納米粒度和自動(dòng)滴定NanoZS

1、納米粒度及 Zeta電位分析儀光散射技術(shù)的新進(jìn)展2003.101CONTENTSZetasizer range光相關(guān)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(cè)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(cè)定水和非水體系中粒子的Zeta電位Zeta 電位可權(quán)威地預(yù)測(cè)分散體系(懸浮液，乳化

2、液)的長(zhǎng)期穩(wěn)定性用光相關(guān)光譜測(cè)量分散體系中粒徑分布32003年5月隆重上市世 界 頂 級(jí) 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(guó)的馬爾文公司總部5 英國(guó)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(shè)計(jì)和生產(chǎn)廠家- 世界上第一臺(tái)相關(guān)處理器- 世界上第一臺(tái)激光衍射法粒度分析儀，- 世界上第一臺(tái)激光PCS粒度分析儀- 世界上第一臺(tái)超聲粒度分析儀- 銷售量占世界第一，僅中國(guó)大陸已有600臺(tái)以上- 已獲得ISO9001標(biāo)準(zhǔn), 歐洲EMC標(biāo)準(zhǔn)認(rèn)證, GMP標(biāo)準(zhǔn)認(rèn) 證，唯一完全

3、符合美國(guó)FDA QSpec要求- 多方位應(yīng)用支持，在中國(guó)設(shè)立正式技術(shù)服務(wù)中心.激 光 粒 度 分 析 技 術(shù) 的 先 鋒6 馬爾文激光粒度分析儀自80年代進(jìn)入我國(guó)以來(lái)，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(zhǔn)確、高效的最佳手段。馬爾文激光粒度分析儀不僅具有準(zhǔn)確分析1m以下真實(shí)粒子的優(yōu)勢(shì)，而且對(duì)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(wú)可比擬的優(yōu)點(diǎn)。7馬爾文光子相關(guān)光譜儀的發(fā)展Zave = 3.6nm8世界第一臺(tái) PCS納米粒度分析系統(tǒng) (1970年) 1970年, 馬爾文數(shù)字相關(guān)器，一個(gè)革命性的光子交叉相關(guān)(PCCS)數(shù)字信號(hào)處理系統(tǒng)，在皇家信號(hào)

4、與雷達(dá)軍工實(shí)驗(yàn)室（Royal Signals and Radar Establishment）開(kāi)發(fā)成功。世界第一臺(tái)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(shù)的先鋒。隨后進(jìn)一步開(kāi)發(fā)了動(dòng)態(tài)光散射的光子相關(guān)（PCS）亞微米測(cè)量技術(shù)。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(dòng)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(dòng)滴定裝置粒徑范圍：2 nm 3000 nm專利高靈敏測(cè)量系統(tǒng),下限測(cè)量無(wú)須高功率激光器。2000年最新M3專利技術(shù)，具有高分辨高準(zhǔn)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(nèi)部溫控技術(shù)和在線pH測(cè)量加以保證。全自動(dòng)三元滴定系統(tǒng)：精確控制、實(shí)時(shí)測(cè)量pH，鹽濃度和電導(dǎo)率的連續(xù)變化。全自動(dòng)結(jié)果自診斷系統(tǒng)：結(jié)果判斷因子(RQF) 保證了每次測(cè)量質(zhì)量。 內(nèi)置ISO13321標(biāo)準(zhǔn)指導(dǎo)操作。12THE ZETASIZER RANGEINTENSITYZETASIZE 型號(hào)測(cè)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(guān)光譜37什么是光相關(guān)光譜( PCS)?測(cè)量納米微粒隨機(jī)運(yùn)動(dòng)(散射)帶來(lái)的波動(dòng)遷移被掃描的粒子進(jìn)行著布朗運(yùn)動(dòng)(Brownian Motion)計(jì)算散射遷移率 測(cè)量水力直徑 粒徑分布應(yīng)用 Stokes-Einstein方程38用PC

20、S測(cè)量小粒子散射光強(qiáng)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(shù)和分散相非常接近)此時(shí)用10mW 功率的He-Ne 激光就不足以PCS測(cè)量粒徑。39用PCS測(cè)量小粒徑時(shí)通常犧牲準(zhǔn)確性，用增加激光能量來(lái)提高散射光強(qiáng)度若保持低能量激光，則因重復(fù)計(jì)算，導(dǎo)致結(jié)果正誤差。40使用高能量激光器的缺點(diǎn)增加樣品吸光度會(huì)導(dǎo)致樣品發(fā)熱，破壞穩(wěn)定性不可預(yù)測(cè)的安全限量增加成本最好的方法是使用高靈敏監(jiān)測(cè)器提高計(jì)數(shù)率41ZETASIZER HS (HIGH SENSITIVITY)馬爾文推出新型光子電子計(jì)數(shù)器檢測(cè)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(cè)量，不需增加激光能量避免熱效應(yīng)，保證結(jié)果準(zhǔn)確使用環(huán)境寬松延長(zhǎng)儀器使用壽命，降低故障率42雪崩式光子電子計(jì)數(shù)檢測(cè)器固態(tài)二極管檢測(cè)器(Solid state diode detectors)當(dāng)光子撞擊時(shí)，產(chǎn)生了電子空穴對(duì)產(chǎn)生的高壓加速了電子運(yùn)動(dòng)被加速的電子獲的足夠的能量進(jìn)一步導(dǎo)致電離度的增加，如同雪崩一樣。最初的光子能雪崩式產(chǎn)生大量的約106 電子這個(gè)數(shù)量級(jí)遠(yuǎn)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(jì)數(shù)器檢測(cè)器43WHATS NEW ABOUT THE APD

22、USED IN THE ZETASIZER?過(guò)去的APD價(jià)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(dá)到靈敏度與可靠性的統(tǒng)一減化操作縮短穩(wěn)定時(shí)間(Improved settling time from power up)44應(yīng)用： 小粒子和表面膠束測(cè)量膠束粒徑及其分布過(guò)去這些樣品要用高檔4700型儀器測(cè)定20mW,488nm 氬離子激光器照射，光電倍增管檢測(cè)器測(cè)定?，F(xiàn)在僅用4 mW 就夠了。45應(yīng)用實(shí)例: Absorbing systemsz- 平均粒徑 (nm)多分散度測(cè)定時(shí)間分計(jì)數(shù)率(KCPS)18.418.418.4345.4346

23、.0346.1180.4179.3181.2177.3177.5178.40.2460.2210.2240.1980.2120.212151515222RUN123456檢測(cè)器PMPMPMAPDAPDAPD4 mW He-Ne laser 測(cè)碳黑樣品計(jì)數(shù)率越高越好，結(jié)果重復(fù)性越好46應(yīng)用實(shí)例: 在吸收體系中Intensity Size distribution1020% in class510501005001000Diameter (nm)4 mW He-Ne 激光 and APD 檢測(cè)器測(cè)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(cè)量時(shí)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(shù)123均值8.7 0.10.0580.0650.0660.063 0.004 測(cè)量時(shí)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(cè)量時(shí)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(cè)量時(shí)間 = 7 分/次51應(yīng)用實(shí)例: 溶液中的蛋白質(zhì)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(cè)量時(shí)間 = 15 分/次0.5% 牛血清蛋白 (BSA)52趨勢(shì)分析隨溫度和時(shí)間的變化分析儀器內(nèi)部精確控溫技術(shù)，無(wú)需外部設(shè)備2 90 度范圍與MPT-2聯(lián)用后隨pH值的變化隨電導(dǎo)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(diǎn)綜述粒度測(cè)定范圍：2nm - 3m唯一具有標(biāo)準(zhǔn)操作規(guī)程（SOP）的納米粒度分析儀器。隨時(shí)間及溫度變化進(jìn)行趨勢(shì)分析。與自動(dòng)滴定（MPT-2）相連接后，可自動(dòng)測(cè)定粒度隨pH、鹽濃度和電導(dǎo)率變化的，最少僅需3ml樣品。溫度控制范圍：2 90 C56Zetasizer Nano S90 特點(diǎn)綜述高效率的雪崩式光電二極管(APD)檢測(cè)器提供了最高的靈敏度(高于光電倍增管檢測(cè)器20倍) ， 5nm以下測(cè)量無(wú)需外接高功率激光器。自動(dòng)調(diào)節(jié)各種樣品的最佳設(shè)置

29、在300,000:1的動(dòng)態(tài)范圍內(nèi)自動(dòng)調(diào)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(shù)據(jù)的重復(fù)性突出的高重現(xiàn)性，由精確的內(nèi)部溫控技術(shù)和在線pH測(cè)量加以保證。操作簡(jiǎn)單，無(wú)須準(zhǔn)直、校正或保養(yǎng)光路密封，防止污染57Zetasizer Nano S90 特點(diǎn)綜述- 軟件：先進(jìn)技術(shù)，操作簡(jiǎn)單全自動(dòng)設(shè)置和測(cè)量：在儀器設(shè)置上，只需最簡(jiǎn)單的培訓(xùn)，包括樣品池位置、衰減器設(shè)置、數(shù)據(jù)記錄、分析和結(jié)果顯示。測(cè)量過(guò)程中，數(shù)據(jù)的質(zhì)量可通過(guò)適時(shí)的光強(qiáng)和數(shù)據(jù)顯示評(píng)估實(shí)驗(yàn)結(jié)果報(bào)告。SOP: 標(biāo)準(zhǔn)的操作程序確保操作的一致性，保證重復(fù)性打印或屏幕顯示報(bào)告使用簡(jiǎn)單，可進(jìn)行個(gè)人化設(shè)計(jì)，只需在指定的位置選擇圖形和

30、輸入?yún)?shù)，就可根據(jù)不同的需要設(shè)計(jì)不同的報(bào)告。測(cè)量數(shù)據(jù)的完全評(píng)估58Zetasizer Nano S90 特點(diǎn)綜述- 軟件：先進(jìn)技術(shù)，操作簡(jiǎn)單樣品數(shù)據(jù)和結(jié)果存儲(chǔ)在測(cè)量文件中，方便進(jìn)行數(shù)據(jù)的比較。數(shù)據(jù)分析數(shù)據(jù)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(shì)分析時(shí)間趨勢(shì)分析所選參數(shù)趨勢(shì)分析全范圍統(tǒng)計(jì)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