纳米粒度和自动滴定NanoZS

马尔文马尔文纳米粒度纳米粒度及及 Zeta电位分析仪电位分析仪光散射技术的新进展2003.10CONTENTSlZetasizer rangel光相关光谱Photon Correlation Spectroscopy(PCS)KPCS 理论概述K马尔文高灵敏的粒度仪 Zetasizer(HS)系列介绍K专利的最新型检测器，激光功率多种选择lZeta 电位KZeta 电位理论概述K多用途滴定器(MPT-1)KNew Zeta Potential Transfer Standard(DTS0050)THE ZETASIZER RANGE l用微量电泳法测定水和非水体系中粒子的Zeta电位KZeta 电位可权威地预测分散体系(悬浮液，乳化液)的长期稳定性l用光相关光谱测量分散体系中粒径分布世世 界界 顶顶 级级 纳纳 米米 颗颗 粒粒 和和 大大 分分 子子 特特 性性 分分 析析 仪仪 器器纳米粒度及纳米粒度及 Zeta电位分析仪电位分析仪 新一代新一代Zetasizer Nano ZS位于英国的马尔文公司总部 英国马尔文仪器有限公司英国马尔文仪器有限公司 _激光粒度分析仪的创始人激光粒度分析仪的创始人-世界上最大的激光粒度分析仪专业设计和生产厂家世界上最大的激光粒度分析仪专业设计和生产厂家-世界上第一台相关处理器世界上第一台相关处理器-世界上第一台激光衍射法粒度分析仪，世界上第一台激光衍射法粒度分析仪，-世界上第一台激光世界上第一台激光PCSPCS粒度分析仪粒度分析仪-世界上第一台超声粒度分析仪世界上第一台超声粒度分析仪-销售量占世界第一，仅中国大陆已有销售量占世界第一，仅中国大陆已有600600台以上台以上-已获得已获得ISO9001ISO9001标准标准,欧洲欧洲EMCEMC标准认证标准认证,GMP,GMP标准认标准认 证，唯一完全符合美国证，唯一完全符合美国FDA FDA QSpecQSpec要求要求-多方位应用支持，在中国设立正式技术服务中心多方位应用支持，在中国设立正式技术服务中心.马尔文光子相关光谱仪的发展马尔文光子相关光谱仪的发展Size distribution(s)51050 1005001000Diameter(nm)510%in classZave=3.6nm世界第一台 PCS纳米粒度分析系统(1970年)1970年,马尔文数字相关器，一个革命性的光子交叉相关(PCCS)数字信号处理系统，在皇家信号与雷达军工实验室（Royal Signals and Radar Establishment）开发成功。世界第一台商用激光粒度分析仪及马尔文仪器公司随之诞生，并成为激光粒度分析仪技术的先锋。随后进一步开发了动态光散射的光子相关（PCS）亚微米测量技术。Zetasizer 1000,2000,3000 (1997年)ZETASIZER 1000Size measurement at 90 deg.2nm to 3 micronsZETASIZER 2000Zeta potential measurement of particles of 5nm to 30 microns size in aqueous and non aqueous systemsZETASIZER 3000Combination of 1000 and 2000 plussize measurement at 12 deg.ZETASIZER 1000 and 2000 can be upgraded to 3000ZETASIZER SerieslZETASIZER 1000 and 2000 can be upgraded to 3000Zetasizer HS系列 纳米粒度及Zeta电位分析仪和MPT-1 自动滴定系统(1999年)The MPT-1 是为是为Zetasizer分析仪特制的高效专用自动滴定装置分析仪特制的高效专用自动滴定装置 粒径范围：2 nm 3000 nm 专利高灵敏测量系统,下限测量无须高功率激光器。2000年最新M3专利技术，具有高分辨高准确性，可分辨混合粒子1mV的Zeta电位差异。突出的高重现性，由精确的内部温控技术和在线pH测量加以保证。全自动三元滴定系统：精确控制、实时测量pH，盐浓度和电导率的连续变化。全自动结果自诊断系统：结果判断因子(RQF)保证了每次测量质量。内置ISO13321标准指导操作。THE ZETASIZER RANGEINTENSITYZETASIZE 型号测量范围 PARAMETER MEASUREDYESYESYESNONOYESYESYESNONOYESYES90o FIXED ALIGNMENT10001000HS S90Nano S5 to 3000nm2 to 3000nm0.6 to 6000nm2 to 3000nmThe New Zetasizer Nano seriesSizeKMeasurement of colloids,emulsions and moleculesKHigh sensitivity and high concentration Zeta potentialKZero maintenance zeta potential measurementMolecular weightKProteins and polymers5 new instrumentsNew ZetaSize(backscatter)New Zeta&Size(backscatter)Size 90 degreesNew Zeta with 90 degree sizeWhat Does a Conventional PCS Instrument Consist Of?PinholeDetector(Photomultiplier/AvalanchePhoto Diode)LaserSample containing particlesScattered lightWHAT DOES A PCS INSTRUMENT CONSIST OF?PinholeDetector(Photomultiplier/AvalanchePhoto Diode)LaserSample containing particlesComputercontainingcorrelator card(7132)Scattered lightZetasizer HS(High Sensitivity)instruments contain an APD detectorTHE INTENSITY OF SCATTERED LIGHTThe intensity of scattered light obtained from a dispersion of particles is dependent uponLaser wavelength Particle size www.malvern.co.ukSCATTERED LIGHT AND PARTICLE SIZEDispersion of smallparticlesLaserThe intensity of scattered light from small particlesis equal in all directionswww.malvern.co.ukSCATTERED LIGHT AND PARTICLE SIZEDispersion of largeparticlesThe intensity of scattered light from large particlesis not equal in all directionsLaserwww.malvern.co.ukBROWNIAN MOTION AND SCATTERED LIGHTBecause the scattered waves of lightare interfering with one anotherWhy does this happen?The Brownian motion of the particles causes the scattered light tofluctuate in intensitywww.malvern.co.ukBROWNIAN MOTION AND SCATTERED LIGHTScreenTwo beams interfere andcancel each other outresulting in a decreased intensity in the scattered lightLet us consider 2 stationary particleswww.malvern.co.ukBROWNIAN MOTION AND SCATTERED LIGHTScreenIf the particles move,Two beams interfere andenhance each otherresulting in an increased intensity in the scattered lightwww.malvern.co.ukBROWNIAN MOTION AND SCATTERED LIGHTMany scattered beams interfere with one anotherresulting in a very complex intensity pattern of specklesScreenConsider many particleswww.malvern.co.ukStokes-Einstein EquationD=Diffusion coefficientwhere d(H)=Hydrodynamic diameterk=Boltzmanns constantT=Absolute temperatureh=Viscosityd(H)=kT3 p h Dwww.malvern.co.ukLaserIncident BeamAxisSampleCellScreenSpecklePatternIntensity FluctuationsLarge ParticlesSmall ParticlesTimeTimeIntensityIntensityHow a Correlator WorksIntensityTime0tttttFor a system of particles undergoing Brownian motion,a speckle pattern is observed where the position of each speckle is seen to be in constant motionThe rate at which these intensity fluctuations occur will depend on the size of the particlesOptical Configuration of a Backscatter DLS InstrumentAPD Detector4mW He-Ne LaserTemperature controlled cell holderAuto-attenuatorTransmission monitorMoveable measurement PositionOptical Configuration of the Zetasizer 3000APD/PM10mW He-Ne laserSize/Zetamode select90o Size cellZeta potential capillary cellCombined receiveropticsModulatorAttenuator(a)=reference beam(b)=scattering beam(b)(a)Zetasizer Nano series(2003年)lMeasurement of size,zeta potential and molecular weight of colloids and molecules Zetasizer Nano series qFully automated and exceptionally easy to use series of instrumentsqIncorporates a combination of technologies qMeets all requirements for ISO 13321,21 CFR Part 11 and has validated hardware and softwareOptical Configuration of the Nano ZSUnique Features Of NIBS Moveable measurement positionlSmall particles or dilute samplesMeasure close to cell centre to maximise measurement volume and minimise flarelConcentrated samplesMeasure close to the cell wall to reduce the light path through the sample and hence minimise multiple scatteringUnique Features Of NIBS Moveable measurement positionPHOTON CORRELATION SPECTROSCOPY(PCS)光相关光谱什么是光相关光谱(PCS)?测量纳米微粒随机运动(散射)带来的波动迁移被扫描的粒子进行着布朗运动(Brownian Motion)计算散射迁移率 测量水力直径 粒径分布应用 Stokes-Einstein方程用PCS测量小粒子散射光强度弱的原因l小粒子 l极稀释的样品(dilute samples)l散射效果不好的粒子，(粒子的折射指数和分散相非常接近)此时用10mW 功率的He-Ne 激光就不足以PCS测量粒径。用PCS测量小粒径时l通常牺牲准确性，用增加激光能量来提高散射光强度l若保持低能量激光，则因重复计算，导致结果正误差。使用高能量激光器的缺点l增加样品吸光度会导致样品发热，破坏稳定性l不可预测的安全限量l增加成本最好的方法是使用高灵敏监测器提高计数率最好的方法是使用高灵敏监测器提高计数率ZETASIZER HS(HIGH SENSITIVITY)l马尔文推出新型光子电子计数器检测器(new generation of avalanche photodiodes(APDs)优越性：K提高灵敏度K可在极低浓度下测量，不需增加激光能量K避免热效应，保证结果准确K使用环境宽松K延长仪器使用寿命，降低故障率雪崩式光子电子计数检测器l固态二极管检测器(Solid state diode detectors)K当光子撞击时，产生了电子空穴对K产生的高压加速了电子运动K被加速的电子获的足够的能量进一步导致电离度的增加，如同雪崩一样。K最初的光子能雪崩式产生大量的约106 电子这个数量级远大于普通的光电备增器(photomultiplier detector)K因此有了新一代的雪崩式光子电子计数器检测器WHATS NEW ABOUT THE APD USED IN THE ZETASIZER?l过去的APD价格昂贵可靠性差，尽管灵敏度高l马尔文专利的新型APD，使用一种新型材料 突出的优越性：K提高了可靠性，达到灵敏度与可靠性的统一K减化操作K缩短稳定时间(Improved settling time from power up)应用：小粒子和表面胶束l测量胶束粒径及其分布l过去这些样品要用高档4700型仪器测定20mW,488nm 氩离子激光器照射，光电倍增管检测器测定。l现在仅用4 mW 就够了。应用实例:Absorbing systemsz-平均粒径平均粒径 (nm)多分散度多分散度测定时间测定时间分分计数率计数率(KCPS)18.418.418.4345.4346.0346.1180.4179.3181.2177.3177.5178.40.2460.2210.2240.1980.2120.212151515222RUN123456检测器检测器PMPMPMAPDAPDAPD4 mW He-Ne laser 测碳黑样品测碳黑样品计数率越高越好，结果重复性越好计数率越高越好，结果重复性越好应用实例:在吸收体系中Intensity Size distribution1020%in class51050 100500 1000Diameter(nm)4 4 mWmW He-He-NeNe 激光激光 and APD and APD 检测器测碳黑样品检测器测碳黑样品0.05%NONIDETz-平均粒径平均粒径(nm)多分散度多分散度RUN123均值均值17.717.718.017.8 0.20.1390.1420.1380.14 0.002 测量时间测量时间=4 分分/次次Intensity Size distribution51050100Diameter(nm)1020%in class0.3%TRITON X-100Intensity Size distribution51050100Diameter(nm)1020%in class平均粒径平均粒径(nm)多分散度多分散度次数次数123均值均值8.88.88.78.7 0.10.0580.0650.0660.063 0.004 测量时间测量时间=4 分分/次次0.08%吐温 20平均粒径平均粒径(nm)多分散度多分散度RUN123MEAN7.77.57.87.7 0.20.0750.1480.0490.090 0.052 测量时间测量时间=4 分分/次次51050100粒径粒径r(nm)1020%in classIntensity Size distributionAPPLICATIONS:Dilute systems51050 100500 1000Diameter(nm)Intensity Size distribution1020%in classGroundwater flocculated with AlCl3(3mg/L)z-平均粒径平均粒径(nm)多分散度多分散度RUN123MEAN174.2174.7171.5173.5 1.70.1910.1810.1860.186 0.005 测量时间测量时间=7 分分/次次应用实例:溶液中的蛋白质51050 100500Diameter(nm)102030%in classIntensity Size distributionz-平均粒径平均粒径(nm)多分散度多分散度RUN123MEAN10.311.411.010.9 0.50.2240.2430.2440.237 0.011 测量时间测量时间=15 分分/次次0.5%牛血清蛋白牛血清蛋白(BSA)趋势分析l随温度和时间的变化分析K仪器内部精确控温技术，无需外部设备K2 90 度范围l与MPT-2联用后K随pH值的变化K随电导率的变化K随添加剂浓度的变化Cyclosporin MicroemulsionsTime after sample preparation(hours)051520251020401008060120z-Average Diameter(nm)Formulation 1Formulation 2Formulation 3Formulation 4Measuring Virus:Antibody Interactions120140160180200z-Average Diameter(nm)Elapsed Time After Mixing(seconds)0200010001500500Antibody 1Antibody 2New MPT-2 autotitratorlAutomation:KpH,conductivity and additive titrationKAutomation of molecular weight measurementKIso-Electric PointlApplications KSample volume less than 3ml for proteinsZetasizer Nano S90 特点综述l粒度测定范围：2nm-3ml唯一具有标准操作规程（SOP）的纳米粒度分析仪器。l随时间及温度变化进行趋势分析。l与自动滴定（MPT-2）相连接后，可自动测定粒度随pH、盐浓度和电导率变化的，最少仅需3ml样品。l温度控制范围：2 90 CZetasizer Nano S90 特点综述l高效率的雪崩式光电二极管(APD)检测器提供了最高的灵敏度(高于光电倍增管检测器20倍)，5nm以下测量无需外接高功率激光器。l自动调节各种样品的最佳设置l在300,000:1的动态范围内自动调节激光衰减器l精确的样品池温度控制2C-90Cl稳定的He-Ne激光器确保数据的重复性l突出的高重现性，由精确的内部温控技术和在线pH测量加以保证。l操作简单，无须准直、校正或保养l光路密封，防止污染Zetasizer Nano S90 特点综述-软件：先进技术，操作简单软件：先进技术，操作简单l全自动设置和测量：在仪器设置上，只需最简单的培训，包括样品池位置、衰减器设置、数据记录、分析和结果显示。测量过程中，数据的质量可通过适时的光强和数据显示评估实验结果报告。lSOP:标准的操作程序确保操作的一致性，保证重复性l打印或屏幕显示报告使用简单，可进行个人化设计，只需在指定的位置选择图形和输入参数，就可根据不同的需要设计不同的报告。l测量数据的完全评估Zetasizer Nano S90 特点综述-软件：先进技术，操作简单软件：先进技术，操作简单l样品数据和结果存储在测量文件中，方便进行数据的比较。l数据分析K数据以图形或表格的形式给出，分布算法适合各种样品包括单分散样品，宽分布样品以及多种模式样品。K温度趋势分析K时间趋势分析K所选参数趋势分析K全范围统计图ApplicationslPaper ManufacturelPharmaceutical formulationlAgrochemical formulationlIntravenous lipid emulsionslCeramics manufacturelMineral processinglDrinking Water/Waste water treatmentlNon-aqueous systemsPaper manufacturelThe interaction of pulp fibers,particles and other additives during the manufacturing process affects a number of important physical properties of the final product.KThese interactions are largely controlled by the zeta potential of the constituents.KKnowledge of the zeta potential allows changes to be made to improve the quality or economy of the process.KProperties affected include flocculation of the pulp,deposition on rollers and wires,filler retention and product strength.Pharmaceutical formulationlMany pharmaceutical products are formulated as emulsions and suspensions.lIn order to ensure efficient dosage,predictable shelf life and batch to batch consistency,particle size must be closely controlled.lZeta potential plays a large part in determining particle size.lProblems such as caking,creaming and changes in efficacy can be investigated by measuring the zeta potential.Agrochemical formulation(1)lA large number of agrochemicals used in spray applications are formulated as granules.KThese have to form stable dispersions for hours when added to the water available locally to the farmer.KFormulations will be different in,say,England and Egypt as the water available contains different ions in different concentrationsKThe formulation has to include surfactants to aid dispersion when the granules are dispersed in waterAgrochemical formulation(2)lThe type and concentration of surfactant are critical.Without some fundamental measurement the choice is a matter of experience and trial and error.KFormulation becomes more complicated as an optimum formulation will often require two surfactants.KMeasurement of zeta potential provides a parameter measured in seconds which indicates the stability of the dispersion when prepared for use.Intravenous lipid emulsionslThese are usually known under the trade name of 慖ntralipid?emulsions,they are used to feed patients through an intravenous drip when food cannot be taken by mouth.KFor adequate nutrition the body requires fats,sugars,amino acids and minerals.Rather than introduce each of these into the body separately,it is obviously more convenient to mix everything into one bag to use in a single drip.KThis causes difficulties as a mixture of these components will almost certainly cause flocculation of the fat emulsion.KMeasurement of the zeta potential of the fat emulsion with addition of each of the additives has been found to be the best way of formulating these systems.Ceramics manufacture(1)lCeramics fall into two general categories,technical or engineering ceramics and 憌hitewareKIn both cases,the particle size distribution and the stability of the dispersion as the 憇lip?determines properties of the final product.KThe thickness and density of the product and the size of voids will all be affected.Ceramics manufacture(2)lThe usual method of formulation involves adding polymer as a dispersing agentKThis is a simple solution to the dispersion problem but has several disadvantages;burning the polymer out during firing causes shrinkage and voids and in addition is costly.KImproving the dispersion using electrostatic forces may involve merely changing the concentration of a few ions in the system.KThis will potentially lead to denser and hence stronger and more consistent product Mineral processing(1)lA large proportion of the separation of useful minerals from the useless 慻angue?is done using a technique called 慒roth flotationKThe mineral is finely ground,added to water and the environment modified such that the target mineral will adhere to collector oils bubbled through the dispersion.KThe oil and mineral float to the surface to be skimmed off.KThe conditions can now be modified to float a different mineralMineral processing(2)lThe controlling parameter that determines the efficiency of this process is the zeta potential.KBy measuring the zeta potential the optimum conditions and concentration of additives can be determined to maximise recovery efficiencyKZeta potential can also be used to study the effect of various pretreatment regimes that are used to maximise recoveryDrinking Water and Waste Water TreatmentlEach treatment plant has its own regime to remove contaminants from local source water or domestic waste waterKUsually a combination of changing the pH,adding electrolytes and polyelectrolytes is used to minimize the turbidity of the water.KAn increase in turbidity indicates that the treatment process needs changing,however it does not help with what changes in treatment are required to reduce turbibidity.KIf the source water changes regularly,measurement of the zeta potential in combination with other parameters such as conductivity and pH,can be used to determine the treatment required.Non-aqueous systemslThere are a number of commercially important dispersions where the dispersing medium is non polar.This is commonly dodecane,Isopar G or hexane.KTypical systems are liquid copier toners and inks.KAs non-polar liquids contain few ions,electrostatic stabilization requires the addition of charge enhancing agents as dispersants.KMeasuring zeta potential helps with selecting the best dispersant and addition of the correct quantity.KMeasuring the zeta potential of these systems requires a specialized cell.The DTS5002 cell for the Zetasizer 2000/3000 and the ZET5126 cell for the Zetasizer 5000产品质量保证及售后服务l获ISO9001 证书lGMP 工厂l中国保税库l售后服务：24小时响应，48小时到现场。l保修：一年保修l免费安装调试，仪器操作培训