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1、马尔文纳米粒度 及 Zeta电位分析仪,光散射技术的新进展 2003.10,CONTENTS,Zetasizer range 光相关光谱Photon Correlation Spectroscopy (PCS) PCS 理论概述 马尔文高灵敏的粒度仪 Zetasizer (HS) 系列介绍 专利的最新型检测器，激光功率多种选择 Zeta 电位 Zeta 电位理论概述 多用途滴定器 (MPT-1) New Zeta Potential Transfer Standard (DTS0050),THE ZETASIZER RANGE,用微量电泳法测定水和非水体系中粒子的Zeta电位 Zeta 电位可
2、权威地预测分散体系(悬浮液，乳化液)的长期稳定性 用光相关光谱测量分散体系中粒径分布,2003年5月隆重上市,世 界 顶 级 纳 米 颗 粒 和 大 分 子 特 性 分 析 仪 器,纳米粒度及 Zeta电位分析仪, 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 _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PCS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600台以上 - 已获得ISO9001标准
3、, 欧洲EMC标准认证, GMP标准认 证，唯一完全符合美国FDA QSpec要求 - 多方位应用支持，在中国设立正式技术服务中心,.,.,.,.,激 光 粒 度 分 析 技 术 的 先 锋,马尔文激光粒度分析仪自80年代进入我国以来，到90年代已基本取代了传统的筛析和离心沉降方法，成为粒度分析快速、准确、高效的最佳手段。马尔文激光粒度分析仪不仅具有准确分析1m以下真实粒子的优势，而且对于透明、半透明，带色或不带色的各种乳化液和干粉的分析研究具有无可比拟的优点。,马尔文光子相关光谱仪的发展,Zave = 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
4、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 1000 Size measurement at 90 deg. 2nm to 3 microns ZETASIZER 2000 Zeta potential measurement o
5、f particles of 5nm to 30 microns size in aqueous and non aqueous systems ZETASIZER 3000 Combination of 1000 and 2000 plus size measurement at 12 deg.,ZETASIZER 1000 and 2000 can be upgraded to 3000,ZETASIZER Series,ZETASIZER 1000 and 2000 can be upgraded to 3000,Zetasizer HS系列 纳米粒度及Zeta电位分析仪和MPT-1 自
6、动滴定系统 (1999年),The MPT-1 是为Zetasizer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 RANGE,2 to 3000nm,The New Ze
7、tasizer Nano series,Size Measurement of colloids, emulsions and molecules High sensitivity and high concentration Zeta potential Zero maintenance zeta potential measurement Molecular weight Proteins and polymers,5 new instruments,New Zeta Size (backscatter) New Zeta & Size (backscatter) Size 90 degr
8、ees New Zeta with 90 degree size,What Does a Conventional PCS Instrument Consist Of?,WHAT DOES A PCS INSTRUMENT CONSIST OF?,Zetasizer HS (High Sensitivity) instruments contain an APD detector,THE INTENSITY OF SCATTERED LIGHT,www.malvern.co.uk,SCATTERED LIGHT AND PARTICLE SIZE,www.malvern.co.uk,SCATT
9、ERED LIGHT AND PARTICLE SIZE,www.malvern.co.uk,BROWNIAN MOTION AND SCATTERED LIGHT,www.malvern.co.uk,BROWNIAN MOTION AND SCATTERED LIGHT,Two beams interfere and cancel each other out resulting in a decreased intensity in the scattered light,Let us consider 2 stationary particles,www.malvern.co.uk,BR
10、OWNIAN MOTION AND SCATTERED LIGHT,If the particles move, Two beams interfere and enhance each other resulting in an increased intensity in the scattered light,www.malvern.co.uk,BROWNIAN MOTION AND SCATTERED LIGHT,Many scattered beams interfere with one another resulting in a very complex intensity p
11、attern of speckles,www.malvern.co.uk,www.malvern.co.uk,Laser,Incident Beam,Axis,Sample,Cell,Screen,Speckle,Pattern,The Speckle Pattern,Intensity Fluctuations,How a Correlator Works,For a system of particles undergoing Brownian motion, a speckle pattern is observed where the position of each speckle
12、is seen to be in constant motion The rate at which these intensity fluctuations occur will depend on the size of the particles,Intensity Fluctuations,Optical Configuration of a Backscatter DLS Instrument,APD Detector,4mW He-Ne Laser,Temperature controlled cell holder,Auto-attenuator,Transmission mon
13、itor,Moveable measurement Position,Optical Configuration of the Zetasizer 3000,Zetasizer Nano series (2003年),Measurement of size, zeta potential and molecular weight of colloids and molecules,Zetasizer Nano series,Fully automated and exceptionally easy to use series of instruments Incorporates a com
14、bination of technologies Meets all requirements for ISO 13321, 21 CFR Part 11 and has validated hardware and software,Optical Configuration of the Nano ZS,Unique Features Of NIBS Moveable measurement position,Small particles or dilute samples Measure close to cell centre to maximise measurement volu
15、me and minimise flare,Concentrated samples Measure close to the cell wall to reduce the light path through the sample and hence minimise multiple scattering,Unique Features Of NIBS Moveable measurement position,PHOTON CORRELATION SPECTROSCOPY (PCS) 光相关光谱,什么是光相关光谱( PCS)?,用PCS测量小粒子,散射光强度弱的原因 小粒子 极稀释的样
16、品(dilute samples) 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,通常牺牲准确性，用增加激光能量来提高散射光强度 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,增加样品吸光度会导致样品发热，破坏稳定性 不可预测的安全限量 增加成本,最好的方法是使用高灵敏监测器提高计数率,ZETASIZER HS (HIGH SENSITIVITY),马尔文推出新型光子电子计数器检测器(new generation of avalanche photodiodes (APD
17、s) 优越性： 提高灵敏度 可在极低浓度下测量，不需增加激光能量 避免热效应，保证结果准确 使用环境宽松 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,固态二极管检测器(Solid state diode detectors) 当光子撞击时，产生了电子空穴对 产生的高压加速了电子运动 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。 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) 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
18、THE ZETASIZER?,过去的APD价格昂贵可靠性差，尽管灵敏度高 马尔文专利的新型APD，使用一种新型材料 突出的优越性： 提高了可靠性，达到灵敏度与可靠性的统一 减化操作 缩短稳定时间(Improved settling time from power up),应用： 小粒子和表面胶束,测量胶束粒径及其分布 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。 现在仅用4 mW 就够了。,应用实例: Absorbing systems,4 mW He-Ne laser 测碳黑样品,计数率越高越好，结果重复性越好,应用实例: 在吸收体系中
19、,4 mW He-Ne 激光 and APD 检测器测碳黑样品,0.05% NONIDET,z- 平均粒径 (nm),多分散度,RUN,1,2,3,均值,17.7,17.7,18.0,17.8 0.2,0.139,0.142,0.138,0.14 0.002,测量时间 = 4 分/次,Intensity Size distribution,5,10,50,100,Diameter (nm),10,20,% in class,0.3% TRITON X-100,Intensity Size distribution,5,10,50,100,Diameter (nm),10,20,% in cla
20、ss,平均粒径 (nm),多分散度,次数,1,2,3,均值,8.8,8.8,8.7,8.7 0.1,0.058,0.065,0.066,0.063 0.004,测量时间 = 4 分/次,0.08% 吐温 20,平均粒径 (nm),多分散度,RUN,1,2,3,MEAN,7.7,7.5,7.8,7.7 0.2,0.075,0.148,0.049,0.090 0.052,测量时间 = 4 分/次,5,10,50,100,粒径r (nm),10,20,% in class,Intensity Size distribution,APPLICATIONS: Dilute systems,5,10,50
21、,100,500,1000,Diameter (nm),Intensity Size distribution,10,20,% in class,Groundwater flocculated with AlCl3 (3mg/L),z- 平均粒径 (nm),多分散度,RUN,1,2,3,MEAN,174.2,174.7,171.5,173.5 1.7,0.191,0.181,0.186,0.186 0.005,测量时间 = 7 分/次,应用实例: 溶液中的蛋白质,0.5% 牛血清蛋白 (BSA),趋势分析,随温度和时间的变化分析 仪器内部精确控温技术，无需外部设备 2 90 度范围 与MPT-
22、2联用后 随pH值的变化 随电导率的变化 随添加剂浓度的变化,Cyclosporin Microemulsions,Time after sample preparation (hours),0,5,15,20,25,10,20,40,100,80,60,120,z-Average Diameter (nm),Formulation 1,Formulation 2,Formulation 3,Formulation 4,New MPT-2 autotitrator,Automation : pH, conductivity and additive titration Automation o
23、f molecular weight measurement Iso-Electric Point Applications Sample volume less than 3ml for proteins,Zetasizer Nano S90 特点综述,粒度测定范围：2nm - 3m 唯一具有标准操作规程（SOP）的纳米粒度分析仪器。 随时间及温度变化进行趋势分析。 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。 温度控制范围：2 90 C,Zetasizer Nano S90 特点综述,高效率的雪崩式光电二极管(APD)检测器提供了最高的
24、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。 自动调节各种样品的最佳设置 在300,000:1的动态范围内自动调节激光衰减器 精确的样品池温度控制2C-90C 稳定的He-Ne激光器确保数据的重复性 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。 操作简单，无须准直、校正或保养 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,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。 S
25、OP: 标准的操作程序确保操作的一致性，保证重复性 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。 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,样品数据和结果存储在测量文件中，方便进行数据的比较。 数据分析 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。 温度趋势分析 时间趋势分析 所选参数趋势分析 全范围统计图,Applications,Paper Manufacture Pharmaceutical formulation
26、 Agrochemical formulation Intravenous lipid emulsions Ceramics manufacture Mineral processing Drinking Water / Waste water treatment Non-aqueous systems,Paper manufacture,The interaction of pulp fibers, particles and other additives during the manufacturing process affects a number of important phys
27、ical properties of the final product. These interactions are largely controlled by the zeta potential of the constituents. Knowledge of the zeta potential allows changes to be made to improve the quality or economy of the process . Properties affected include flocculation of the pulp, deposition on
28、rollers and wires, filler retention and product strength.,Pharmaceutical formulation,Many pharmaceutical products are formulated as emulsions and suspensions. In order to ensure efficient dosage, predictable shelf life and batch to batch consistency, particle size must be closely controlled. Zeta po
29、tential plays a large part in determining particle size. Problems such as caking, creaming and changes in efficacy can be investigated by measuring the zeta potential.,Agrochemical formulation (1),A large number of agrochemicals used in spray applications are formulated as granules. These have to fo
30、rm stable dispersions for hours when added to the water available locally to the farmer. Formulations will be different in, say, England and Egypt as the water available contains different ions in different concentrations The formulation has to include surfactants to aid dispersion when the granules
31、 are dispersed in water,Agrochemical formulation (2),The type and concentration of surfactant are critical. Without some fundamental measurement the choice is a matter of experience and trial and error. Formulation becomes more complicated as an optimum formulation will often require two surfactants
32、. Measurement of zeta potential provides a parameter measured in seconds which indicates the stability of the dispersion when prepared for use.,Intravenous lipid emulsions,These are usually known under the trade name of 慖ntralipid?emulsions, they are used to feed patients through an intravenous drip
33、 when food cannot be taken by mouth. For 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. This causes difficulties as a mi
34、xture of these components will almost certainly cause flocculation of the fat emulsion. Measurement 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),Ceramics fall into two general
35、 categories, technical or engineering ceramics and 憌hiteware In both cases, the particle size distribution and the stability of the dispersion as the 憇lip? determines properties of the final product. The thickness and density of the product and the size of voids will all be affected.,Ceramics manufa
36、cture (2),The usual method of formulation involves adding polymer as a dispersing agent This 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. Improving the dispersion using electr
37、ostatic forces may involve merely changing the concentration of a few ions in the system. This will potentially lead to denser and hence stronger and more consistent product,Mineral processing (1),A large proportion of the separation of useful minerals from the useless 慻angue?is done using a techniq
38、ue called 慒roth flotation The 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. The oil and mineral float to the surface to be skimmed off. The conditions can now be modified to float a dif
39、ferent mineral,Mineral processing (2),The controlling parameter that determines the efficiency of this process is the zeta potential. By measuring the zeta potential the optimum conditions and concentration of additives can be determined to maximise recovery efficiency Zeta potential can also be use
40、d to study the effect of various pretreatment regimes that are used to maximise recovery,Drinking Water and Waste Water Treatment,Each treatment plant has its own regime to remove contaminants from local source water or domestic waste water Usually a combination of changing the pH , adding electroly
41、tes and polyelectrolytes is used to minimize the turbidity of the water. An 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. If the source water changes regularly, measurement of the
42、 zeta potential in combination with other parameters such as conductivity and pH, can be used to determine the treatment required.,Non-aqueous systems,There are a number of commercially important dispersions where the dispersing medium is non polar. This is commonly dodecane, Isopar G or hexane. Typ
43、ical systems are liquid copier toners and inks. As non-polar liquids contain few ions, electrostatic stabilization requires the addition of charge enhancing agents as dispersants. Measuring zeta potential helps with selecting the best dispersant and addition of the correct quantity. Measuring 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,获ISO9001 证书 GMP 工厂 中国保税库 售后服务：24小时响应，48小时到现场。 保修：一年保修 免费安装调试，仪器操作培训,