association with surfactant molecules,ampli?es the resulting variations into macroscopic properties (bulk or interfacial rheology,interactions between colloidal particles ...).

?Corresponding author.Tel.:+33(0)383175292;fax:+33(0)383379977.E-mail address:Alain.Durand@ensic.inpl-nancy.fr (A.Durand).

Thermo-thickening behavior of mixtures of amphiphilic poly-mers and nonionic surfactants has been well described and studied [4,5,8].The application was essentially focused on the control the rheological behavior of aqueous formulations with temperature.Thermal gelation of mixtures containing hydrophobically modi?ed poly(sodium acrylate)and tetraethylene glycol monododecylether was attributed to the thermo-induced formation of vesicles by the nonionic surfactant above 20?C.These vesicles formed bridges between amphiphilic macromolecules through hydrophobic asso-ciations and increased the reticulation of the physical network.In that work,the initial idea was to examine how mixtures of amphiphilic polymers and nonionic surfactants could be used to increase the stability of nanoemulsions with temperature taking advantage of previously described phenomena.Nevertheless,in some conditions,polymer-surfactant systems may undergo phase separation,particularly when nonionic species are involved.In addition,the partitioning of the components (the polymer and the nonionic surfactant)between aqueous and oil phase as well as its variation with temperature may in?uence the colloidal stability of the dispersion.Thus colloidal aspects have to be studied in close combination with phase behavior [8].

The aim of this work was ?rst to investigate the phase behavior of aqueous mixtures containing a nonionic surfactant (tetraethy-lene glycol monododecylether,C 12E 4),an amphiphilic polymer (poly(sodium acrylate)hydrophobically modi?ed with azobenzene

0927-7757/$–see front matter ? 2011 Elsevier B.V. All rights reserved.doi:10.1016/j.colsurfa.2011.12.051

116J.Galindo-Alvarez et al./Colloids and Surfaces A:Physicochem.Eng.Aspects 396 (2012) 115–121

Na +

CH CH

2

COO-

CH 2

CH C NH N

N

100-x

x

Fig.1.Chemical formula of azobenzene substituted poly(sodium acrylate),noted HMPA x .Polymers used in that work had x values equal to 1.3and 3.2%.A ran-dom distribution of azobenzene substituents in poly(sodium acrylate)backbone was assumed.

groups randomly attached along the chains,HMPA)and 0.3M NaNO 3aqueous solution as a function of composition,degree of substitution of HMPA and temperature.Besides,temperature sen-sitivity of polymer/surfactant association was utilized in order to control the colloidal stability of nanoemulsions as a function of temperature.

2.Experimental

2.1.Materials

All chemicals were purchased from Aldrich ?

and used with-out further puri?https://www.wendangku.net/doc/b716106440.html,liQ ?water was used for preparation of all aqueous solutions.Pure tetraethyleneglycol n-dodecyl ether,C 12E 4was used for all experiments.Hydrocarbon oil was used for emulsion preparation,n-dodecane (98%purity).

At 20?C,the density of neat C 12E 4is 0.946g/mL while that of dodecane is 0.745g/mL.

2.2.Synthesis of modi?ed poly(sodium acrylate)

Amphiphilic polymers combined a poly(sodium acrylate)back-bone with azobenzene groups randomly attached along the chains (HMPA x ,Fig.1).Details about the synthesis and characterization of those polymers are to be found elsewhere [9].The amount of grafted azobenzene groups was determined by 1H NMR in D 2O (Fig.2)and expressed as a mole fraction relatively to sodium acry-late units (x in %).In the 1H NMR spectra,the areas of the signal corresponding to aromatic hydrogen atoms (A 1)and that of the signal corresponding to methyne hydrogen atoms (A 2)were used to calculate x with the following equation:

x (%)=

1009

×

A 1

A 2

(1)

2.3.Rheological behavior of coacervates

The rheological properties of coacervates were determined with a dynamic oscillatory and shear rate controlled ARES-RFS rheome-ter (TA instruments).A plate/plate geometry device with a 40mm diameter (aluminum coated)and a 1.5mm gap was used.Dynamic strain frequency sweep at 50%strain was carried out at various temperatures (4,20,25and 37?C).Conversely,temperature sweep was carried out at a given frequency of 10rad/s.Frequency sweep and temperature sweep measurements were carried out,after at least 48h of equilibrium,for the polymer-rich coacervates.

2.4.Emulsion formulation and preparation

For all reported experiments,solutions and emulsions were not protected from natural light.Thus we will consider that the azobenzene groups of HMPA x are essentially in trans form [10].The aqueous phase initially contained polymer,surfactant and NaNO 3(at a concentration of 0.3M).HMPA x and C 12E 4were always previously dissolved in the aqueous phase.In what follows,the

concentration of any water-soluble stabilizer (HMPA x or C 12E 4)will be expressed in g/L with reference to the volume of aqueous phase only.The amount of oil in the emulsion will be expressed in volume fraction with reference to the total volume of emulsion (aqueous phase and oil phase).

Emulsions were prepared as follows.Polymer/surfactant mix-ture was dissolved under magnetic stirring in the aqueous phase during 20h.The required amount of oil was then added.The two-phase mixture was stirred magnetically during 1h at 1000rpm followed by sonication (50%pulsed mode)using a Vibracell model 600W (Sonics &Materials Inc,Danbury,CT)during 2min.Emulsion container was immersed into an ice bath during sonication process.The distance of the tip from the bottom of the tube was adjusted.After sonication,samples of the batch emulsion were stored at temperatures between 4and 37?C for ageing studies.

2.5.Average droplet diameter measurement

Average hydrodynamic droplet diameters were measured by dynamic light scattering at low concentration using a HPPS from Malvern.Although this apparatus was able to measure relatively concentrated samples,emulsions were diluted.Dilution was car-ried out with a 0.3M solution of NaNO 3.It was checked that the dilution did not change signi?cantly the results.The diameter obtained is an average value based on the light intensity (three con-secutive measurements for each sample).Taking into account the observed variations between two consecutive measurements,we could consider that the obtained average values are known within an interval of ±5nm.

As a control experiment,a dodecane emulsion (5%volume dode-cane)was prepared in the presence of C 12E 4(6g/L)and HMPA 3.2(2g/L).The average droplet diameter determined by HPPS was com-pared to the complete droplet size distribution given by a laser granulometer (Mastersizer 2000from Malvern).The intensity aver-age value was 186nm (HPPS)while the volume weighted mean was 169nm (Mastersizer).In addition,the “polydispersity index”(PDI)provided by HPPS was a reasonable way to appreciate if the sample size distribution could be considered as monomodal.All samples considered in that work had PDI values lower than 0.3,which can be considered as characteristic of monomodal samples.

3.Results and discussion

3.1.Formulation of aqueous mixtures and nanoemulsions

Aqueous phase was composed of tetraethyleneglycol n-dodecyl ether (C 12E 4),hydrophobically modi?ed poly(sodium acrylate)(HMPA x )and 0.3M NaNO 3aqueous solution.HMPA x was syn-thesized by random attachment of azobenzene groups along poly(sodium acrylate)backbone as described previously (Fig.1)[9].The amount of grafted azobenzene groups,x ,was determined by 1H NMR (Eq.(1))and expressed as mole percents relatively to repeat units (100%meaning that one azobenzene group is attached onto each repeat unit).Two HMPA x were used in that study with x =1.3and 3.2%which will be named HMPA 1.3and HMPA 3.2respectively.For the preparation of nanoemulsions,an aliphatic hydrocarbon oil was used,n-dodecane.Except otherwise stated,polymer and surfactant concentrations will be always expressed in g/L with ref-erence to the volume of aqueous phase.

An emulsion prepared with 0.3M NaNO 3,C 12E 4(2wt%of oil)and dodecane (50%in volume)exhibited a phase inversion temperature (PIT)around 24?C,as determined by conductivity measurements (data not shown).This value is close to that of the aqueous system water/C 12E 4/dodecane for which the PIT temper-ature was found to be 25?C,which is consistent with the general

J.Galindo-Alvarez et al./Colloids and Surfaces A:Physicochem.Eng.Aspects396 (2012) 115–121

117

Fig.2.Typical1H NMR in D2O of a poly(sodium acrylate)hydrophobically modi?ed with azobenzene groups randomly attached along the chains.

result that the presence of salt does not affect the af?nity of sur-factant for each phase[11].It has been shown for amphiphilic polymers with a similar structure to those used in that study,that the amount of adsorbed polymer signi?cantly increased with ionic strength[12,13].All the study was carried out with a concentra-tion of sodium nitrate equal to0.3M in the aqueous phase so as to ensure a suf?cient coverage of the surface of nanodroplets and thus avoid any limitation caused by that parameter.

3.2.Behavior of polymer/surfactant mixtures in aqueous phase

As a consequence of HLB number of C12E4(9.7),its aqueous sol-ubility is very sensitive to temperature around room temperature. Thus for the C12E4/water binary system the phase diagram indi-cates that for surfactant concentrations below10wt%(which will be always the case in this study),micellar phase(L1)co-exists with surfactant solution(W)above4?C(which is the cloud point tem-perature).Above ca.20?C,surfactant solution(W)co-exists with lamellar phase(L?)up to68?C[14].

Hydrophobically modi?ed poly(sodium acrylate)is soluble in water,and the presence of0.3M NaNO3does not affect polymer solubility when alone in solution.

Aqueous phases containing C12E4,HMPA x and0.3M NaNO3 exhibited phase separation as a function of composition and temperature.A concentrated phase formed which contained the majority of the polymer,together with a dilute phase in which an excess of polymer and surfactant was https://www.wendangku.net/doc/b716106440.html,ing HMPA3.2,a direct titration of polymer remaining in the dilute phase was car-ried out at20?C in a previous study[15].It was showed that,in the phase separation zone,less than15%of HMPA3.2remained in the dilute phase.Thus,we concluded that this phase separation was of the associative type,i.e.relying on the formation of a physical network involving hydrophobic associations between hydropho-bic units of HMPA3.2and micellar aggregates of C12E4.Because of the high ionic strength of the aqueous medium(0.3M NaNO3)the swelling of the physical network was not high enough and water was expelled into the dilute phase.Indeed,when aqueous phases were prepared without the presence of salt,no phase separation was observed over the explored range of compositions.

In the present study,after mixing the various components and letting the systems reach equilibrium,three different macroscopic forms were encountered(Fig.3):(a)a concentrated upper phase coexisting with a dilute lower phase,(b)a concentrated lower phase coexisting with a dilute upper phase,(c)a uniform phase without any detectable macroscopic phase separation.The case (c)should correspond to a situation where the composition of the aqueous phase is such that the physical network formed by C12E4 and HMPA x swells into the whole volume.

Given the respective densities of various components of aqueous mixtures(see Section2)and taking into account the phase diagram of surfactant/water binary system(see above),the form(a)was considered to be a“surfactant-rich coacervate”and the form(b)a “polymer-rich coacervate”.As for the form(c),it will be designated as“macroscopically uniform system”.

We systematically investigated the phase separation of aqueous mixtures as a function of surfactant concentration(up to20g/L), HMPA x concentration(up to15g/L)and temperature(20?C and 37?C).These data are presented under the form of composition maps showing the type of aqueous system obtained as a function of C12E4and HMPA x concentrations.

When considering the aqueous mixtures C12E4/HMPA1.3/0.3M NaNO3at20?C,their phase behavior can be separated into three composition zones(Fig.4).At low HMPA1.3concentrations and high enough C12E4concentrations,surfactant-rich coacervates are formed.In the rest of the diagram,polymer-rich coacervates are formed except at very low C12E4concentrations,for which macroscopically uniform systems exist.For very low surfactant concentrations,the physical network swells enough to extend to the whole aqueous phase.Otherwise,in the rest of the diagram, associations between surfactant micelles and HMPA1.3macro-molecules lead to phase separation with one of the components dominating according to the composition.

118J.Galindo-Alvarez et al./Colloids and Surfaces A:Physicochem.Eng.Aspects 396 (2012) 115–

121

Fig.3.Types of aqueous systems obtained at equilibrium with C 12E 4/HMPA x /0.3M NaNO 3mixtures:(a)“surfactant-rich coacervate”,(b)“polymer-rich coacervate”and (c)“macroscopically uniform system”.For discussion see text.

When temperature was increased up to 37?C (Fig.5),the zone corresponding to surfactant-rich coacervate was widened as well as the one corresponding to macroscopically uniform sys-tems.On the contrary,polymer-rich coacervate was con?ned into a reduced zone.Thus,the transition undergone by C 12E 4from micelles to lamellar phase favored the formation of more extended complexes involving macromolecules which occupied the whole volume of aqueous phase provided that enough macromolecules were present in the mixture.Otherwise,surfactant-rich coacervate was formed.

Now turning to the aqueous mixtures C 12E 4/HMPA 3.2/0.3M NaNO 3at 20?C and 37?C,the observed phase behavior

was

5

10

15

20

16

12

8

4

[C 12E 4

] (g /L )

[HMPA 1.3

] (g/L)

Fig.4.Types of aqueous systems obtained at equilibrium with C 12E 4/HMPA 1.3/0.3M NaNO 3mixtures at 20?C as a function of polymer and surfactant concentrations (in g/L).“Surfactant-rich coacervate”(?),“polymer-rich coacervate”( )and “macro-scopically uniform system”( ).

similar to that of the other aqueous mixture C 12E 4/HMPA 1.3/0.3M NaNO 3provided that HMPA x concentration was expressed in moles of hydrophobic units per volume unit (Fig.6).This con?rms that phase separation is controlled by the hydrophobic association between polymer and surfactant.Indeed,for higher x values,more C 12E 4molecules are needed to associate with each HMPA x macro-molecule.

3.3.Thermo-thickening behavior of polymer-rich phase

The rheological behavior of polymer-rich coacervates was studied by oscillatory experiments between 4and 37?C.The polymer-rich coacervate formed at 4?C in the aqueous

system

05

10

15

20

16

12

8

4

[C 12E 4

] (g /L )

[HMPA 1.3

] (g/L)

Fig.5.Types of aqueous systems obtained at equilibrium with C 12E 4/HMPA 1.3/0.3M NaNO 3mixtures at 37?C as a function of polymer and surfactant concentrations (in g/L).For symbols see caption of Fig.4.

J.Galindo-Alvarez et al./Colloids and Surfaces A:Physicochem.Eng.Aspects 396 (2012) 115–121

119

04

8

5 10

-4

1 10

-3

1,5 10

-3

2 10

-3

[C 12E 4

] (g /L )

[HMPA x ] (moles of azobenzene groups/L)

Fig.6.Types of aqueous systems obtained at equilibrium with C 12E 4/HMPA x /0.3M NaNO 3mixtures at 37?C as a function of polymer and surfactant concentrations (in g/L for C 12E 4and in moles of azobenzene groups/L for HMPA x ).For HMPA 1.3,symbols are the same as in Fig.4.For HPMA 3.2,“surfactant-rich coacervate”( ),“polymer-rich coacervate”( )and “macroscopically uniform system”( ).

C 12E 4/HMPA 3.2/0.3M NaNO 3was ?rst examined.For [C 12E 4]=6g/L and [HMPA 3.2]=2g/L,this aqueous system underwent a thermal transition from “polymer rich coacervate”at 4?C to “macroscopi-cally uniform system”at 37?C.

Although the coacervate behaved as a viscoelastic ?uid at temperatures up to 25?C,storage and loss modulus (G’and G”,respectively)came to an intersection (gel point)at 37?C.This behavior was better evidenced by monitoring the variation of G’and G”with temperature between 4and 37?C (Fig.7).Both mod-uli reached a minimum near 20?C and increased signi?cantly when temperature exceeded 24?C,a temperature associated to the trans-formation of micelles into lamellar phase [14].A similar curve was obtained with the other ternary system C 12E 4/HMPA 1.3/0.3M NaNO 3except that the magnitude of increase above PIT was more reduced (data not shown).Thermothickening of aqueous solutions containing C 12E 4and a hydrophobically modi?ed

poly(sodium

10

-1

10

10

1

10

2

40

3020100Temperature (°C)

G ’ a n d G ’’ (P a )

Fig.7.Elastic (G’, )and viscous (G”,?)moduli of the aqueous system with [C 12E 4]=6g/L,[HMPA 3.2]=2g/L as a function of temperature (increasing and decreasing curves).For each series of data,upper curves are obtained when increas-ing

temperature.

Fig.8.Types of diphasic systems obtained after addition of n-dodecane to the aqueous system C 12E 4/HMPA 1.3/0.3M NaNO 3.(a)Coacervate forming an interfacial layer ([C 12E 4]=6g/L,[HMPA 1.3]=2g/L,25%oil,25?C);(b)coacervate at interface with polymer in excess in the aqueous phase ([C 12E 4]=1g/L,[HMPA 1.3]=6g/L,25%oil,25?C);Coacervate at interface with polymer in excess in the oil phase ([C 12E 4]=20g/L,[HMPA 1.3]=4g/L,25%oil,37?C).

acrylate)carrying aliphatic hydrocarbon chains was reported to occur in the same temperature range [4].On this basis,we can reasonably attribute the observed variation to the transition of C 12E 4from micellar aggregates to lamellar phase.The physical net-work is strengthened because of the formation of bigger surfactant aggregates which increase the reticulation between HMPA x macro-molecules.This increased reticulation brings about a macroscopic transition from “polymer rich coacervate”at low temperatures to “macroscopically uniform system”at temperatures above 25?C because of the simultaneous swelling of the physical network which extends to all aqueous phase.

3.4.Partitioning of polymer in the presence of n-dodecane

Various amounts of dodecane were added to aqueous sys-tems C 12E 4/HMPA 1.3/0.3M NaNO 3and the partitioning of HMPA 1.3between the two phases was systematically investigated as a func-tion of oil content (25and 50%in volume)and temperature (20and 37?C).

At 20?C,after dodecane addition,all samples exhibited a clear oil phase and an aqueous phase containing HMPA 1.3(Fig.8).More pre-cisely,HMPA 1.3was contained in an interfacial layer in contact with the upper oil phase with eventually an excess in the lower aqueous layer.The same observation was made for 25and 50%oil in vol-ume.Thus,at this temperature,the coacervate formed by HMPA 1.3and C 12E 4was able to accumulate at oil/water interface and kept a dominant hydrophilicity.

At 37?C,when the oil content was 25%,two situations were found (Figs.8and 9).In a large part of the composition map,the situation was the same as previously,i.e.HMPA 1.3was present in the aqueous phase,in the interfacial coacervate and sometimes in excess in the lower aqueous phase.Nevertheless,for high C 12E 4concentrations and low concentrations of HMPA 1.3,the polymer in

120J.Galindo-Alvarez et al./Colloids and Surfaces A:Physicochem.Eng.Aspects 396 (2012) 115–

121

05

10

15

20

16

12

8

4

[C 12E 4

] (g /L )

[HMPA 1.3

] (g/L)

Fig.9.Types of biphasic systems obtained after addition of n-dodecane to the aque-ous system C 12E 4/HMPA 1.3/0.3M NaNO 3as a function of polymer and surfactant concentrations (in g/L)at 37?C.Polymer in excess was in the aqueous phase ( ).Polymer in excess was in the oil phase (?).

excess was present in the oil phase.In that part of the composition map,the excess of C 12E 4as compared to HMPA 1.3was such that the polymer was fully contained in the coacervate and dehydration of surfactant polar heads upon increasing temperature led to the partition of this coacervate into the oil phase.The exact physical state of the coacervate in the oil phase is not known and should be further investigated.Nevertheless,the partitioning in favor of the upper oil phase was clear.Thus,in those conditions,the coacervate accumulates at interface but exhibits a dominant hydrophobic-ity,which is caused by the dehydration of C 12E 4molecules above PIT.

When 50%oil was added and setting temperature at 37?C,HMPA 1.3appeared to be only in the aqueous phase,either in the coacervate (accumulated at interface)or in excess in the lower phase.The increased volume fraction of oil modi?ed C 12E 4concentration and the conditions were no longer convenient for partitioning of coacervate in favor of the oil phase.

More work is required to better understand the conditions in which a polar amphiphilic polymer like HMPA 1.3may be involved in a coacervate which swells preferentially in an apolar phase like dodecane.In addition,further studies should detail what is the physical state of the coacervate in dodecane.Neverthe-less,these ?rst results show that in convenient concentration conditions,the coacervate involving HMPA and C 12E 4exhibits a hydrophilic/hydrophobic balance (HLB)which varies with temper-ature and particularly according to its position relatively to the PIT observed with C 12E 4.Thus,in addition to its mechanical properties,the HLB of the coacervate strongly depends on temperature (at a given ionic strength).This may induce signi?cant variations in the colloidal stability of nanoemulsions formed in the presence of this coacervate.

3.5.Colloidal stability of nanoemulsions at various temperatures

Nanoemulsions were prepared by dispersing dodecane (5%in volume)in the aqueous system C 12E 4/HMPA 3.2/0.3M NaNO 3(2g/L HMPA 3.2and 6g/L C 12E 4)using ultrasounds.

The initial average droplet size was around 200nm.Nanoemul-sion samples were stored at various temperatures (between 4and 37?C)and the average droplet size was monitored (Fig.10).The longest shelf life was reached at 37?C for which it

exceeded

Fig.10.Variation of average droplet diameter (nm)with time (h)at various stor-age temperatures,20?C ( ),27?C (?)and 37?C ( ).The aqueous phase contained HMPA 3.2at 2g/L,C 12E 4/at 6g/L in 0.3M NaNO 3and 5%dodecane in volume.Dotted lines are guides for the eyes.

90days (without any signi?cant change in average droplet size).Nanoemulsion shelf life decreased at lower temperatures and was less than 1day at 4?C.This behavior is totally different from that observed with polymer or surfactant alone.Indeed,with C 12E 4no nanoemulsion could be prepared at 20?C or above and with HMPA 3.2nanoemulsions prepared at 20?C exhibited a signi?cant increase of average droplet size (from 200to 500nm)over 50h.Consequently,the formation of the physical network involving HMPA 3.2and C 12E 4and the variation of its mechanical properties with temperature may be reasonably considered to be at the origin of this enhanced temperature stability of the formed nanoemul-sions.In addition,as shown previously,with an excess of C 12E 4,the af?nity of the polymer-surfactant complex for the oil phase is greatly increased at 37?C.Thus we can assume that,at 37?C,the interfacial layer stabilizing oil droplet is composed of associated HMPA 3.2and C 12E 4molecules forming a dense super?cial network which prevents emulsion ageing (by coalescence or Ostwald ripen-ing).The formation of a thick elastic membrane around oil droplets has already been proposed to explain the very long storage stability of nanoemulsions in the case of the formation of elastic complexes between cationic polyelectrolyte and anionic surfactant [16].Nev-ertheless,it is the ?rst time that such phenomenon is reported for nonionic surfactant and applied to temperature-induced gel for-mation.

Nanoemulsions formed in that way may undergo fast ageing by simply cooling down to below 20?C,which could be an easy method for separating the two phases by centrifugation for instance,thanks to the increase of droplet size.

4.Conclusion

Phase separation occurring in aqueous mixtures of tetraethyleneglycol dodecylether (C 12E 4)and hydrophobically modi?ed poly(sodium acrylate)was systematically investigated as a function of polymer and surfactant concentrations as well as temperature.It was shown that increasing temperature up to 37?C strongly modi?ed the macroscopic phase separation behavior of aqueous systems,a fact which was interpreted as a result of the transition in the self-organization of C 12E 4from micelles to lamel-lar phase.This transition was also evidenced through rheological measurements which revealed the contribution of this transition to the strengthening of the associative physical network involving

J.Galindo-Alvarez et al./Colloids and Surfaces A:Physicochem.Eng.Aspects396 (2012) 115–121121

C12E4and HMPA x macromolecules.These bulk phenomena were applied for enhancing the temperature stability of nanoemulsions by strengthening the mechanical properties of interfacial?lms formed by macromolecules and surfactants at oil/water interface. Signi?cant improvement of colloidal stability was observed at temperatures above20?C.

Current investigations examine the possibility to generalize the reported results to other mixtures of amphiphilic polymers and sur-factants.Other investigations are related to the application of such thermally stable nanoemulsions to miniemulsion polymerization without the use of ultra-hydrophobe additives.

Acknowledgements

We would like to acknowledge the?nancial support of Agence Nationale de la Recherche for the research stay of J.Galindo-Alvarez (project n?ANR-06-BLAN-0174).

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With的用法全解

With的用法全解 with结构是许多英语复合结构中最常用的一种。学好它对学好复合宾语结构、不定式复合结构、动名词复合结构和独立主格结构均能起很重要的作用。本文就此的构成、特点及用法等作一较全面阐述,以帮助同学们掌握这一重要的语法知识。 一、 with结构的构成 它是由介词with或without+复合结构构成,复合结构作介词with或without的复合宾语,复合宾语中第一部分宾语由名词或代词充当,第二部分补足语由形容词、副词、介词短语、动词不定式或分词充当,分词可以是现在分词,也可以是过去分词。With结构构成方式如下: 1. with或without-名词/代词+形容词; 2. with或without-名词/代词+副词; 3. with或without-名词/代词+介词短语; 4. with或without-名词/代词 +动词不定式; 5. with或without-名词/代词 +分词。 下面分别举例: 1、 She came into the room,with her nose red because of cold.(with+名词+形容词,作伴随状语)

2、 With the meal over , we all went home.(with+名词+副词,作时间状语) 3、The master was walking up and down with the ruler under his arm。(with+名词+介词短语,作伴随状语。) The teacher entered the classroom with a book in his hand. 4、He lay in the dark empty house,with not a man ,woman or child to say he was kind to me.(with+名词+不定式,作伴随状语)He could not finish it without me to help him.(without+代词 +不定式,作条件状语) 5、She fell asleep with the light burning.(with+名词+现在分词,作伴随状语) Without anything left in the with结构是许多英 语复合结构中最常用的一种。学好它对学好复合宾语结构、不定式复合结构、动名词复合结构和独立主格结构均能起很重要的作用。本文就此的构成、特点及用法等作一较全面阐述,以帮助同学们掌握这一重要的语法知识。 二、with结构的用法 with是介词,其意义颇多,一时难掌握。为帮助大家理清头绪,以教材中的句子为例,进行分类,并配以简单的解释。在句子中with结构多数充当状语,表示行为方式,伴随情况、时间、原因或条件(详见上述例句)。 1.带着,牵着…… (表动作特征)。如: Run with the kite like this.

with用法归纳

with用法归纳 (1)“用……”表示使用工具,手段等。例如: ①We can walk with our legs and feet. 我们用腿脚行走。 ②He writes with a pencil. 他用铅笔写。 (2)“和……在一起”,表示伴随。例如: ①Can you go to a movie with me? 你能和我一起去看电影'>电影吗? ②He often goes to the library with Jenny. 他常和詹妮一起去图书馆。 (3)“与……”。例如: I’d like to have a talk with you. 我很想和你说句话。 (4)“关于,对于”,表示一种关系或适应范围。例如: What’s wrong with your watch? 你的手表怎么了? (5)“带有,具有”。例如: ①He’s a tall kid with short hair. 他是个长着一头短发的高个子小孩。 ②They have no money with them. 他们没带钱。 (6)“在……方面”。例如: Kate helps me with my English. 凯特帮我学英语。 (7)“随着,与……同时”。例如: With these words, he left the room. 说完这些话,他离开了房间。 [解题过程] with结构也称为with复合结构。是由with+复合宾语组成。常在句中做状语,表示谓语动作发生的伴随情况、时间、原因、方式等。其构成有下列几种情形: 1.with+名词(或代词)+现在分词 此时,现在分词和前面的名词或代词是逻辑上的主谓关系。 例如:1)With prices going up so fast, we can't afford luxuries. 由于物价上涨很快,我们买不起高档商品。(原因状语) 2)With the crowds cheering, they drove to the palace. 在人群的欢呼声中,他们驱车来到皇宫。(伴随情况) 2.with+名词(或代词)+过去分词 此时,过去分词和前面的名词或代词是逻辑上的动宾关系。

独立主格with用法小全

独立主格篇 独立主格,首先它是一个“格”,而不是一个“句子”。在英语中任何一个句子都要有主谓结构,而在这个结构中,没有真正的主语和谓语动词,但又在逻辑上构成主谓或主表关系。独立主格结构主要用于描绘性文字中,其作用相当于一个状语从句,常用来表示时间、原因、条件、行为方式或伴随情况等。除名词/代词+名词、形容词、副词、非谓语动词及介词短语外,另有with或without短语可做独立主格,其中with可省略而without不可以。*注:独立主格结构一般放在句首,表示原因时还可放在句末;表伴随状况或补充说明时,相当于一个并列句,通常放于句末。 一、独立主格结构: 1. 名词/代词+形容词 He sat in the front row, his mouth half open. Close to the bank I saw deep pools, the water blue like the sky. 靠近岸时,我看见几汪深池塘,池水碧似蓝天。 2. 名词/代词+现在分词 Winter coming, it gets colder and colder. The rain having stopped, he went out for a walk.

The question having been settled, we wound up the meeting. 也可以The question settled, we wound up the meeting. 但含义稍有差异。前者强调了动作的先后。 We redoubled our efforts, each man working like two. 我们加倍努力,一个人干两个人的活。 3. 名词/代词+过去分词 The job finished, we went home. More time given, we should have done the job much better. *当表人体部位的词做逻辑主语时,不及物动词用现在分词,及物动词用过去分词。 He lay there, his teeth set, his hands clenched, his eyes looking straight up. 他躺在那儿,牙关紧闭,双拳紧握,两眼直视上方。 4. 名词/代词+不定式 We shall assemble at ten forty-five, the procession to start moving at precisely eleven. We divided the work, he to clean the windows and I to sweep the floor.

with用法小结

with用法小结 一、with表拥有某物 Mary married a man with a lot of money . 马莉嫁给了一个有着很多钱的男人。 I often dream of a big house with a nice garden . 我经常梦想有一个带花园的大房子。 The old man lived with a little dog on the lonely island . 这个老人和一条小狗住在荒岛上。 二、with表用某种工具或手段 I cut the apple with a sharp knife . 我用一把锋利的刀削平果。 Tom drew the picture with a pencil . 汤母用铅笔画画。 三、with表人与人之间的协同关系 make friends with sb talk with sb quarrel with sb struggle with sb fight with sb play with sb work with sb cooperate with sb I have been friends with Tom for ten years since we worked with each other, and I have never quarreled with him . 自从我们一起工作以来,我和汤姆已经是十年的朋友了,我们从没有吵过架。 四、with 表原因或理由 John was in bed with high fever . 约翰因发烧卧床。 He jumped up with joy . 他因高兴跳起来。 Father is often excited with wine . 父亲常因白酒变的兴奋。 五、with 表“带来”,或“带有,具有”,在…身上,在…身边之意

with的用法

with[wIT] prep.1.与…(在)一起,带着:Come with me. 跟我一起来吧。/ I went on holiday with my friend. 我跟我朋友一起去度假。/ Do you want to walk home with me? 你愿意和我一道走回家吗 2.(表带有或拥有)有…的,持有,随身带着:I have no money with me. 我没有带钱。/ He is a man with a hot temper. 他是一个脾气暴躁的人。/ We bought a house with a garden. 我们买了一座带花园的房子。/ China is a very large country with a long history. 中国是一个具有历史悠久的大国。3.(表方式、手段或工具)以,用:He caught the ball with his left hand. 他用左手接球。/ She wrote the letter with a pencil. 她用铅笔写那封信。4.(表材料或内容)以,用:Fill the glass with wine. 把杯子装满酒。/ The road is paved with stones. 这条路用石头铺砌。5.(表状态)在…的情况下,…地:He can read French with ease. 他能轻易地读法文。/ I finished my homework though with difficulty. 虽然有困难,我还是做完了功课。6.(表让步)尽管,虽然:With all his money, he is unhappy. 尽管他有钱,他并不快乐。/ With all his efforts, he lost the match. 虽然尽了全力,他还是输了那场比赛。7.(表条件)若是,如果:With your permission, I’ll go. 如蒙你同意我就去。8.(表原因或理由)因为,由于:He is tired with work. 他工作做累了。/ At the news we all jumped with joy. 听到这消息我们都高兴得跳了起来。9.(表时间)当…的时候,在…之后:With that remark, he left. 他说了那话就离开了。/ With daylight I hurried there to see what had happened. 天一亮我就去那儿看发生了什么事。10. (表同时或随同)与…一起,随着:The girl seemed to be growing prettier with each day. 那女孩好像长得一天比一天漂亮。11.(表伴随或附带情况)同时:I slept with the window open. 我开着窗户睡觉。/ Don’t speak with your mouth full. 不要满嘴巴食物说话。12.赞成,同意:I am with you there. 在那点上我同你意见一致。13.由…照看,交…管理,把…放在某处:I left a message for you with your secretary. 我给你留了个信儿交给你的秘书了。/ The keys are with reception. 钥匙放在接待处。14 (表连同或包含)连用,包含:The meal with wine came to £8 each. 那顿饭连酒每人8英镑。/ With preparation and marking a teacher works 12 hours a day. 一位老师连备课带批改作业每天工作12小时。15. (表对象或关系)对,关于,就…而言,对…来说:He is pleased with his new house. 他对他的新房子很满意。/ The teacher was very angry with him. 老师对他很生气。/ It’s the same with us students. 我们学生也是这样。16.(表对立或敌对)跟,以…为对手:The dog was fighting with the cat. 狗在同猫打架。/ He’s always arguing with his brother. 他老是跟他弟弟争论。17.(在祈使句中与副词连用):Away with him! 带他走!/ Off with your clothes! 脱掉衣服!/ Down with your money! 交出钱来! 【用法】1.表示方式、手段或工具等时(=以,用),注意不要受汉语意思的影响而用错搭配,如“用英语”习惯上用in English,而不是with English。2.与某些抽象名词连用时,其作用相当于一个副词:with care=carefully 认真地/ with kindness=kindly 亲切地/ with joy=joyfully 高兴地/ with anger=angrily 生气地/ with sorrow=sorrowfully 悲伤地/ with ease=easily 容易地/ with delight=delightedly 高兴地/ with great fluency =very fluently 很流利地3.表示条件时,根据情况可与虚拟语气连用:With more money I would be able to buy it. 要是钱多一点,我就买得起了。/ With better equipment, we could have finished the job even sooner. 要是设备好些,我们完成这项工作还要快些。4.比较with 和as:两者均可表示“随着”,但前者是介词,后者是连词:He will improve as he grows older. 随着年龄的增长,他会进步的。/ People’s ideas change with the change of the times. 时代变了,人们的观念也会变化。5.介词with和to 均可表示“对”,但各自的搭配不同,注意不要受汉语意思的影响而用错,如在kind, polite, rude, good, married等形容词后通常不接介词with而接to。6.复合结构“with+宾语+宾语补足语”是一个很有用的结构,它在句中主要用作状语,表示伴随、原因、时间、条件、方式等;其中的宾语补足语可以是名词、形容词、副词、现在分词、过去分词、不定式、介词短语等:I went out with the windows open. 我外出时没有关窗户。/ He stood before his teacher with his head down. 他低着头站在老师面前。/ He was lying on the bed with all his clothes on. 他和衣躺在床上。/ He died with his daughter yet a schoolgirl. 他去世时,女儿还是个小学生。/ The old man sat there with a basket beside her. 老人坐在那儿,身边放着一个篮子。/ He fell asleep with the lamp burning. 他没熄灯就睡着了。/ He sat there with his eyes closed. 他闭目坐在那儿。/ I can’t go out with all these clothes to wash. 要洗这些衣服,我无法出去了。这类结构也常用于名词后作定语:The boy with nothing on is her son. 没穿衣服的这个男孩子是她儿子。 (摘自《英语常用词多用途词典》金盾出版社) - 1 -

(完整版)with的复合结构用法及练习

with复合结构 一. with复合结构的常见形式 1.“with+名词/代词+介词短语”。 The man was walking on the street, with a book under his arm. 那人在街上走着,腋下夹着一本书。 2. “with+名词/代词+形容词”。 With the weather so close and stuffy, ten to one it’ll rain presently. 天气这么闷热,十之八九要下雨。 3. “with+名词/代词+副词”。 The square looks more beautiful than even with all the light on. 所有的灯亮起来,广场看起来更美。 4. “with+名词/代词+名词”。 He left home, with his wife a hopeless soul. 他走了,妻子十分伤心。 5. “with+名词/代词+done”。此结构过去分词和宾语是被动关系,表示动作已经完成。 With this problem solved, neomycin 1 is now in regular production. 随着这个问题的解决,新霉素一号现在已经正式产生。 6. “with+名词/代词+-ing分词”。此结构强调名词是-ing分词的动作的发出者或某动作、状态正在进行。 He felt more uneasy with the whole class staring at him. 全班同学看着他,他感到更不自然了。 7. “with+宾语+to do”。此结构中,不定式和宾语是被动关系,表示尚未发生的动作。 So in the afternoon, with nothing to do, I went on a round of the bookshops. 由于下午无事可做,我就去书店转了转。 二. with复合结构的句法功能 1. with 复合结构,在句中表状态或说明背景情况,常做伴随、方式、原因、条件等状语。With machinery to do all the work, they will soon have got in the crops. 由于所有的工作都是由机器进行,他们将很快收完庄稼。(原因状语) The boy always sleeps with his head on the arm. 这个孩子总是头枕着胳膊睡觉。(伴随状语)The soldier had him stand with his back to his father. 士兵要他背对着他父亲站着。(方式状语)With spring coming on, trees turn green. 春天到了,树变绿了。(时间状语) 2. with 复合结构可以作定语 Anyone with its eyes in his head can see it’s exactly like a rope. 任何一个头上长着眼睛的人都能看出它完全像一条绳子。 【高考链接】 1. ___two exams to worry about, I have to work really hard this weekend.(04北京) A. With B. Besides C. As for D. Because of 【解析】A。“with+宾语+不定式”作状语,表示原因。 2. It was a pity that the great writer died, ______his works unfinished. (04福建) A. for B. with C. from D.of 【解析】B。“with+宾语+过去分词”在句中作状语,表示状态。 3._____production up by 60%, the company has had another excellent year. (NMET) A. As B.For C. With D.Through 【解析】C。“with+宾语+副词”在句中作状语,表示程度。

with用法

with结构是许多英语复合结构中最常用的一种。学好它对学好复合宾语结构、不定式复合结构、动名词复合结构和独立主格结构均能起很重要的作用。本文就此的构成、特点及用法等作一较全面阐述,以帮助同学们掌握这一重要的语法知识。 一、with结构的构成 它是由介词with或without+复合结构构成,复合结构作介词with或without的复合宾语,复合宾语中第一部分宾语由名词或代词充当,第二部分补足语由形容词、副词、介词短语、动词不定式或分词充当,分词可以是现在分词,也可以是过去分词。With结构构成方式如下: 1. with或without-名词/代词+形容词; 2. with或without-名词/代词+副词; 3. with或without-名词/代词+介词短语; 4. with或without-名词/代词+动词不定式; 5. with或without-名词/代词+分词。 下面分别举例: 1、She came into the room,with her nose red because of cold.(with+名词+形容词,作伴随状语) 2、With the meal over ,we all went home.(with+名词+副词,作时间状语) 3、The master was walking up and down with the ruler under his arm。(with+名词+介词短语,作伴随状语。)The teacher entered the classroom with a book in his hand. 4、He lay in the dark empty house,with not a man ,woman or child to say he was kind to me.(with+名词+不定式,作伴随状语)He could not finish it without me to help him.(without+代词+不定式,作条件状语) 5、She fell asleep with the light burning.(with+名词+现在分词,作伴随状语) 6、Without anything left in the cupboard,she went out to get something to eat.(without+代词+过去分词,作为原因状语) 二、with结构的用法 在句子中with结构多数充当状语,表示行为方式,伴随情况、时间、原因或条件(详见上述例句)。

【初中英语】with的用法

【With的基本用法与独立主格】 with结构是许多英语复合结构中最常用的一种。学好它对学好复合宾语结构、不定式复合结构、动名词复合结构和独立主格结构均能起很重要的作用。 一、with结构的构成 它是由介词with或without+复合结构构成,复合结构作介词with或without的复合宾语,复合宾语中第一部分宾语由名词或代词充当,第二部分补足语由形容词、副词、介词短语、动词不定式或分词充当,分词可以是现在分词,也可以是过去分词。With结构构成方式如下: 1. with或without-名词/代词+形容词; 2. with或without-名词/代词+副词; 3. with或without-名词/代词+介词短语; 4. with或without-名词/代词+动词不定式; 5. with或without-名词/代词+分词。 下面分别举例: 1、She came into the room,with her nose red because of cold.(with+名词+形容词,作伴随状语) 2、With the meal over, we all went home.(with+名词+副词,作时间状语) 3、The master was walking up and down with the ruler under his arm。(with+名词+介词短语,作伴随状语。) 4、He could not finish it without me to help him.(without+代词+不定式,作条件状语) 5、She fell asleep with the light on.(with+名词+现在分词,作伴随状语) 二、with结构的用法 with是介词,其意义颇多,一时难掌握。为帮助大家理清头绪,以教材中的句子为例,进行分类,并配以简单的解释。在句子中with结构多数充当状语,表示行为方式,伴随情况、时间、原因或条件(详见上述例句)。 1. 带着,牵着……(表动作特征)。如: Run with the kite like this. 2. 附加、附带着……(表事物特征)。如: A glass of apple juice, two glasses of coke, two hamburgers with potato chips, rice and fish. 3. 和……(某人)一起。 a. 跟某人一起(居住、吃、喝、玩、交谈……) 。如: Now I am in China with my parents. Sometimes we go out to eat with our friends. He / She's talking with a friend. b. 跟go, come 连用,有"加入"到某方的意思。如: Do you want to come with me? 4. 和play一起构成短语动词play with 意为"玩耍……,玩弄……" 如: Two boys are playing with their yo-yos. 5. 与help 一起构成help...with...句式,意为"帮助(某人) 做(某事)"。如: On Monday and Wednesday, he helps his friends with their English. 6. 表示面部神情,有“含着……,带着……”如: "I'm late for school," said Sun Y ang, with tears in his eyes. 7. 表示"用……" 如:

介词with的用法

介词with的用法 1.表示人与人的协同关系,意为“一起”“和” go with 与..一起去 play with 与...一起玩 live with 与...一起住/生活 work with 与...一起工作 make friends with 与....交朋友 talk with sb = talk to sb fight with 与...打架/战斗 cooperate with 与...一起合作 2.表示“带有”“拥有” tea with honey 加蜂蜜的茶 a man with a lot of money 一个有很多钱的人 a house with a big garden 一个带有大花园的房子 a chair with three legs 一张三条腿的椅子 a girl with golden hair 金发的女孩 3.表示“用”某种工具或手段 write with a pencil 用铅笔写字 cut the apple with a knife 用刀切苹果 4.表示“在...身边”“在...身上” I don’t have any money with me. 我身上没带钱。 Take an umbrella with you in case it rains 带把伞以防下雨。 5.表示“在...之下” With the help of sb = with one’s help 在某人的帮助下 6.表示“随着” with the development of ... 随着...的发展 float with the wind 随风飘动

7.常见带有with的动词短语 agree with sb/sth 同意某人或某事deal with sth = do with sth 处理某事 help sb with sth 在...上帮助某人 fall in love with sb/sth 爱上某人/某物 get on with sb 与某人相处 get on well with sb 与某人相处得好 have nothing to do with sb 与某人无关compare A with B 将A和B作比较communicate with sb 与某人交流 argue with sb = quarrel with sb 与某人吵架Have fun with sth 玩的开心 Get away with sth 做坏事不受惩罚 Chat with sb 跟某人闲谈 Charge sb with sth 指控某人。。。 Put up with sth 忍受 8.常见带with的形容词固定搭配 be satisfied with 对...满意 be content with sth 对...满足 be angry with sb 生某人的气 be strict with sb 对某人严格 be patient with sb 对某人有耐心 be popular with sb 受某人欢迎 be filled with sth 装满... 充满..... = be full of sth What’s wrong/the matter with sb/sth be familiar with sb/sth 熟悉某人或某物 be connected with sb/sth 与....有关 Be decorated with 被。。。装饰 Be impressed with/by

with用法归纳

with用法归纳 (1)“用……”表示使用工具,手段等。例如: ①We canwalkwith ourlegsandfeet. 我们用腿脚行走。 ②Hewrites withapencil。她用铅笔写。 (2)“与……在一起”,表示伴随。例如: ①Can you gotoamovie with me?您能与我一起去瞧电影’>电影不? ②He often goes to thelibrarywithJenny、她常与詹妮一起去图书馆。 (3)“与……"。例如: I'd like to have a talk with you、我很想与您说句话、 (4)“关于,对于”,表示一种关系或适应范围。例如: What’s wrong with yourwatch?您得手表怎么了? (5)“带有,具有"。例如: ①He's a tallkid withshort hair. 她就是个长着一头短发得高个子小孩。 ②Theyhaveno money with them、她们没带钱。 (6)“在……方面”。例如: Kate helpsme with myEnglish. 凯特帮我学英语。 (7)“随着,与……同时”、例如: With thesewords, he lefttheroom、说完这些话,她离开了房间。[解题过程] with结构也称为with复合结构。就是由with+复合宾语组成。常在句中做状语,表示谓语动作发生得伴随情况、时间、原因、方式等。其构成有下列几种情形: 1。with+名词(或代词)+现在分词 此时,现在分词与前面得名词或代词就是逻辑上得主谓关系。 例如:1)Withprices going up so fast, we can’t afford luxuries、由于物价上涨很快,我们买不起高档商品。(原因状语) 2)Withthe crowds cheering, they drove to thepalace。 在人群得欢呼声中,她们驱车来到皇宫、(伴随情况) 2、with+名词(或代词)+过去分词

with结构及用法

with 结构 一:with结构的形式 它是由介词with或without+复合结构构成,复合结构作介词with或without的复合宾语,复合宾语中第一部分宾语由名词或代词充当,第二部分补足语由形容词、副词、介词短语、动词不定式或分词充当,分词可以是现在分词,也可以是过去分词。With结构构成方式如下: 1. with或without 名词/代词 例句:Yesterday I saw Mary with a gun. 2. with或without 名词/代词+ 形容词 例句:He is used to sleeping with the windows open. 3. with或without 名词/代词+ 副词 例句:She left the room with all the lights on. 4. with或without 名词/代词+ 介词短语 例句:He walked into the dark street with a stick in his hand. 5. with或without 名词/代词+ 动词不定式 例句:With so much work to do, I have no time for a holiday. 6. with或without 名词/代词+ Ving 例句:We found the house easily with the little boy leading the way.(现在分词表示主动动作,即分词所表示的动作是由with后的宾语发出来的) 7. with或without 名词/代词+ Ved With all the things bought, she went home happily.(过去分词表示被动,with后面的宾语与过去分词之间是被动关系) 8. with或without 名词/代词+ 补语 例句:Possibly this person died without anyone knowing where the coins were hidden. He wondered if he could slide out of the lecture hall without anyone noticing (him). 9. with或without 名词/代词+ 动词不定式和+ Ving/Ved的区别 加不定式是指将要进行的动作,加分词是指主动或被动动作. 10. with+名词/代词+名词 例句:He died with his daughter a schoolgirl. 他在他女儿是个小学生的时候死了 二:with复合结构的句法功能 1. with 复合结构,在句中表状态或说明背景情况该结构常做伴随、方式、原因、条件等状语。 例句:With machinery to do all the work, they will soon have got in the crops. 由于所有的工作都是由机器进行,他们将很快收完庄稼。(原因状语) The boy always sleeps with his head on the arm. 这个孩子总是头枕着胳膊睡觉。(伴随状语) The soldier had him stand with his back to his father. 士兵要他背对着他父亲站着。(方式状语)With spring coming on, trees turn green. 春天到了,树变绿了。(时间状语) 2. with复合结构可以作定语 Anyone with its eyes in his head can see it’s exactly like a rope. 任何一个头上长着眼睛的人都能看出它完全像一条绳子。

with的用法大全

with的用法大全 with结构是许多英语复合结构中最常用的一种。学好它对学好复合宾语结构、不定式复合结构、动名词复合结构和独立主格结构均能起很重要的作用。本文就此的构成、特点及用法等作一较全面阐述,以帮助同学们掌握这一重要的语法知识。 一、with结构的构成 它是由介词with或without+复合结构构成,复合结构作介词with或without的复合宾语,复合宾语中第一部分宾语由名词或代词充当,第二部分补足语由形容词、副词、介词短语、动词不定式或分词充当,分词可以是现在分词,也可以是过去分词。With结构构成方式如下: 1. with或without-名词/代词+形容词; 2. with或without-名词/代词+副词; 3. with或without-名词/代词+介词短语; 4. with或without-名词/代词+动词不定式; 5. with或without-名词/代词+分词。 下面分别举例: 1、She came into the room,with her nose red because of cold.(with+名词+形容词,作伴随状语) 2、With the meal over ,we all went home.(with+名词+副词,作时间状语)

3、The master was walking up and down with the ruler under his arm。(with+名词+介词短语,作伴随状语。) The teacher entered the classroom with a book in his hand. 4、He lay in the dark empty house,with not a man ,woman or child to say he was kind to me.(with+名词+不定式,作伴随状语) He could not finish it without me to help him.(without+代词+不定式,作条件状语) 5、She fell asleep with the light burning.(with+名词+现在分词,作伴随状语) 6、Without anything left in the cupboard,she went out to get something to eat.(without+代词+过去分词,作为原因状语) 二、with结构的用法 在句子中with结构多数充当状语,表示行为方式,伴随情况、时间、原因或条件(详见上述例句)。 With结构在句中也可以作定语。例如: 1.I like eating the mooncakes with eggs. 2.From space the earth looks like a huge water-covered globe with a few patches of land sticking out above the water. 3.A little boy with two of his front teeth missing ran into the house. 三、with结构的特点 1. with结构由介词with或without+复合结构构成。复合结构中第一部分与第二部分语法上是宾语和宾语补足语关系,而在逻辑上,却具有主谓关系,也就是说,可以用第一部分

With 的用法

With得用法 1.With sb/sthdoing 表主动且进行 2.Withsth being done表被动且进行 3.withsth done表被动且完成 4.with sth todo表示将来 1.从语法角度瞧: with 就是介词,所以后面跟得就是宾语;宾语后面得可以被称为就是宾补。 1.Withoutanyone noticing, Istol e into the room、 With so many children talking and laughing, Icouldn’tsettle down to my work、 2.With so much work beingdone, I can’t spare any minute。 3.With so muchworkdone, Ihad a niceday。 4.With a lot of problems to settle, the newly elected president is having a hardtime。 Lie 说谎-lied-lied—lying Lie躺;存在;位于-lay-lain—lying

Lay 放置;产卵下蛋-laid—laid-laying He lied说谎to me that he hadn't seen the bag that I had laid 放置on the counter、Infact itwaslying存在beside him on the ground。 Hissuggestion aiming(aim) to remov eyourbadhabit is acceptable。 His suggestion aimed(aim) atremoving your bad habit isacceptable. 迎合cater for 做出调整make adjustments 在这之前previous to this 协商negotiate 为…而准备bemeant for/be intendedfor 明年将被开展得建造工程不就是很容易被及时完成、The buildingproject to be carriedoutnext year is not easyto complete. Require doing=need doing = want d oing以主动表被动 All cars requiretesting/to be tested。 Pull through康复;完成十分困难得事情

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