压汞仪原理课件

关于汞(网上资源)

Mercury(onlineresources)关于汞安全的网上资源请看如下网站:Onlineresourcesregardingmercurysafetyareavailableatthefollowingsites:/mercury/index.html

(环保局EnvironmentalProtectionAgency)/Region1/steward/neeat/mercury/

(新英格兰环境救助队,提供汞的医疗救助信息和设备及怎样防止汞及其它废弃物的污染.TheNewEnglandEnvironmentalAssistanceTeam“NEEATeam”,providesmedicalfacilitieswithinformationonmercuryandhowtopreventpollutionbyminimizingmercuryandotherwaste)/region01/steward/neeat/mercury/disposal.html

(汞处置选项和汞溅出处置盒DisposalOptionsandSpillKits)/msds/m1599.htm

(汞安全数据表MaterialSafetydataSheet)©2001,2002QuantachromeInstruments关于汞(网上资源)

Mercury(onlinereso1Analysis

BasicTheory浸润/非浸润Wetting/Non-wetting

接触角ContactAngleWashburn方程压力生成PressureGeneration

体积的电容测量Capacitancemeasurementofvolume©2001,2002QuantachromeInstrumentsAnalysis

BasicTheory浸润/非浸润W2基本原理

TheFundamentalPrinciple非浸润在颗粒之间的液态汞被压入孔中,被汞侵入的孔径是所用压力的函数.这个特性被用来表征广泛的微粒和固体材料.Theforcedintrusionofliquidmercurybetweenparticlesandintoporesasafunctionofappliedpressureisroutinelyemployedtocharacterizeawiderangeofparticulateandsolidmaterials.©2001,2002QuantachromeInstruments基本原理

TheFundamentalPrinciple3浸润/接触角

Wetting/ContactAngles浸润<90非浸润>90©2001,2002QuantachromeInstruments浸润/接触角

Wetting/ContactAngle4ContactAngle:Hgonavarietyofmaterials©2001,2002QuantachromeInstrumentsContactAngle:Hgonavariet5毛细管现象

Capillarity毛细上升Capillaryrise

<90毛细下降Capillarydepression

>90©2001,2002QuantachromeInstruments毛细管现象

Capillarity毛细上升Capillary6Washburn方程andWherePisinMPaandrinµm©2001,2002QuantachromeInstrumentsWashburn方程andWherePisinM7压汞法

MercuryIntrusion在颗粒之间的液态汞被压入孔中,被汞侵入的孔径是所用压力的函数.这个特性被用来表征广泛的微粒和固体材料.

Theforcedintrusionofliquidmercurybetweenparticlesandintoporesisroutinelyemployedtocharacterizeawiderangeofparticulateandsolidmaterials.

绝大多数材料都能满足仪器对样品直径的分析要求,即样品直径应限制在2.5cm以内(对于GT共同，为10mm以内).

Mostmaterialscanbeanalyzedsolongasthesamplecanbeaccommodatedintheinstrument,whichtypicallyrestrictsthesampledimensionstonomorethan2.5cm(GT:10mm).

©2001,2002QuantachromeInstruments压汞法

MercuryIntrusion在颗粒之间的液态汞8我们从压汞法中能了解什么?

WhatCanWeLearnFromMercuryIntrusion?孔体积Porevolume

孔径分布Poresizedistribution

孔面积PoreArea

孔结构Porestructure

粒度分布Particlesizedistribution©2001,2002QuantachromeInstruments我们从压汞法中能了解什么?

WhatCanWeLear9

孔体积测定范围最主要依赖于仪器的压力范围,但也依赖于接触角.Poresizerangedependspredominantlyontheinstrumentpressurerangebutalsoonthecontactangle.

孔径上限受可得到的最低填充压力限制,而孔径下限则受最高填充压力限制.

Thelargestporesizeislimitedbythelowestfillingpressureattainableandthesmallestporesizebythehighest.

可测定粉末样品的粒度分布.Theparticlesizedistributionofpowderscanbedetermined.

应用©2001,2002QuantachromeInstruments孔体积测定范围最主要依赖于仪器的压力范围,但也依赖于接触角10大孔样品的孔径分布图©2001,2002QuantachromeInstruments大孔样品的孔径分布图©2001,2002Quantac11

在压制和烧结过程的研究中压汞法是极其有用的分析工具.

Mercuryintrusionisanextremelyusefulanalyticaltoolintheinvestigationofbothcompactionandsinteringprocesses.

在一次测量中，能分析光纤、含纤维材料、织物及过滤介质的孔直径、渗透性和孔曲率.Fibers,fibrousmats,fabricsandfiltermediaingeneralcanbeanalyzedforporesize,fiberdiameter,permeabilityandtortuosityinasinglemeasurement.与汞能形成汞齐的材料不能用压汞法分析。Thosematerialsthatamalgamatewithmercurycannotbeanalyzed.应用©2001,2002QuantachromeInstruments应用©2001,2002QuantachromeI12压汞实验的必要条件

ExperimentalRequirements

样品管(膨胀计)Cell(penetrometer)toholdthetestsample.真空/填充装置,用于从样品管和样品的孔中去除空气并将汞转移进样品管.Vacuumfillingapparatustoremoveairfromthecellandporeswithinthesampleandfortransferringmercuryintothesamplecell.压力发生器.Pressuregenerator能容纳样品管的高压仓(高压腔).High-pressurevesseltocontainthesamplecell.测量电路:监测汞体积的改变,它是所用压力值的函数Measuringcircuitstomonitorchangeinmercuryvolumeasafunctionofappliedpressure.

液压油:传导发生器产生的压力至样品管.Hydraulicfluidtotransmitthepressurefromthegeneratortothesamplecell.©2001,2002QuantachromeInstruments压汞实验的必要条件

ExperimentalRequire13样品管SampleCell样品管或膨胀计:用来装样品,并便于注汞/排汞体积的测量.Thesamplecellorpenetrometer(sometimescalledadilatometer)isusedbothtocontainthesampleandtofacilitatethemeasurementofintrusionandextrusionvolumes.©2001,2002QuantachromeInstruments样品管SampleCell样品管或膨胀计:©2001,14样品管SampleCell样品管或膨胀计:通过金属外套和电极帽(平板电极)进行注汞/排汞体积的测量.Thesamplecellorpenetrometerisusedbothtocontainthesampleandtofacilitatethemeasurementofintrusionandextrusionvolumesviametalsheathandelectrodecap.©2001,2002QuantachromeInstruments样品管SampleCell样品管或膨胀计:©2001,15CONVENIENCE:

Penetrometers(samplecells):onestyleaccommodatesbothpowdersandbulksolidsforreducedpenetrometerinventoryrequirements.Removablemetalsheathallowseasyviewingofpenetrometerstemtoconfirmproperfillandnopowderelutriation(fluidization).Macrocelloptionforcorecylindersupto2.5cmdiameterand3.5cmlong.FIGURE:POREMASTERSHORTSAMPLECELLASSEMBLYFORLOWPRESSUREMEASUREMENTSShortsamplecell(P/N74012)2mmID(P/N74014)4mmIDUpperCellHousing(shortcell)(P/N04000-6405)O-ring(P/N51001-112)CellcontactassemblyP/N01559©2001,2002QuantachromeInstrumentsCONVENIENCE:FIGURE:POREMASTER16压力Pressure>>注汞Intrusion©2001,2002QuantachromeInstruments压力Pressure>>注汞Intrusion©20017实验综述ExperimentalOverview电容法测量体积Volumemeasurement–capacitancetechnique接触角Contactangle(130º-140º)样品管抽真空Samplecellevacuation(preventelutriation)汞填充Fillwithmercury低压注汞/排汞Lowpressureintrusion/extrusion转移至液压系统,排除空气Transfertohydraulicsystem,airpurge高压注汞/排汞(扫描或步进方式) Highpressureintrusion/extrusion(scanorstep)©2001,2002QuantachromeInstruments实验综述ExperimentalOverview电容法测量18实验结果综述ResultsOverview©2001,2002QuantachromeInstruments实验结果综述ResultsOverview©2001,19压力值pressure体积变化Volumechange滞留entrapment可逆压缩(无迟滞或滞留)Reversiblecompression(nohysteresisorentrapment)内部孔的迟滞Hysteresisfrominternalpores颗粒间的空隙可能排出其中的汞,也可能不依赖于粉末压紧后的刚性Interparticlevoidsmaygiveuptheirmercuryornotdependingontherigidityofthepowder“compact”颗粒重排Particlerearrangement(大孔/空间largepores/spaces)(小孔/空间smallpores/spaces)曲线的总体观察GeneralObservationsSeegraphicalrepresentationnext…©2001,2002QuantachromeInstruments压力值pressure体积变化Volumechange滞留20举例:三段式注汞曲线

Example:3StagesofMercury“Intrusion”粉末压缩PowderCompression空体积填充VoidFilling孔填充PoreFilling©2001,2002QuantachromeInstruments举例:三段式注汞曲线

Example:3Stageso21表观孔直径Apparentporediameter(logscale)volume(Large)(Small)曲线的总体观察GeneralObservations©2001,2002QuantachromeInstruments表观孔直径Apparentporediameter(l22大孔在低压填充,小孔在高压填充

Largeporesfillatlowpressures,smallerporesathigherpressures.

颗粒间的空隙也在低压填充并能干扰数据判读Interparticlevoidsalsofillatlowerpressuresandcaninterferewiththeinterpretationofdata.

松散的粉末在增压的影响下能被压紧

Loosepowdersmaycompactundertheinfluenceoftheincreasingpressure.

logPApparentVolumeIntruded实验结果综述ResultsOverview©2001,2002QuantachromeInstruments大孔在低压填充,小孔在高压填充23迟滞现象Hysteresis注汞曲线不能顺原路返回(排汞曲线位于注汞曲线上方)

Intrusioncurvesarenotretraceable(Extrusioncurveslieabovetheintrusioncurve)注汞和排汞之间的的改变能解释迟滞现象Canbeexplainedbychangesinbetweenintrusionandextrusion一些汞会残留在孔中….Somemercuryremainsinthepores…©2001,2002QuantachromeInstruments迟滞现象Hysteresis注汞曲线不能顺原路返回(排汞曲线24滞留现象Entrapment

滞留现象:汞遗留在孔中.

Mercuryleftbehindinthepores:entrapment

在第一次循环之后,滞留现象终止.Entrapmentceasesafterthefirstfewcycles

具有复杂网状结构的孔会产生这样的滞留Complexnetworkofporesresponsibleforsuchentrapment©2001,2002QuantachromeInstruments滞留现象Entrapment滞留现象:汞遗留在孔中.©25样品室Samplecompartment

样品管管颈大小Stemsize

巨型管Macrocell

粉末样品Powders

样品准备:选择和装填样品管

SamplePreparation:SelectingandLoadingSampleCell

©2001,2002QuantachromeInstruments样品室Samplecompartment样品准备:选择和26慢抽(细抽)真空Fineevacuation

时间,压力Time,pressure快抽(粗抽)真空Coarseevacuation时间,压力Time,pressure样品准备:抽真空参数

SamplePreparation:EvacuationParameters©2001,2002QuantachromeInstruments慢抽(细抽)真空Fineevacuation样品准备:抽27Analysis

LowPressureRangeIntrusion/ExtrusionFillpressureRepeats©2001,2002QuantachromeInstrumentsAnalysis

LowPressureRange©28Analysis

DensityWeighings©2001,2002QuantachromeInstrumentsAnalysis

DensityWeighings©229Analysis

HighPressureTransferofsamplecellRangeIntrusion/ExtrusionScanning/StepwiseRepeats©2001,2002QuantachromeInstrumentsAnalysis

HighPressureTransf30报告(数据处理)Reports(DataReduction)文件综合FileIntegration

减除空白BlankSubtraction

单位Units

孔径分布PoreSizeDistributions

其它计算OtherCalculations

进一步解释FurtherInterpretation©2001,2002QuantachromeInstruments报告(数据处理)Reports(DataReductio31

报告(数据处理)Reports(DataReduction)

文件综合FileIntegration合并低压和高压文件MergingLowPressure&HighPressureFiles

合并后可观察到迟滞程度WhatHappenstoHysteresis?©2001,2002QuantachromeInstruments报告(数据处理)Reports(DataReduc32报告(数据处理)Reports(DataReduction)

减除空白BlankSubtraction空管Emptycell偏离零点的原因:Deviationsfromzero:受热Heating遇冷Cooling可压缩性Compressibility电介质改变Dielectricchange其它Other©2001,2002QuantachromeInstruments报告(数据处理)Reports(DataReductio33报告(数据处理)Reports(DataReduction)

单位Units压力Pressure

尺寸Size

半径/直径Radius/Diameter©2001,2002QuantachromeInstruments报告(数据处理)Reports(DataReductio34报告(数据处理)Reports(DataReduction)

孔径分布PoreSizeDistributions累积量(积分)CumulativedV/dr(微分)dV/dlogr(对半径对数的微分)直方图(柱状图)Histograms

内插法Interpolation©2001,2002QuantachromeInstruments报告(数据处理)Reports(DataReductio35报告(数据处理)Reports(DataReduction)

进一步阐述FurtherInterpretations汞滞留Entrapment

接触角迟滞Contactanglehysteresis

压实/扭曲Compaction/buckling

压碎强度分布Crushstrengthdistribution©2001,2002QuantachromeInstruments报告(数据处理)Reports(DataReductio36压实Compaction©2001,2002QuantachromeInstruments压实Compaction©2001,2002Quant37Calculations©2001,2002QuantachromeInstrumentsCalculations©2001,2002Quant38表面积计算

SurfaceAreaCalculation©2001,2002QuantachromeInstruments表面积计算

SurfaceAreaCalculation39表面积计算(续)

SurfaceArea(continued)©2001,2002QuantachromeInstruments表面积计算(续)

SurfaceArea(continu40表面积SurfaceAreabetween34.5(r=0.0213m)and414MPa(r=0.00178m)

图1是一条累积孔体积曲线，该曲线显示出进入孔道的总体积以及颗粒间的空隙对施加的压力的曲线。利用公式积分计算可得所有孔道以及注汞压力P下的孔隙的表面积.

曲线上最开始的斜率很陡，是因为汞压入了大孔和颗粒间的空隙。在接近于5000psia以上出现变化意味着汞开始注入半径为0.02μm的孔内，而且随着压力升高，汞逐渐压入更窄的孔道内。在大于30,000psia未呈现明显的压入，则表明孔径小于0.0035μm的孔极少。

压力(psia)10000 20000 30000 40000 50000 60000©2001,2002QuantachromeInstruments表面积SurfaceAreabetween34.5(r41孔径/面积分布PoreSize/AreaDistribution是体积孔径分布(孔体积/单位孔半径)isthevolumeporesizedistribution(porevolume/unitporeradius)是孔面积分布(孔面积/单位孔半径)istheporesurfaceareadistribution(surfacearea/unitporeradius)

©2001,2002QuantachromeInstruments孔径/面积分布PoreSize/AreaDistrib42孔径/体积/面积分布图

PoreSize/Volume/AreaDistributionareavolume©2001,2002QuantachromeInstruments孔径/体积/面积分布图

PoreSize/Volume/43报告(数据处理)Reports(DataReduction)

其它计算OtherCalculations

密度Density

孔隙率Porosity---材料中孔隙的总体积与整个材料的体积之间的比率

颗粒粒径ParticleSize

孔喉比Throat/PoreRatio

压缩率Compressibility---可压缩的程度

渗透率Permeability---液体或气体通过多孔材料的流速

孔曲率Tortuosity---弯曲的性质或状态

分形维数FractalDimension©2001,2002QuantachromeInstruments报告(数据处理)Reports(DataReductio44孔隙率Porosity

=porosityHg=mercurydensityHe=heliumdensity©2001,2002QuantachromeInstruments孔隙率Porosity=porosity©20045颗粒的孔隙率

ParticlePorosity

颗粒间的孔隙率

Interparticleporosity

通过测量颗粒间的空体积 Thisisameasureofthevoidvolumebetweentheparticles.

颗粒内的孔隙率

Intraparticleporosity 通过测量颗粒间内被孔占据的体积 Thisisameasureofthevolumeoccupiedbyporeswithintheparticles.©2001,2002QuantachromeInstruments颗粒的孔隙率ParticlePorosity颗粒间的46颗粒的孔隙率(续)ParticlePorosity(continued)需要松装体积(堆密度)信息,这可以直接输入,也可以从汞置换重量中计算得到.

Requiresbulkvolume(density)informationwhichcanbeinputdirectlyorcalculatedfromtheweightofmercurydisplaced.©2001,2002QuantachromeInstruments颗粒的孔隙率(续)ParticlePorosity(co47ParticleSizeTheories

MS(Mayer-Stowe)TheorySS(Smith-Stermer)Theory©2001,2002QuantachromeInstrumentsParticleSizeTheoriesMS(Ma48粒径计算原理

ParticleSizeTheories©2001,2002QuantachromeInstruments粒径计算原理

ParticleSizeTheories©49粒径计算原理

ParticleSizeTheories©2001,2002QuantachromeInstruments粒径计算原理

ParticleSizeTheories©50(通常为10.73for=140anda=37.5%)Mayer-StoweTheory(MS)=穿透压力breakthroughpressure(N/m)=比例常数proportionalityconstant=颗粒直径

particlediameter(m)©2001,2002QuantachromeInstruments(通常为10.73for=140anda51Smith-StermerTheory(SS)是一个描述在固定直径D的颗粒之间注汞的核心文件.isakernelthatdescribesmercuryintrusionbetweenparticlesoffixeddiameterD.是粒径分布istheparticlesizedistribution©2001,2002QuantachromeInstrumentsSmith-StermerTheory(SS)是一个描述52ParticleSizeDistributions©2001,2002QuantachromeInstrumentsParticleSizeDistributions©253Pore-ThroatRatiosThroatPore©2001,2002QuantachromeInstrumentsPore-ThroatRatiosThroatPore©54孔曲率PoreTortuosityDeff=有效扩散系数effectivediffusivityDb=自由(散装)流体的扩散系数bulkfluiddiffusivityc=孔体积分数porevolumefraction=扭曲系数tortuosityfactor©2001,2002QuantachromeInstruments孔曲率PoreTortuosityDeff=有效扩散系55渗透率PermeabilityK=渗透率permeability=粉末床的孔隙率powderbedporositydp=平均孔直径averageporediameter©2001,2002QuantachromeInstruments渗透率PermeabilityK=渗透率permeabi56分形维数FractalDimension(D)

和普通维数（0，1，2，3）相对应的维数称为分形维数。通常，它们的维数值不是整数。分形维数是表征表面粗糙度的参数Aparameterthatcharacterizesthedegreeofroughnessofasurface

最完美的平坦表面D=2

AperfectlyflatsurfacehasD=2最粗糙的表面D=3

AcompletelyroughsurfacehasD=3

真实表面:2<D<3Realsurfaceshave2<D<3©2001,2002QuantachromeInstruments分形维数FractalDimension(D)和普通维57关于分形维数(D)–历史

在欧氏空间中，人们习惯把空间看成三维的，习惯于整数的维数。分形理论把维数视为分数。为了定量地描述客观事物的“非规则”程度，1919年，数学家从测度的角度引入了维数概念，将维数从整数扩大到分数，从而突破了一般拓扑集维数为整数的界限。©2001,2002QuantachromeInstruments关于分形维数(D)–历史

在欧氏空间中，人们习惯把58关于分形维数

(D)-概念

分维的概念:首先画一个线段、正方形和立方体，它们的边长都是1。将它们的边长二等分，此时，原图的线度缩小为原来的1/2，而将原图等分为若干个相似的图形。其线段、正方形、立方体分别被等分为2^1、2^2和2^3个相似的子图形，其中的指数1、2、3，正好等于与图形相应的经验维数。一般说来，如果某图形是由把原图缩小为1/a的相似的b个图形所组成，有：

a^D=b,

D=logb/loga的关系成立，则指数D称为相似性维数，D可以是整数，也可以是分数。©2001,2002QuantachromeInstruments关于分形维数(D)-概念©2001,2002Quan59关于分形维数

(D)分形几何与传统几何相比有什么特点：

从整体上看，分形几何图形是处处不规则的。例如，海岸线和山川形状，从远距离观察，其形状是极不规则的。

在不同尺度上，图形的规则性又是相同的。上述的海岸线和山川形状，从近距离观察，其局部形状又和整体形态相似，它们从整体到局部，都是自相似的。当然，也有一些分形几何图形，它们并不完全是自相似的。其中一些是用来描述一般随即现象的，还有一些是用来描述混沌和非线性系统的。©2001,2002QuantachromeInstruments关于分形维数(D)分形几何与传统几何相比有什么特点：©260为什么要研究分形？

分形形态是自然界普遍存在的，研究分形，是探讨自然界的复杂事物的客观规律及其内在联系的需要，分形提供了新的概念和方法。

分形具有广阔的应用前景，在分形的发展过程中，许多传统的科学难题，由于分形的引入而取得显著进展。

分形作为一种新的概念和方法，正在许多领域开展应用探索。80年代初国外开始的“分形热”经久不息。美国著名物理学家惠勒说过：今后谁不熟悉分形，谁就不能被称为科学上的文化人。©2001,2002QuantachromeInstruments为什么要研究分形？

分形形态是自然界普遍存在的，研究分形61分形维数

(D)-计算过程作图Plot:log(dv/dp)vslogP拟合直线,测定斜率SFitstraightline;determineslope,S分形维数FractalDimension,D=4+S

(斜率是负值slopeisnegative)©2001,2002QuantachromeInstruments分形维数(D)-计算过程作图Plot:log(dv/62FractalDimension(D)©2001,2002QuantachromeInstrumentsFractalDimension(D)©2001,263FractalDimension(D)D=2.9取压力值2~20的数据Log(P)

©2001,2002QuantachromeInstrumentsFractalDimension(D)D=2.9取压64FractalDimension(D)D=2.03取压力值1000~5000的数据Log(P)

©2001,2002QuantachromeInstrumentsFractalDimension(D)D=2.03取65需注意的问题MoreResults粉末在低压下可能重排,即它们被压成一体或被压缩. Powdersmayrearrangeatlowpressures,i.e.theycompactorcompress.一些非常软的低密度材料,如硅胶会有类似压弯曲的过程.Someveryweaklowdensitymaterials,suchassilicagels,mayalsoundergoasimilarprocessof”buckling”.

如果样品弹性是可逆的,固体压缩与迟滞现象不是通常的相关.

Solidcompression,whichifelasticisreversible,isnotnormallyassociatedwithsignificanthysteresis.©2001,2002QuantachromeInstruments需注意的问题MoreResults粉末在低压下可能重排,66需注意的问题(续)MoreResults对于海绵材料,在汞有机会进入其中之前,它能通过孔的收缩被压缩.当汞侵入后,汞能够改变孔结构并导致报告的孔径小于实验开始时存在的孔径.

Spongymaterialsmaycompressbyshrinkageoftheporesbeforemercuryhasanopportunitytointrudeintothem.Whenthemercurydoesintrude,itisintoanalteredporestructureandmayreportsizessmallerthanexistinthestartingmaterial.©2001,2002QuantachromeInstruments需注意的问题(续)MoreResults对于海绵材料,在67压缩率(海绵材料)

Compressibility(Spongymaterial)2500050001000015000200001.00.80.60.40.20Pressure,psiReversiblecompression©2001,2002QuantachromeInstruments压缩率(海绵材料)

Compressibility(Spo68压缩率Compressibility©2001,2002QuantachromeInstruments压缩率Compressibility©2001,200269一些实际经验

SomePracticalObservations最大的可能压力约为400MPa(60,000psior4,000个大气压),汞不能进入孔直径3.6nm以下的孔.所以,该技术不能用于评估微孔(2nm以下的孔).

Atthemaximumpossiblepressure,approximately400MPa(60,000psior4,000atmospheres),mercuryisabletopenetrateintoporesnosmallerthan3.6nm(36angstroms).Therefore,thistechniquecannotbeusedtoevaluatemicropores(lessthan2nmdiameterbyIUPACdefinition).©2001,2002QuantachromeInstruments一些实际经验

SomePracticalObservat70滞留现象Entrapment不是所有被压入的汞在减压过程中都能被排出.当外部压力降低时,少量汞无力从孔网中流出而残留或深陷在样品中.

Notallintrudedmercuryisextrudedfromthesampleduringdepressurization.Retained,orentrappedmercuryresultsfromtheinabilityofmercurytoflowbackoutofaporenetworksufficientlyquicklywhentheexternalpressureisdropped.

一般来说,降压越快,残流的汞越多.这是由于在孔网中汞流的有限的抗张强度所致.

Typically,thefasterthedepressurizationthegreaterthequantityofentrappedmercury.Thisisduetothelimitedtensilestrengthofthethreadofmercuryrunningthroughtheporenetwork.©2001,2002QuantachromeInstruments滞留现象Entrapment不是所有被压入的汞在减压过程中都71StandardMethodsASTMD4404-84(1998)e1StandardTestMethodforDeterminationofPoreVolumeandPoreVolumeDistributionofSoilandRockbyMercuryIntrusionPorosimetry

D4284-92StandardTestMethodforDeterminingPoreVolumeDistributionofCatalystsbyMercuryIntrusionPorosimetry

D2873-94(1999)e1StandardTestMethodforInteriorPorosityofPoly(VinylChloride)(PVC)ResinsbyMercuryIntrusionPorosimetry©2001,2002QuantachromeInstrumentsStandardMethodsASTM©2001,272StandardMethodsBSiBS7591-1:1992Porosityandporesizedistributionofmaterials.Methodofevaluationbymercuryporosimetry.USPUSP<267>©2001,2002QuantachromeInstrumentsStandardMethodsBSi©2001,2073MercuryPorosimetryReviewWhy?Largeporesoutsidetherangeofgassorption.Sequentialfromexteriortointerior(cfgassorption).Porestructureinformation.Additionaldatasuchas:CompressionParticlesizeFractalsPermeability©2001,2002QuantachromeInstrumentsMercuryPorosimetryReviewWhy?74关于汞(网上资源)

Mercury(onlineresources)关于汞安全的网上资源请看如下网站:Onlineresourcesregardingmercurysafetyareavailableatthefollowingsites:/mercury/index.html

(环保局EnvironmentalProtectionAgency)/Region1/steward/neeat/mercury/

(新英格兰环境救助队,提供汞的医疗救助信息和设备及怎样防止汞及其它废弃物的污染.TheNewEnglandEnvironmentalAssistanceTeam“NEEATeam”,providesmedicalfacilitieswithinformationonmercuryandhowtopreventpollutionbyminimizingmercuryandotherwaste)/region01/steward/neeat/mercury/disposal.html

(汞处置选项和汞溅出处置盒DisposalOptionsandSpillKits)/msds/m1599.htm

(汞安全数据表MaterialSafetydataSheet)©2001,2002QuantachromeInstruments关于汞(网上资源)

Mercury(onlinereso75Analysis

BasicTheory浸润/非浸润Wetting/Non-wetting

接触角ContactAngleWashburn方程压力生成PressureGeneration

体积的电容测量Capacitancemeasurementofvolume©2001,2002QuantachromeInstrumentsAnalysis

BasicTheory浸润/非浸润W76基本原理

TheFundamentalPrinciple非浸润在颗粒之间的液态汞被压入孔中,被汞侵入的孔径是所用压力的函数.这个特性被用来表征广泛的微粒和固体材料.Theforcedintrusionofliquidmercurybetweenparticlesandintoporesasafunctionofappliedpressureisroutinelyemployedtocharacterizeawiderangeofparticulateandsolidmaterials.©2001,2002QuantachromeInstruments基本原理

TheFundamentalPrinciple77浸润/接触角

Wetting/ContactAngles浸润<90非浸润>90©2001,2002QuantachromeInstruments浸润/接触角

Wetting/ContactAngle78ContactAngle:Hgonavarietyofmaterials©2001,2002QuantachromeInstrumentsContactAngle:Hgonavariet79毛细管现象

Capillarity毛细上升Capillaryrise

<90毛细下降Capillarydepression

>90©2001,2002QuantachromeInstruments毛细管现象

Capillarity毛细上升Capillary80Washburn方程andWherePisinMPaandrinµm©2001,2002QuantachromeInstrumentsWashburn方程andWherePisinM81压汞法

MercuryIntrusion在颗粒之间的液态汞被压入孔中,被汞侵入的孔径是所用压力的函数.这个特性被用来表征广泛的微粒和固体材料.

Theforcedintrusionofliquidmercurybetweenparticlesandintoporesisroutinelyemployedtocharacterizeawiderangeofparticulateandsolidmaterials.

绝大多数材料都能满足仪器对样品直径的分析要求,即样品直径应限制在2.5cm以内(对于GT共同，为10mm以内).

Mostmaterialscanbeanalyzedsolongasthesamplecanbeaccommodatedintheinstrument,whichtypicallyrestrictsthesampledimensionstonomorethan2.5cm(GT:10mm).

©2001,2002QuantachromeInstruments压汞法

MercuryIntrusion在颗粒之间的液态汞82我们从压汞法中能了解什么?

WhatCanWeLearnFromMercuryIntrusion?孔体积Porevolume

孔径分布Poresizedistribution

孔面积PoreArea

孔结构Porestructure

粒度分布Particlesizedistribution©2001,2002QuantachromeInstruments我们从压汞法中能了解什么?

WhatCanWeLear83

孔体积测定范围最主要依赖于仪器的压力范围,但也依赖于接触角.Poresizerangedependspredominantlyontheinstrumentpressurerangebutalsoonthecontactangle.

孔径上限受可得到的最低填充压力限制,而孔径下限则受最高填充压力限制.

Thelargestporesizeislimitedbythelowestfillingpressureattainableandthesmallestporesizebythehighest.

可测定粉末样品的粒度分布.Theparticlesizedistributionofpowderscanbedetermined.

应用©2001,2002QuantachromeInstruments孔体积测定范围最主要依赖于仪器的压力范围,但也依赖于接触角84大孔样品的孔径分布图©2001,2002QuantachromeInstruments大孔样品的孔径分布图©2001,2002Quantac85

在压制和烧结过程的研究中压汞法是极其有用的分析工具.

Mercuryintrusionisanextremelyusefulanalyticaltoolintheinvestigationofbothcompactionandsinteringprocesses.

在一次测量中，能分析光纤、含纤维材料、织物及过滤介质的孔直径、渗透性和孔曲率.Fibers,fibrousmats,fabricsandfiltermediaingeneralcanbeanalyzedforporesize,fiberdiameter,permeabilityandtortuosityinasinglemeasurement.与汞能形成汞齐的材料不能用压汞法分析。Thosematerialsthatamalgamatewithmercurycannotbeanalyzed.应用©2001,2002QuantachromeInstruments应用©2001,2002QuantachromeI86压汞实验的必要条件

ExperimentalRequirements

样品管(膨胀计)Cell(penetrometer)toholdthetestsample.真空/填充装置,用于从样品管和样品的孔中去除空气并将汞转移进样品管.Vacuumfillingapparatustoremoveairfromthecellandporeswithinthesampleandfortransferringmercuryintothesamplecell.压力发生器.Pressuregenerator能容纳样品管的高压仓(高压腔).High-pressurevesseltocontainthesamplecell.测量电路:监测汞体积的改变,它是所用压力值的函数Measuringcircuitstomonitorchangeinmercuryvolumeasafunctionofappliedpressure.

液压油:传导发生器产生的压力至样品管.Hydraulicfluidtotransmitthepressurefromthegeneratortothesamplecell.©2001,2002QuantachromeInstruments压汞实验的必要条件

ExperimentalRequire87样品管SampleCell样品管或膨胀计:用来装样品,并便于注汞/排汞体积的测量.Thesamplecellorpenetrometer(sometimescalledadilatometer)isusedbothtocontainthesampleandtofacilitatethemeasurementofintrusionandextrusionvolumes.©2001,2002QuantachromeInstruments样品管SampleCell样品管或膨胀计:©2001,88样品管SampleCell样品管或膨胀计:通过金属外套和电极帽(平板电极)进行注汞/排汞体积的测量.Thesamplecellorpenetrometerisusedbothtocontainthesampleandtofacilitatethemeasurementofintrusionandextrusionvolumesviametalsheathandelectrodecap.©2001,2002QuantachromeInstruments样品管SampleCell样品管或膨胀计:©2001,89CONVENIENCE:

Penetrometers(samplecells):onestyleaccommodatesbothpowdersandbulksolidsforreducedpenetrometerinventoryrequirements.Removablemetalsheathallowseasyviewingofpenetrometerstemtoconfirmproperfillandnopowderelutriation(fluidization).Macrocelloptionforcorecylindersupto2.5cmdiameterand3.5cmlong.FIGURE:POREMASTERSHORTSAMPLECELLASSEMBLYFORLOWPRESSUREMEASUREMENTSShortsamplecell(P/N74012)2mmID(P/N74014)4mmIDUpperCellHousing(shortcell)(P/N04000-6405)O-ring(P/N51001-112)CellcontactassemblyP/N01559©2001,2002QuantachromeInstrumentsCONVENIENCE:FIGURE:POREMASTER90压力Pressure>>注汞Intrusion©2001,2002QuantachromeInstruments压力Pressure>>注汞Intrusion©20091实验综述ExperimentalOverview电容法测量体积Volumemeasurement–capacitancetechnique接触角Contactangle(130º-140º)样品管抽真空Samplecellevacuation(preventelutriation)汞填充Fillwithmercury低压注汞/排汞Lowpressureintrusion/extrusion转移至液压系统,排除空气Transfertohydraulicsystem,airpurge高压注汞/排汞(扫描或步进方式) Highpressureintrusion/extrusion(scanorstep)©2001,2002QuantachromeInstruments实验综述ExperimentalOverview电容法测量92实验结果综述ResultsOverview©2001,2002QuantachromeInstruments实验结果综述ResultsOverview©2001,93压力值pressure体积变化Volumechange滞留entrapment可逆压缩(无迟滞或滞留)Reversiblecompression(nohysteresisorentrapment)内部孔的迟滞Hysteresisfrominternalpores颗粒间的空隙可能排出其中的汞,也可能不依赖于粉末压紧后的刚性Interparticlevoidsmaygiveuptheirmercuryornotdependingontherigidityofthepowder“compact”颗粒重排Particlerearrangement(大孔/空间largepores/spaces)(小孔/空间smallpores/spaces)曲线的总体观察GeneralObservationsSeegraphicalrepresentationnext…©2001,2002QuantachromeInstruments压力值pressure体积变化Volumechange滞留94举例:三段式注汞曲线

Example:3StagesofMercury“Intrusion”粉末压缩PowderCompression空体积填充VoidFilling孔填充PoreFilling©2001,2002QuantachromeInstruments举例:三段式注汞曲线

Example:3Stageso95表观孔直径Apparentporediameter(logscale)volume(Large)(Small