毛细管流变仪课件.ppt
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1、1 IntroductionPolymers are used because:They are cheap to form into shape in molten stateTherefore,We need to understand how they flow when moltenalso important in:food processing,pharmaceuticals,paints,inks,pastes,slurries etc.Very important in Polymer ProcessingBut,molten polymers are complicated
2、systems.Temperature dependent Rate dependent Time dependent Work dependent(and thats before we add lubricants,fillers,plasticisers,foaming agents etc!)In between a liquid and a solidmolecular structure of sample temperature pressure time shear rate (T,p,t,g)=g g.Shear viscosity definitiong g-shear r
3、ate.-shear stress =g g.-shear viscosityViscosity is a measure of resistance of a fluid against the applied shear force.Shear viscosity is only one part of Rheology.It is the dominant effect for pressure in extruders,injection moulding machines and dies.1.E+001.E+021.E+041.E+061.E+081.E-051.E-031.E-0
4、11.E+011.E+031.E+05Shear rate (s-1)Viscosity (Pa.s)Typical process shear ratesRelaxationCoatingFree surfaceMixingExtrusion Injection moulding2.Structure2.16kg Single point test(generates one number)MFI die(2.095mm diameter)Defined by standards(ISO1133)Simple Cheap Easy to use Pressure drivenMelt Flo
5、w Indexer(MFI)Melt Flow Indexer(MFI)Single point test Does not generate engineering units-(grams per 10 minutes)Mainly a shear flow measurement-neglects extension Very low shear rate test(g gapp=2.4 MFI)But,1.E+001.E+021.E+041.E+061.E+081.E-051.E-031.E-011.E+011.E+031.E+05Shear rate (s-1)Viscosity (
6、Pa.s)Typical process shear ratesRelaxationCoatingFree surfaceMixingExtrusion Injection mouldingMFItestCapillary RheometerMeasure:Pressure dropPiston Capillary die Pressure transducer Polymer melt Set:Piston speedDie DimsCapillary rheometryWe set:Temperature,piston speed,die geometryWe measure:Melt p
7、ressure(long&short dies)Giving us:Shear stress(at a range or rates)Extensional stress(at a range or rates)Capillary rheometryLong die:shearShort die:extension3 Shear viscosity 完全发展区剪切应力的计算 管壁处22rPrLL2PrLPR23 Shear viscosity 不可压缩性流体剪切速率的计算)zv(r00rz-g2rzp11rv0rz0r-)rR(zp41v220r-zp8Rrdr)rR(zp21drvr2Q04
8、220R0rR0-30NwR4QgL2R3 Shear viscosityGiven quantity:piston speed wall shear rateMeasured quantity:pressure drop wall shear stressvPLBARRELPLPlPwENTRANCELENGTH FULLY DEVELOPEDFLOW REGION0Z0LMeasuring PrinciplePressure drop through a capillary/slit dieNon-Newtonian fluid rheological equation of state:
9、(power law)=K(a)n =K.a n-1n =log /log aNewtonian fluidshear rate,=4Q/r3 shear stress,=Pr/2L shear viscosity,=/Shear Flow Analysiswhere:K=consistency index (Pa.sn)n=power law(non-Newtonian)index Q=volumetric flow rate m3/min r=capillary radius(m)L=capillary length(m).P=pressure drop (Pa)g g.g g.(g)(g
10、).g g.g g.Calculation of Entrance Pressure Drops1.Historical Bagley-Method according to DIN 11443full 10 20 30 40High shear rateLow shear rateL/DPges(L/D=0)=Entrance Pressure Drop Principle:Measurement of the Full Pressure Drop at constant Shear rate and different L/D ratio Linear extrapolation to L
11、/D=0E.B.Bagley,J.Appl.Physics 28(1957),624 DDnLPDLDLPDLPPDLPfullfullentfull-/Calculation of Entrance Pressure Dropsfull10 20 30 40L/D Calculation of Entrance Pressure Drops3.Reasons for the Errors in ExtrapolationReasons:at small L/D-values non-linearities occur for all samples at the moment there i
12、s no theoretical approach at high L/D-values non-linearities due to wall slip,compressibility.(theoretical predictionfull 2 4 6 8 10 12L/DNon-linearities at small L/DHistorical BagleyTrue curve Kelly,Coates,Dobbie,Fleming,Plastics,Rubber and Composites Processing and Applications1996,vol.25,No.7,313
13、.Datas not true to scaleCalculation of Entrance Pressure Drops4.Solution:Double capillary systemfull 5 10 15 20L/DInnovation:Measurement-no Extrapolation needed!Simultaneous measurement of full pressure drop along capillary die and entrance pressure drop on orifice die Pshear=Pfull-PoOrifice die(pin
14、 hole with neglectable L/D-ratio)Capillary die with L/D=16 The Rosand Double Capillary System with orifice dieMeasure the die entrance pressure drop directly Rabinowitsch CorrectionrzRr rzd1Rdrg-drdvzdrdrdvrdrdrdvrdrvr2QzR02zR0202zR0-RzrvrzrzwRQgdw0233)3ddQ(R1ww3wQg)3dlndln(4)3dd(4wawaawawggggggFor
15、non-Newtonian flow profile Rabinowitsch Correctionn=d(log )d(log g g).Corrected shear flow(polymer melts)If n=0.5,=1.25*g gc.4 Q R3Apparent shear rate(Newtonian material)g ga=.polyethylene 0.3 to 0.6polypropylene0.3 to 0.4PVC 0.2 to 0.5polyamide0.6 to 0.9.g ga.4 Q R33n+14ng gc =.Optional,but try to
16、keep consistency!Wall Slip correctionWall Slip A fundamental assumption in most rheology is velocity at the metal wall=0 Slip is well known to occur in PVC,HDPE and metallocene catalysed polymers Difficult to measure-can be approximated using capillary rheometry Slip is affected by fillers and lubri
17、cants Evidence of wall slip Unfilled HDPE at 200C ;Data from Rosand OLR80100120140160180200220507090110130150170190210230250Shear Strain Rate(/s)Shear Stress(kPa)8 x 0.5 mm12 x 0.75 mm16 x 1 mmLine of constantShear StressWall Slip Correction 4 VsWall SlipNo Wall Slipgapp1/RslipshearfullQQQRv4sliptru
18、eappgg.2slip3true3appRv4R4Rgg.Mooney,M.,J.Rheology 2,210(1931)Wall Slip Measurement Slip component of flowrate,Q=R2 v Vs mm/s w kPaPE Vs=1.50(w/100)3.20 w 90 kPaPVC Vs=9.5(w/100)2.28 Some typical slip velocitiesMany materials only slip above a critical stress,typically 0.1 MPaExtensional Flow Analys
19、is4 Extensional Flow Analysis4 Extensional Flow Analysis 4 Extensional Flow Analysis4 Extensional Flow Analysis 拉伸黏度是在实际纺丝过程即非稳态拉伸流中的黏度。表观拉伸黏度定义为:dzdzAzFTzREEa/)(/)(11gIDGLRFFFFzF)(采用摄影的方法,对稳态的丝条拍照,从照片量取纤维直径沿轴向的变化数据)(/4)(/422zdWzdQzExtensional Flow Analysis5 melt fracture 实际成型加工及流变测量中,物料流动状态受诸多因实际成型
20、加工及流变测量中,物料流动状态受诸多因素影响,常常出现不稳定流动情形。许多情况下,流素影响,常常出现不稳定流动情形。许多情况下,流场边界条件存在一个临界值。一旦超越该临界值,就场边界条件存在一个临界值。一旦超越该临界值,就会发生从层流到湍流,从平整到波动,从管壁无滑移会发生从层流到湍流,从平整到波动,从管壁无滑移到有滑移的转变,破坏了事先假定的稳定流动条件。到有滑移的转变,破坏了事先假定的稳定流动条件。研究这类熔体流动不稳定性及壁滑现象是从研究这类熔体流动不稳定性及壁滑现象是从“否定否定”意义上讨论高分子的流变性质,具有重要意义。该问意义上讨论高分子的流变性质,具有重要意义。该问题的工程学意义
21、是,当工艺过程条件不合适,会造成题的工程学意义是,当工艺过程条件不合适,会造成制品外观、规格尺寸及材质均一性严重受损,直接影制品外观、规格尺寸及材质均一性严重受损,直接影响产品的质量和产率,严重时甚至使生产无法进行。响产品的质量和产率,严重时甚至使生产无法进行。高分子流动不稳定性主要表现为挤出过程中的熔体破高分子流动不稳定性主要表现为挤出过程中的熔体破裂现象、拉伸过程(纤维纺丝和薄膜拉伸成型)中的裂现象、拉伸过程(纤维纺丝和薄膜拉伸成型)中的拉伸共振现象及辊筒加工过程中的物料断裂现象等。拉伸共振现象及辊筒加工过程中的物料断裂现象等。熔体在管壁发生滑移与此类现象密切相关。可以肯定熔体在管壁发生滑
22、移与此类现象密切相关。可以肯定地说,这些现象与高分子液体的非线性粘弹行为,尤地说,这些现象与高分子液体的非线性粘弹行为,尤其是弹性行为有关,是高分子液体弹性湍流的表现。其是弹性行为有关,是高分子液体弹性湍流的表现。熔体的挤出破裂行为:在挤出过程中,熔体的挤出破裂行为:在挤出过程中,当熔体剪切速率超过某一临界剪切速率当熔体剪切速率超过某一临界剪切速率时,挤出物表面开始出现畸变的现象。时,挤出物表面开始出现畸变的现象。表现为:最初表面粗糙,而后随剪切速表现为:最初表面粗糙,而后随剪切速率(或切应力)的增大,分别出现波浪率(或切应力)的增大,分别出现波浪型、鲨鱼皮型、竹节型、螺旋型畸变,型、鲨鱼皮型
23、、竹节型、螺旋型畸变,直至无规破裂。直至无规破裂。从现象上分,挤出破裂行为可归为两类从现象上分,挤出破裂行为可归为两类:一类称一类称LDPE(低密度聚乙烯)型。破裂(低密度聚乙烯)型。破裂特征是先呈现粗糙表面,当挤出超过临特征是先呈现粗糙表面,当挤出超过临界剪切速率发生熔体破裂时,呈现无规界剪切速率发生熔体破裂时,呈现无规破裂状。属于此类的材料多为带支链或破裂状。属于此类的材料多为带支链或大侧基的聚合物,如聚苯乙烯、丁苯橡大侧基的聚合物,如聚苯乙烯、丁苯橡胶、支化的聚二甲基硅氧烷等。胶、支化的聚二甲基硅氧烷等。一类称一类称HDPE(高密度聚乙烯)型。熔体破裂(高密度聚乙烯)型。熔体破裂的特征是
24、先呈现粗糙表面,而后随着剪切速率的特征是先呈现粗糙表面,而后随着剪切速率的提高逐步出现有规则畸变,如竹节状、螺旋的提高逐步出现有规则畸变,如竹节状、螺旋型畸变等。很高时,出现无规破裂。属于此类型畸变等。很高时,出现无规破裂。属于此类的材料多为线型分子聚合物,如聚丁二烯、乙的材料多为线型分子聚合物,如聚丁二烯、乙烯烯-丙烯共聚物,线型的聚二甲基硅氧烷、聚丙烯共聚物,线型的聚二甲基硅氧烷、聚四氟乙烯等。四氟乙烯等。这种分类不够严格,有些材料的熔体破裂行为这种分类不够严格,有些材料的熔体破裂行为不具有这种典型性不具有这种典型性 流变曲线的差别:流变曲线的差别:属于属于LDPE型的熔体,其流变曲线上可
25、明确标型的熔体,其流变曲线上可明确标出临界剪切速率或临界剪切力出临界剪切速率或临界剪切力 位置,曲线在临位置,曲线在临界剪切速率之前为光滑曲线,之后出现波动,界剪切速率之前为光滑曲线,之后出现波动,但基本为一连续曲线但基本为一连续曲线 属于属于HDPE型的熔体,其流变曲线在达到临界型的熔体,其流变曲线在达到临界剪切速率后变得复杂。随着剪切速率的提高,剪切速率后变得复杂。随着剪切速率的提高,流变曲线出现大幅度压力振荡或剪切速率突变流变曲线出现大幅度压力振荡或剪切速率突变,曲线不连续,有时使流变测量不能进行,曲线不连续,有时使流变测量不能进行 造成熔体破裂现象的机理十分复杂,肯定地说造成熔体破裂现
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