MS2000-朱天兴

1、马尔文仪器有限马尔文仪器有限公司公司朱天兴朱天兴 Malvern Instruments Ltd. UKLondon.MalvernEdinburgh.Birmingham. 总部在英国 全球约300名员工 在全球超过70个国家和地区有办事 机构 拥有5个独立的子公司 思百吉集团 (Spectris)成员. .全球最大的激光粒度仪生产厂家由原英国雷达研究所的工程师于二战后创建1970年代生产出世界上第一台PCS纳米粒度仪1970年代生产出世界上第一台衍射法激光粒度仪世界上第一台超声粒度仪的发明者2003年底收购了英国BOHLIN公司马尔文仪器有限公司马尔文仪器有限公司 _激光粒度分析仪的创始人

2、激光粒度分析仪的创始人 - - 销售量占世界第一和中国第一，仅中国大销售量占世界第一和中国第一，仅中国大陆已有陆已有10001000套以上套以上. . 共有员工30人, 其中销售人员9人,维修工程师8人,应用专家6人 在上海,北京,广州,成都有办事处 在上海,北京,广州,成都有维修部 2005年5月份在上海成立了亚太区技术中心 Malvern Instruments China粒度，粒度，Zeta电位及图像分析仪器电位及图像分析仪器Mastersizer系列衍射法激光粒度仪Zetasizer Nano系列PCS法纳米粒度及ZETA电位分析仪Spraytec系列喷雾粒度仪Morphologi G

3、2粒度和图像分析仪在线激光粒度仪流变仪流变仪旋转流变仪毛细管流变仪沥青流变仪粘度计 马尔文仪器有限公司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- - 能向用户提供马尔文公司所独有的能向用户提供马尔文公司所独有的, , 唯一能被唯一能被ISO, EMC,GMP, FDA, EMC,GMP, FDA等多家国际认证机构承认的等多家国际认证机构承认的 Qspec报告，以帮助用户通过报告，以帮助用户通过ISOISO等认证。等认证。- - 马尔文公司总部设有马尔文公司总部设有HelpDesk,HelpDesk,保证保证2424小时内回复用户疑问。在全小时内回复用户疑问。在全世界设

4、有多个应用实验室，提供最佳技术支持。世界设有多个应用实验室，提供最佳技术支持。- - 20052005年在中国上海正式建立亚太技术中心年在中国上海正式建立亚太技术中心，设有专门的应用实验室，设有专门的应用实验室，免费为全国用户测试样品并提供技术支持。免费为全国用户测试样品并提供技术支持。- - 马尔文专家定期巡回中国为用户服务。马尔文专家定期巡回中国为用户服务。 - -在北京，上海和广州设有专门的维修部在北京，上海和广州设有专门的维修部.1977- IEE McRobert Award1977- Queens Award for Technical Achievement1981- Queen

5、s Award for Export Achievement1987- TASC Award for Analytical Equipment1988- Queens Award for Technical Achievement1988- Queens Award for Export Achievement1993- Engineering Safe Workers Award1994- British Safety Council Award and?.er.But what can it actually do ?光散射现象光散射现象Large particles scatter li

6、ghtat small angles对照射光产生的散射对照射光产生的散射,大粒子散射角大粒子散射角 度小度小,小粒子散射角度大小粒子散射角度大0 .3 /3 /3 0 /3 0 0角 度散射光强粒子直径减少粒子直径减少10倍，散射光强减弱一百万倍倍，散射光强减弱一百万倍 !根据瑞利散射定律：根据瑞利散射定律： I D6 / 4 散射光强 粒子直径 光源波长HeNeLaser2mw Power0. 63 m wavel engt hSpat i alFi l t erPar t i cl essuspendedi nGasorl i qui dFour i erTr ansf or mLensU

7、nscat t er edLi ghtScat t er edLi ghtMul t iEl ementDet ect orObscur at i onDet ect or技术难点：检测器面积有限；小粒子散射光弱；杂散光影响Low Angle Laser Light ScatteringCalculation of the Result小小 角角 激激 光光 散散 射射 理理 论论Mie Theory米氏理论- 真实粒子可能是任何形状- 入射到颗粒的光的出路包括散射,透射,反射,折射, 与颗粒的光学特性有关.小 角 激 光 散 射 理 论- 较早的激光衍射系统因光学构造和计算机的限制而不能利用

8、完全的米氏理论, 只能用米氏理论的近似或子集, 如: Fraunhofer 理论.- Fraunhofer 假设假设:1. 粒子是完全不透明的扁平状粒子是完全不透明的扁平状(类似硬币类似硬币); 2. 所有到达颗粒的光均被散射所有到达颗粒的光均被散射, 散射光与粒子散射光与粒子 表面光学性质无关表面光学性质无关 。但是但是 真正的颗粒真正的颗粒看起来不象硬币！看起来不象硬币！小 角 激 光 散 射 理 论- 显然,自然界的颗粒几乎没有符合Fraunhofer 假设的, 所以, 用该理论分析所有类型的材料都将引起结果的偏差, 特别对于超微粒子误差较大.- 当然, Malvern 激光粒度仪保留了

9、Fraunhofer 选项, 以便与其它仪器比对结果.- 为了真实粒子计算结果的准确性, 请选择完全的米氏理论!Particle Diameter (m.)%0 10 20 010 20 30 40 50 60 70 80 90 100 0.1 1.0 10.0 100.02OAD2NAD2OHD如何判断激光粒度分析仪的优劣？如何判断激光粒度分析仪的优劣？主要看:粒度测量范围：粒度测量范围：注意小粒子散射（0.5微米）如何检测。激光光源：激光光源：功率高、波长短、稳定性好为优。检测器的特点：检测器的特点：形状, 检测角大小，如何克服光强衰减。是否使用完全的米氏理论：是否使用完全的米氏理论：近似

10、的米氏理论，造成适用范围受限制，漏检几率增大等问题。扫描速度扫描速度：速度快可提高数据准确性,重复性和稳定性。准确性和重复性指标：准确性和重复性指标：越高越好可自动对中，无需更换镜头，可自动校正。分散器对样品分散能力：分散器对样品分散能力：是否带超声和搅拌，超声功率和搅拌速度是否足够大，是否连续可调。样品池样品池拆卸，清洗是否方便。是否符合国际标准 ( ISO13320 )。 小颗粒的检测方法小颗粒的检测方法- 1. Low Angle Laser Light Scattering A Multi Lens Technique In the past, and in some cases wi

11、th old technology equipmentstill being manufactured today, this problem was solved byusing multiple lenses to make a measurement (Sympatec). In this diagram the larger particles were measured with a long focal length lens. Note! the light scattered from the small particles misses the detector and is

12、 not measuredLong focal length lens Low Angle Laser Light ScatteringA Multi Lens TechniqueBy combining experiments from several different ranges, all particlesizes can be measured. However, in each measurement, the particles with sizes outside any particular range must contribute to the light scatte

13、ring, and hence give errors in the result. Short focal length lensLong focal length lensLaserDetectorFourierLens. Multiple LasersWhy do we need them?HeN eL aser2mwPow er0.63 mw avelengthSpatialFilterParticlessuspendedinGasorliquidFourierTransformL ensUnscatteredL ightScatteredL ightM ultiElementDete

14、ctorObscurationDetectorBy placing another laser at a different angle, the larger angle scattered light from the small particles now hits the detector. This extends the size range of the system. Or does it?Multiple LasersWhy do we need them?HeN eL aser2mwPow er0.63 mw avelengthSpatialFilterParticless

15、uspendedinGasorliquidFourierTransformL ensUnscatteredL ightScatteredL ightM ultiElementDetectorObscurationDetectorRemember a 0.1 micron particle scatters 1 million times less light than a 1 micron particle. The same tiny detectors are being used again to try and measure a tiny fraction of the light

16、of the main laser. Multiple LasersWhy do we need them?HeN eL aser2mwPow er0.63 mw avelengthSpatialFilterParticlessuspendedinGasorliquidFourierTransformL ensUnscatteredL ightScatteredL ightM ultiElementDetectorObscurationDetectorIn reality, the amount of light from these small particles is too small

17、for these detectors to measure, and the signal is lost in the electronic noise of the system. .亚微米粒度测定方法亚微米粒度测定方法激光衍射法（激光衍射法（ 0.02微米）微米） 真实粒子的粒度分布最佳方法（米氏理论）PCS法法 （3 0.002微米）微米） 亚微米粒子粒度测量经典方法（米氏理论）PIDS法法 （1 0.04微米）微米） 球形乳胶颗粒粒度测量的理想方法关于PIDS.Leeds & Northrup 公司1985年发明Leeds & Northrup 公司1989年放弃此

18、专利原因：与真实情况差距太大 PIDS理论假设为：单峰 球形 窄分布粒子 要求最低粒子浓度高于米氏理论的5倍左右 因此，小粒子受到大粒子掩蔽。E.g. 在0.25umTiO 2悬液+ 1滴40umTiO2，前者峰消失 与PCS对比: PIDS不能测zeta电位,不适于真实粒子 球形乳胶颗粒是唯一能被PIDS分辨的材料， 也仅能分辨 0.1/0.3um, 83/204/503nm的混合粒子 关于PIDS.与激光衍射法混合？方法不同，原理不同，结果表述不同 两种方法对测试体系的要求矛盾 1微米连接处信息丢失，误差明显激光衍射法与PCS法混合，如何？激光衍射法与显微镜法混合，如何？激光衍射法与筛法混

19、合，如何？苹果和桃子混合得到苹果和桃子混合得到 橘子？橘子？ PIDS STORYSUMMARYn So PIDS is a trick. Itll only work on the type of sample ( 83, 204, 503nm)n These mixtures have been designed in order to show sub-micron resolution. Theyre the only type of material that can be resolved.n Adding huge amounts of larger material to th

20、ese latices produces no effect they cant see it!n马尔文马尔文MASTERSIZER 2000可以轻松地分辨可以轻松地分辨3峰样品峰样品典型仪器Multi-Wavelength内部结构 PIDsMalvern Trimodal SampleOne way to Combat ?Malvern Trimodal Samplecompetitors resultsMalvern Trimodal SampleCompetitors resultsMastersizer 2000 光路设计FA: 前倾角检测器； LA: 大角检测器； BS: 背散射光检

21、测器5 latices resolved on the Mastersizer 2000 .and allows users to get results like thisMS2000 The RF errors quantified550mm focal length lensWet measurement - sample confined to +/- 1.2mm from centre of cell - error therefore 1.2/550 X 100% 0.2%!The median is identical - the distribution is broadene

22、d by 0.2% at top and 0.2% at bottom.So is both trivial (smaller than the other errors present) and can be predicted fully and therefore allowed forMastersizer 2000有哪些性能突破有哪些性能突破?激光光源激光光源如何保证高准确性，重复性和分如何保证高准确性，重复性和分辨率？辨率？偏振光源：偏振光源：632.8nm + 466 nm。激光器波长越短, 衍射光强度越大（成四次方的反比关系），所以，上述衍射光强度分别为750nm光源的2和10

23、倍，大大提高了检测灵敏度。 检测系统：检测系统：由扇形宽范围的前向，侧向和背向三维多元固体硅光电检测器群组，暗场光学标线和多元自动快速光路准直系统组成。 .非均匀排列，检测器灵敏度随角度增大而提高 对落出主检测器的小粒子散射光，用副检测器使接受角由40度提高到135度，从而实现了全量程直接测量各种真实粒径，实际分辨率最高。如何保证高准确性，重复性和分如何保证高准确性，重复性和分辨率？辨率？MS 2000 光学系统特点：光学系统特点：1. 光源、光路不变，保证了可进行完全的背景扣除2. 避免了不同方法混合测试而带来的误差3. 适用于球型及非球型的真实超微粒子完全的米氏理论 - 保证被测结果计算的

24、可靠性SOP 功能 - 消除外界人为操作误差及外部环境影响 检测器数目及排列检测器数目及排列- Do More detectors give more Resolution?The resolution of this ruler is governed by the number of divisions, and the dead space in betweenDo More detectors give more Resolution?The length of the red arrow can be determined 1mmDo More detectors give more

25、 Resolution?To measure with more precision, we need to add more divisions.Do More detectors give more Resolution?However, it can be easily seen that there is a limit.The conclusion?Do More detectors give more Resolution?For any system, there is an optimum number of measurement channels. Adding more

26、adds no further information, and can reduce this information A LITTLE ON RESOLUTION (1) The true distribution is the straight line. By trying to oversample the distribution and over resolve it, we only look at the noise. Theres no extra resolution at all! = Coulterresult A LITTLE ON RESOLUTION (2)n

27、Resolution comes from:- - Increased signal to noise (noise free data) - Spacing of detectors to optimise the available signal - Optimum number of detectors for width of distribution (0.1-600u 30, 0.05-900 40)Malvern MS 2000-DetectorMalvern Mastersizer 2000 detector under microscopeA little bit about

28、 detectorsclaim to have an optimum X detector. What does this mean? 扫描速度扫描速度1000次/秒- Mastersizer 2000有哪些性能突破有哪些性能突破?- - 动态测定范围加宽:0.02-2000微米- 粒度分布的分辨率提高，特别是在亚微米区- 准确性达 1%; 重复性达0.5%- 扫描速度达1000次/秒; 一次测量仅需2秒- 高度智能化-“插拔式”: 分散器快速更换- SOP 操作: ISO 标准化要求- 开放式软件设计及数据库: 无需用户编程Developing an SOP(Standard Operati

29、ng Procedure)Why develop an SOP?To ensure that all results are compared in the same mannerOne cannot expect the same results from different methodsStandardizationISO9000/GMP/GLP/ValidationWhat do we need from an SOP?RepeatabilityRepeatability Repeatability Repeatability Stability StabilityPrecisionP

30、recision or.Hydro 2000 MU标准体积湿法分散器标准体积湿法分散器独特的最新一代湿法分散器使用微型泵复合搅拌头，内置超声， 配合 600 到 1000ml 烧杯 气压平衡移泵机理，极易插入烧杯或取出防飞溅控制功能操作方便、快速、灵活，适合于科学研究Hydro 2000MuUses the same well-proven pump and stirrer as the microUses beakers as the sample tankHas control of pump, stir and ultrasonication as on the MicrosHas a

31、unique gas balance lifting mechanism for the pump and stirrerMalvern MS 2000-Wet Sample CellScirocco 2000 全自动喷射式干法进样器全自动喷射式干法进样器全自动控制所有参数可互换的采样盘能被系统识别可迅速与湿法分散器互换低噪音，无须隔音罩最强的干粉分散能力全封闭测量，不污染环境和光路Feed rate and air pressure (0 - 4 bar) monitored and controlled from the software.Vacuum monitoring to ensu

32、re repeatability of results82 dB = 1/2 current noise levels. 扫描速度扫描速度1000次/秒- What is velocity biasing?A laser diffraction measurement is based on the particle population in the laser beam during each sweep of the measurement.If small particles pass through the laser beam more slowly than large part

33、icles then they will be present in more sweeps than larger, faster moving particles.This means that when the sweeps are integrated, there will be a marked bias towards the fines.This effect is known as “velocity bias”.What causes velocity biasing?The most common cause of velocity biasing in a dry po

34、wder feeder is discharging a cloud of particles into still air.The fine particles lose momentum almost immediately and hang suspended in space while the large particles have sufficient inertia to keep moving.How do you avoid it?Have a totally enclosed air cell with a carefully controlled air flow wh

35、ich ensures that the small particles are conveyed through the laser beam at the same speed as the large particles.Any system without an enclosed air cell must be carefully evaluated to ensure that an apparently “finer” result is not simply the result of velocity biasing.Velocity Biasing illustrated.

36、A cloud of 10 particles is fired through a laser beam in still air.5 X 100-micron particles . and 5 X 3-micron particles.Velocity Biasing illustrated.The large particles have more mass and therefore pass rapidly through the beam The large particles have more mass and therefore pass rapidly through t

37、he beam The small particles have little mass and slow down very quickly in the still airRemember: Mass X Velocity = MomentumA sequence of eighteen grabs of the detectors would look like this.1)The large particles have arrived in the beam. Cumulative Total: 5 large 0 smallA sequence of eighteen grabs

38、 of the detectors would look like this.2)The large particles have arrived in the beam. Cumulative Total: 10 large 1 smallA sequence of eighteen grabs of the detectors would look like this.Cumulative Total:12 large 4 small 3)The large particles are now leaving the beam A sequence of eighteen grabs of

39、 the detectors would look like this.Cumulative Total: 13 large 8 small4)The large particles are now leaving the beam A sequence of eighteen grabs of the detectors would look like this.Cumulative Total: 13 large 13 small5)The large particles have now left the beam A sequence of eighteen grabs of the

40、detectors would look like this.Cumulative Total: 13 large 18 small6)The small particles continue to be countedA sequence of eighteen grabs of the detectors would look like this.Cumulative Total: 13 large 23 small7)The small particles continue to be countedA sequence of eighteen grabs of the detector

41、s would look like this.9)The small particles continue to be countedCumulative Total: 13 large 28 smallA sequence of eighteen grabs of the detectors would look like this.10)The small particles continue to be countedCumulative Total: 13 large 33 smallA sequence of eighteen grabs of the detectors would

42、 look like this.11)The small particles continue to be countedCumulative Total: 13 large 38 smallA sequence of eighteen grabs of the detectors would look like this.12)The small particles continue to be countedCumulative Total: 13 large 43 smallCumulative Total: 13 large 48 smallA sequence of eighteen

43、 grabs of the detectors would look like this.13)The small particles continue to be countedCumulative Total: 13 large 53 smallA sequence of eighteen grabs of the detectors would look like this.14)The small particles continue to be countedCumulative Total: 13 large 53 smallA sequence of eighteen grabs

44、 of the detectors would look like this.15)The small particles continue to be countedCumulative Total: 13 large 58 smallA sequence of eighteen grabs of the detectors would look like this.16)The small particles continue to be countedCumulative Total: 13 large 62 smallA sequence of eighteen grabs of th

45、e detectors would look like this.17)The small particles continue to be countedCumulative Total: 13 large 53 smallA sequence of eighteen grabs of the detectors would look like this.18)One small particle is left.Cumulative Total: 13 large 53 smallDividing the cumulative totals by 18 to obtain an avera

46、ge (which is what happens in laser diffraction)we discover that the 50:50 proportion of the particleshas become 2.94 : 0.722 thats 4.07 :1 in favour of the small particlesAnd now - no biasingA cloud of 10 particles is fired through a laser beam in an enclosed air cell.5 X 100-micron particles . and

47、5 X 3-micron particles.And now - no biasingBecause there is no still air to stop the small particles, they all move through the beam at the same speed.Cumulative Total: 0 large 0 smallAnd now - no biasingBecause there is no still air to stop the particles, they all move through the beam at the same speed.Cumulative Total: 0 large 3 smallAnd now - no biasingAll the particles are in the beam.Cumulative Total: 5 large 8 smallAnd now - no biasing.and pass through at the same speed