1、納米粒度及 Zeta電位分析儀光散射技術的新進展2003.101CONTENTSZetasizer range光相關光譜Photon Correlation Spectroscopy (PCS)PCS 理論概述馬爾文高靈敏的粒度儀 Zetasizer (HS) 系列介紹專利的最新型檢測器，激光功率多種選擇Zeta 電位Zeta 電位理論概述多用途滴定器 (MPT-1)New Zeta Potential Transfer Standard (DTS0050)2THE ZETASIZER RANGE 用微量電泳法測定水和非水體系中粒子的Zeta電位Zeta 電位可權威地預測分散體系(懸浮液，乳化

2、液)的長期穩(wěn)定性用光相關光譜測量分散體系中粒徑分布32003年5月隆重上市世 界 頂 級 納 米 顆 粒 和 大 分 子 特 性 分 析 儀 器納米粒度及 Zeta電位分析儀 新一代Zetasizer Nano ZS4位于英國的馬爾文公司總部5 英國馬爾文儀器有限公司 _激光粒度分析儀的創(chuàng)始人- 世界上最大的激光粒度分析儀專業(yè)設計和生產廠家- 世界上第一臺相關處理器- 世界上第一臺激光衍射法粒度分析儀，- 世界上第一臺激光PCS粒度分析儀- 世界上第一臺超聲粒度分析儀- 銷售量占世界第一，僅中國大陸已有600臺以上- 已獲得ISO9001標準, 歐洲EMC標準認證, GMP標準認 證，唯一完全

3、符合美國FDA QSpec要求- 多方位應用支持，在中國設立正式技術服務中心.激 光 粒 度 分 析 技 術 的 先 鋒6 馬爾文激光粒度分析儀自80年代進入我國以來，到90年代已基本取代了傳統(tǒng)的篩析和離心沉降方法，成為粒度分析快速、準確、高效的最佳手段。馬爾文激光粒度分析儀不僅具有準確分析1m以下真實粒子的優(yōu)勢，而且對于透明、半透明，帶色或不帶色的各種乳化液和干粉的分析研究具有無可比擬的優(yōu)點。7馬爾文光子相關光譜儀的發(fā)展Zave = 3.6nm8世界第一臺 PCS納米粒度分析系統(tǒng) (1970年) 1970年, 馬爾文數字相關器，一個革命性的光子交叉相關(PCCS)數字信號處理系統(tǒng)，在皇家信號

4、與雷達軍工實驗室（Royal Signals and Radar Establishment）開發(fā)成功。世界第一臺商用激光粒度分析儀及馬爾文儀器公司隨之誕生，并成為激光粒度分析儀技術的先鋒。隨后進一步開發(fā)了動態(tài)光散射的光子相關（PCS）亞微米測量技術。9Zetasizer 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 i

5、n aqueous and non aqueous systemsZETASIZER 3000Combination of 1000 and 2000 plussize measurement at 12 deg.ZETASIZER 1000 and 2000 can be upgraded to 300010ZETASIZER SeriesZETASIZER 1000 and 2000 can be upgraded to 300011Zetasizer HS系列 納米粒度及Zeta電位分析儀和MPT-1 自動滴定系統(tǒng)(1999年)The MPT-1 是為Zetasizer分析儀特制的高效專

6、用自動滴定裝置粒徑范圍：2 nm 3000 nm專利高靈敏測量系統(tǒng),下限測量無須高功率激光器。2000年最新M3專利技術，具有高分辨高準確性，可分辨混合粒子1mV的Zeta電位差異。突出的高重現(xiàn)性，由精確的內部溫控技術和在線pH測量加以保證。全自動三元滴定系統(tǒng)：精確控制、實時測量pH，鹽濃度和電導率的連續(xù)變化。全自動結果自診斷系統(tǒng)：結果判斷因子(RQF) 保證了每次測量質量。 內置ISO13321標準指導操作。12THE ZETASIZER RANGEINTENSITYZETASIZE 型號測量范圍 PARAMETER MEASUREDYESYESYESNONOYESYESYESNONOYES

7、YES90o FIXED ALIGNMENT10001000HS S90Nano S5 to 3000nm2 to 3000nm0.6 to 6000nm2 to 3000nm13The New Zetasizer Nano seriesSizeMeasurement of colloids, emulsions and moleculesHigh sensitivity and high concentration Zeta potentialZero maintenance zeta potential measurementMolecular weightProteins and pol

8、ymers145 new instrumentsNew ZetaSize (backscatter)New Zeta & Size (backscatter)Size 90 degreesNew Zeta with 90 degree size15What Does a Conventional PCS Instrument Consist Of?PinholeDetector(Photomultiplier/AvalanchePhoto Diode)LaserSample containing particlesScattered light16WHAT DOES A PCS INSTRUM

9、ENT CONSIST OF?PinholeDetector(Photomultiplier/AvalanchePhoto Diode)LaserSample containing particlesComputercontainingcorrelator card (7132)Scattered lightZetasizer HS (High Sensitivity) instruments contain an APD detector17THE INTENSITY OF SCATTERED LIGHTThe intensity of scattered light obtained fr

10、om a dispersion of particles is dependent uponLaser wavelength Particle size 18SCATTERED LIGHT AND PARTICLE SIZEDispersion of smallparticlesLaserThe intensity of scattered light from small particlesis equal in all directions19SCATTERED LIGHT AND PARTICLE SIZEDispersion of largeparticlesThe intensity

11、 of scattered light from large particlesis not equal in all directionsLaser20BROWNIAN 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 intensity21BROWNIAN

12、MOTION AND SCATTERED LIGHTScreenTwo beams interfere andcancel each other outresulting in a decreased intensity in the scattered lightLet us consider 2 stationary particles22BROWNIAN MOTION AND SCATTERED LIGHTScreenIf the particles move,Two beams interfere andenhance each otherresulting in an increas

13、ed intensity in the scattered light23BROWNIAN MOTION AND SCATTERED LIGHTMany scattered beams interfere with one anotherresulting in a very complex intensity pattern of specklesScreenConsider many particles24Stokes-Einstein EquationD = Diffusion coefficientwhere d(H) = Hydrodynamic diameterk = Boltzm

14、anns constantT = Absolute temperatureh = Viscosityd(H) = kT3 p h D25LaserIncident BeamAxisSampleCellScreenSpecklePatternThe Speckle Pattern26Intensity FluctuationsLarge ParticlesSmall ParticlesTimeTimeIntensityIntensity27How a Correlator Works28For a system of particles undergoing Brownian motion, a

15、 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 particlesIntensity Fluctuations29Optical Configuration of a Backscatter DLS InstrumentAPD Detector4mW He-Ne LaserTempera

16、ture controlled cell holderAuto-attenuatorTransmission monitorMoveable measurement Position30Optical Configuration of the Zetasizer 3000APD/PM10mW He-Ne laserSize / Zetamode select90o Size cellZeta potential capillary cellCombined receiveropticsModulatorAttenuator(a) = reference beam(b) = scattering

17、 beam(b)(a)31 Zetasizer Nano series (2003年)Measurement of size, zeta potential and molecular weight of colloids and molecules 32Zetasizer Nano series Fully automated and exceptionally easy to use series of instrumentsIncorporates a combination of technologies Meets all requirements for ISO 13321, 21

18、 CFR Part 11 and has validated hardware and software33Optical Configuration of the Nano ZS34Unique Features Of NIBS Moveable measurement positionSmall particles or dilute samplesMeasure close to cell centre to maximise measurement volume and minimise flare35Concentrated samplesMeasure close to the c

19、ell wall to reduce the light path through the sample and hence minimise multiple scatteringUnique Features Of NIBS Moveable measurement position36PHOTON CORRELATION SPECTROSCOPY (PCS)光相關光譜37什么是光相關光譜( PCS)?測量納米微粒隨機運動(散射)帶來的波動遷移被掃描的粒子進行著布朗運動(Brownian Motion)計算散射遷移率 測量水力直徑 粒徑分布應用 Stokes-Einstein方程38用PC

20、S測量小粒子散射光強度弱的原因小粒子 極稀釋的樣品(dilute samples)散射效果不好的粒子，(粒子的折射指數和分散相非常接近)此時用10mW 功率的He-Ne 激光就不足以PCS測量粒徑。39用PCS測量小粒徑時通常犧牲準確性，用增加激光能量來提高散射光強度若保持低能量激光，則因重復計算，導致結果正誤差。40使用高能量激光器的缺點增加樣品吸光度會導致樣品發(fā)熱，破壞穩(wěn)定性不可預測的安全限量增加成本最好的方法是使用高靈敏監(jiān)測器提高計數率41ZETASIZER HS (HIGH SENSITIVITY)馬爾文推出新型光子電子計數器檢測器(new generation of avalanch

21、e photodiodes (APDs)優(yōu)越性：提高靈敏度可在極低濃度下測量，不需增加激光能量避免熱效應，保證結果準確使用環(huán)境寬松延長儀器使用壽命，降低故障率42雪崩式光子電子計數檢測器固態(tài)二極管檢測器(Solid state diode detectors)當光子撞擊時，產生了電子空穴對產生的高壓加速了電子運動被加速的電子獲的足夠的能量進一步導致電離度的增加，如同雪崩一樣。最初的光子能雪崩式產生大量的約106 電子這個數量級遠大于普通的光電備增器( photomultiplier detector)因此有了新一代的雪崩式光子電子計數器檢測器43WHATS NEW ABOUT THE APD

22、USED IN THE ZETASIZER?過去的APD價格昂貴可靠性差，盡管靈敏度高馬爾文專利的新型APD，使用一種新型材料 突出的優(yōu)越性：提高了可靠性，達到靈敏度與可靠性的統(tǒng)一減化操作縮短穩(wěn)定時間(Improved settling time from power up)44應用： 小粒子和表面膠束測量膠束粒徑及其分布過去這些樣品要用高檔4700型儀器測定20mW,488nm 氬離子激光器照射，光電倍增管檢測器測定。現(xiàn)在僅用4 mW 就夠了。45應用實例: Absorbing systemsz- 平均粒徑 (nm)多分散度測定時間分計數率(KCPS)18.418.418.4345.4346

23、.0346.1180.4179.3181.2177.3177.5178.40.2460.2210.2240.1980.2120.212151515222RUN123456檢測器PMPMPMAPDAPDAPD4 mW He-Ne laser 測碳黑樣品計數率越高越好，結果重復性越好46應用實例: 在吸收體系中Intensity Size distribution1020% in class510501005001000Diameter (nm)4 mW He-Ne 激光 and APD 檢測器測碳黑樣品470.05% NONIDETz- 平均粒徑 (nm)多分散度RUN123均值17.717.7

24、18.017.8 0.20.1390.1420.1380.14 0.002 測量時間 = 4 分/次Intensity Size distribution51050100Diameter (nm)1020% in class480.3% TRITON X-100Intensity Size distribution51050100Diameter (nm)1020% in class平均粒徑 (nm)多分散度次數123均值8.7 0.10.0580.0650.0660.063 0.004 測量時間 = 4 分/次490.08% 吐溫 20平均粒徑 (nm)多分散度RUN123

25、MEAN7.7 0.20.0750.1480.0490.090 0.052 測量時間 = 4 分/次51050100粒徑r (nm)1020% in classIntensity Size distribution50APPLICATIONS:Dilute systems510501005001000Diameter (nm)Intensity Size distribution1020% in classGroundwater flocculated with AlCl3 (3mg/L)z- 平均粒徑 (nm)多分散度RUN123MEAN174.2174.7171.5173

26、.5 1.70.1910.1810.1860.186 0.005 測量時間 = 7 分/次51應用實例: 溶液中的蛋白質51050100500Diameter (nm)102030% in classIntensity Size distributionz- 平均粒徑 (nm)多分散度RUN123MEAN10.311.411.010.9 0.50.2240.2430.2440.237 0.011 測量時間 = 15 分/次0.5% 牛血清蛋白 (BSA)52趨勢分析隨溫度和時間的變化分析儀器內部精確控溫技術，無需外部設備2 90 度范圍與MPT-2聯(lián)用后隨pH值的變化隨電導率的變化隨添加劑濃度

27、的變化53Cyclosporin MicroemulsionsTime after sample preparation (hours)051520251020401008060120z-Average Diameter (nm)Formulation 1Formulation 2Formulation 3Formulation 454New MPT-2 autotitratorAutomation :pH, conductivity and additive titrationAutomation of molecular weight measurementIso-Electric Poi

28、ntApplications Sample volume less than 3ml for proteins55Zetasizer Nano S90 特點綜述粒度測定范圍：2nm - 3m唯一具有標準操作規(guī)程（SOP）的納米粒度分析儀器。隨時間及溫度變化進行趨勢分析。與自動滴定（MPT-2）相連接后，可自動測定粒度隨pH、鹽濃度和電導率變化的，最少僅需3ml樣品。溫度控制范圍：2 90 C56Zetasizer Nano S90 特點綜述高效率的雪崩式光電二極管(APD)檢測器提供了最高的靈敏度(高于光電倍增管檢測器20倍) ， 5nm以下測量無需外接高功率激光器。自動調節(jié)各種樣品的最佳設置

29、在300,000:1的動態(tài)范圍內自動調節(jié)激光衰減器精確的樣品池溫度控制2C-90C穩(wěn)定的He-Ne激光器確保數據的重復性突出的高重現(xiàn)性，由精確的內部溫控技術和在線pH測量加以保證。操作簡單，無須準直、校正或保養(yǎng)光路密封，防止污染57Zetasizer Nano S90 特點綜述- 軟件：先進技術，操作簡單全自動設置和測量：在儀器設置上，只需最簡單的培訓，包括樣品池位置、衰減器設置、數據記錄、分析和結果顯示。測量過程中，數據的質量可通過適時的光強和數據顯示評估實驗結果報告。SOP: 標準的操作程序確保操作的一致性，保證重復性打印或屏幕顯示報告使用簡單，可進行個人化設計，只需在指定的位置選擇圖形和

30、輸入參數，就可根據不同的需要設計不同的報告。測量數據的完全評估58Zetasizer Nano S90 特點綜述- 軟件：先進技術，操作簡單樣品數據和結果存儲在測量文件中，方便進行數據的比較。數據分析數據以圖形或表格的形式給出，分布算法適合各種樣品包括單分散樣品，寬分布樣品以及多種模式樣品。溫度趨勢分析時間趨勢分析所選參數趨勢分析全范圍統(tǒng)計圖59ApplicationsPaper ManufacturePharmaceutical formulationAgrochemical formulationIntravenous lipid emulsionsCeramics manufacture

31、Mineral processingDrinking Water / Waste water treatmentNon-aqueous systems60Paper manufactureThe interaction of pulp fibers, particles and other additives during the manufacturing process affects a number of important physical properties of the final product.These interactions are largely controlle

32、d 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 rollers and wires, filler retention and product strength.61Pharmaceutical formul

33、ationMany 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 potential plays a large part in determining particle size. Problems such as caking,

34、creaming and changes in efficacy can be investigated by measuring the zeta potential.62Agrochemical formulation (1)A large number of agrochemicals used in spray applications are formulated as granules. These have to form stable dispersions for hours when added to the water available locally to the f

35、armer. Formulations will be different in, say, England and Egypt as the water available contains different ions in different concentrationsThe formulation has to include surfactants to aid dispersion when the granules are dispersed in water63Agrochemical formulation (2)The type and concentration of

36、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.Measurement of zeta potential provides a parameter measured in seconds which indica

37、tes the stability of the dispersion when prepared for use.64Intravenous lipid emulsionsThese 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.For adequate nutrition the body requires fats, su

38、gars, 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 mixture of these components will almost certainly cause flocculation of the fat emulsion.

39、 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.65Ceramics manufacture (1)Ceramics fall into two general categories, technical or engineering ceramics and 憌hitewareIn both cases, the particle

40、 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.66Ceramics manufacture (2)The usual method of formulation involves adding polymer as a dispersing agentTh

41、is 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 electrostatic forces may involve merely changing the concentration of a few ions in the system.Th

42、is will potentially lead to denser and hence stronger and more consistent product 67Mineral processing (1)A large proportion of the separation of useful minerals from the useless 慻angue?is done using a technique called 慒roth flotationThe mineral is finely ground, added to water and the environment m

43、odified 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 different mineral68Mineral 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 efficien