Titel der Präsentation - Hansen solubility parameter

Titel der Präsentation - Hansen solubility parameter

High-efficient and automatic determination of Hansen Solubility (dispersibility) parameters of micro-, nano-particles and quantum dots by instrumental in-situ visualization and quantification of sedimentation behavior under normal or high gravity. Dietmar Lerche, LUM GmbH, Berlin, Germany 1 First of all: Its not only me; its a team work Many thanks to: Sebastian S Wolfgang Peukert Doris Segets Institute of Particle Technology (LFG), FAU, Erlangen, Germany Titus Sobisch Luis Rodriguez Sonja Horvat LUM GmbH & Dr. Lerche KG, Berlin, Germany The Next STEP in Dispersion Analysis www.lum-gmbh.com, www.dispersion-letters.com 2012 LUM GmbH 2 Introduction

1. [email protected] are essential to innovative products. 2. A dispersion or formulation step into a liquid phase is often mandatory. 3. The liquid/continuous phase must suite the specific requirements, dispersed state of particles should not change over product life time. Particle and its surrounding liquid have to be adjusted to each other The Next STEP in Dispersion Analysis www.lum-gmbh.com, www.dispersion-letters.com 2012 LUM GmbH 3 Relevant particles characteristics for dispersion A. Geometrical characteristics Size, Size Distribution, Shape B. Surface characteristics Surface morphology, chemical composition, ions, surfactance, coating materials (e.g. polymers), pickering particles Hansen Solubility Parameter since 50 years

The Next STEP in Dispersion Analysis www.lum-gmbh.com, www.dispersion-letters.com 2012 LUM GmbH 4 How to determine the HSP of particles? Experimental task: 1. to choose a set of test liquids covering more or less the 3D-Hansen space (or interested part) 2. to disperse particles into different test liquids 3. to detect the behavior How suspensed do they stay 4. to score the observation from 0 to 1 5. to calculate HSP (e.g. HSPiP Software package) The Next STEP in Dispersion Analysis & Materials Testingwww.lum-gmbh.com www.dispersionletters.com 5 2014 LUM GmbH Why does not everyone use the HSP approach? 1. Quantification of particle behavior in liquids/continous phases C. Hansen introduced quantification as a merit of sedimentation time or velocity subjective time consuming for nano 2. Ranking of liquids: Good

or Bad M. Bixenman et al. (2010) Quality control of cleaniless of electronic parts Score 1 2 3 4 5 6 Descriptio n Easily dispersed, very stable Dispersion Takes a bit to disperse, resonably stable Disperses but fairly soon starts to settle Pretty reluctant to disperse Some hint of dispersal Just sits and laughs at the solvent 3. No standardized routine method. The Next STEP in Dispersion Analysis & Materials Testingwww.lum-gmbh.com www.dispersionletters.com 6 2014 LUM GmbH How to determine the HSP of particles? Experimental task: 1. to choose a set of test liquids covering more or less the 3D-Hansen space (or interested part) 2. to disperse particles into different test liquids

3. to instrumentally detect the behavior 4. to automatically score the observation from 0 to 1 5. to calculate HSP (e.g. HSPiP Software package) The Next STEP in Dispersion Analysis & Materials Testingwww.lum-gmbh.com www.dispersionletters.com 7 2014 LUM GmbH In-situ visualization of dispersion state by STEP-Technology Conventional one point techniques Space and Time resolved Extinction Profiles t1 > t 0 12 channels, l = 870, 470 nm NIR VL Animation see: Youtube channel LUM GmbH X-Ray The Next STEP in Dispersion Analysis & Materials Testingwww.lum-gmbh.com

www.dispersionletters.com 8 2014 LUM GmbH In-situ visualization of particle sedimentation Transmission: It,p Tt,p = I0 Meniscus Extinction/Concentration: It,p - lg = Et,p = e . ct,p . d I0 Bottom last profile Meniscus Bottom start start last profile

LUMiSizer experiments. Visualization and analysis by Software Package SEPView The Next STEP in Dispersion Analysis & Materials Testingwww.lum-gmbh.com www.dispersionletters.com 9 2014 LUM GmbH General SOP: 1. Select appropriate continuous phase/liquid List of liquids used for Finn Talc 15 Liquid HSPs available from HSPiP The Next STEP in Dispersion Analysis & Materials Testingwww.lum-gmbh.com www.dispersionletters.com 10 2014 LUM GmbH General SOP: 2. Disperse particles into continuous phases, measure sedimentation at earth or higher gravity of up to 12 samples simultaneously. Isopropanol LUMiSizer: Time Interval: 2s to hours 10s Temperatur: 4 to 25C

Acceleration 6 to 2300 times earth gravity Methanol n-Heptane N-Methylformamide The Next STEP in Dispersion Analysis & Materials Testingwww.lum-gmbh.com www.dispersionletters.com 11 2014 LUM GmbH General SOP: 3. Calculate sedimentation time (ST) based on Integral Extinction (IE) ST = time to reach E0 + 0.15 Sedimentation time (or any appropriate value according to sedimentation kinetics) E0 = extinction of

pure liquid The Next STEP in Dispersion Analysis & Materials Testingwww.lum-gmbh.com www.dispersionletters.com 12 2014 LUM GmbH General SOP: 3. Calculate sedimentation time (ST) based on Integral Extinction (IE) Absolute ST of Finn Calc dispersed in different liquids The Next STEP in Dispersion Analysis & Materials Testingwww.lum-gmbh.com www.dispersionletters.com 13 2014 LUM GmbH General SOP: 4. Relative sedimentation times RST Accounts for density & viscosity differences = ( , ) , Proposed by C. Hansen 40

liquids 30 Extention for dimensionless RST , 20 10 [-] Accounts also for gravity and optical path RST = ( , ) 0 DMF DMSO ACN EtAc NMF BAc PC The Next STEP in Dispersion Analysis & Materials Testingwww.lum-gmbh.com www.dispersionletters.com THF

liquids IPA Diox MeOH Hept CHex Hex 2014 LUM GmbH 14 General SOP: 5. Score RST to 0, 1 6. Calculate HSPs Finn Talc M15 Normalization of RST Score by rounding norm = max d =12.1 MPa0.5; P =17.7 MPa0.5 h =3.9 MPa0.5; R0 =9.1 MPa0.5 by HSPiP-software, Abbott Lerche et al., Dispersion Letters 5 (2015) 13 - 18 Sss et al., in preparation

The Next STEP in Dispersion Analysis & Materials Testingwww.lum-gmbh.com www.dispersionletters.com 15 2014 LUM GmbH Application Carbon Black List of liquids used for CB study Liquid 1. n-hexane (Hex) 2. triethylamine (TEA) purity / % 95 99.5 purpose company screening screening 99 screening C.Roth, Germany

C.Roth, Germany Sigma-Aldrich, Germany 99.8 screening C.Roth, Germany > 99.5 99.5 99.5 99.8 99.5 screening screening screening screening screening C.Roth, C.Roth, C.Roth,

C.Roth, C.Roth, 99.5 screening C.Roth, Germany 99.5 screening C.Roth, Germany 99.9 screening C.Roth, Germany 98 screening Merck, Germany 99.8 99 screening

validation C.Roth, Germany C.Roth, Germany 99 validation C.Roth, Germany 99.8 validation C.Roth, Germany 99 validation C.Roth, Germany 3. pxylene (Xyl) 4. N-methyl-2-pyrrolidone (NMP) 5. 1.4-dioxane (Diox) 6. ethyl acetate (EA) 7. tetrahydrofuran (THF) 8. isopropyl alcohol (IPA) 9. acetonitrile (ACN)

10. N,N-dimethylformamide (DMF) 11. dimethyl sulfoxide (DMSO) 12. methanol (MeOH) 13. 2-butoxyethanol acetate (BAc) 14. acetone (Act) 15. n-pentane (Pent) 16. methyl acetate (MA) 17. dimethyl carbonate (DMC) 18. 1.4-butanediol (BD) Germany Germany Germany Germany Germany The Next STEP in Dispersion Analysis & Materials Testingwww.lum-gmbh.com www.dispersionletters.com 16 2014 LUM GmbH HSP of Carbon black: Integral extinction in different liquids Region of IE to determine RST.

must include best and worst solvent. Integral Extinction (IE) calculated of a ROI of 15 mm below meniscus 17 HSPs of Carbon Black Comparison of Printex L & Printex U Score by rounding D / MPa0.5 P / MPa0.5 H / MPa0.5 R / MPa0.5 Printex L 16.56 9.5 9.42 5 Printex U

17.35 8.22 7.29 4.3 HSP in same range, but different due to manufacturing process Developed approach sensitive to distinguish both products Processing (energy, time) alters surface properties of CB 1 min sonotrode 15 min sonic bath 15 HSP HSP 15 D P H 10

10 1 2 3 15 5 0 0 D P H 10 5 5 10 min sonotrode HSP

D P H Score by rounding 1 2 3 0 1 2 3 Stock concentration of Carbon Black 0.7 g/l, A: 1. 15 sec Vortex + 15 min US bath, 2. diluted to 0.014 g/l, 3. again 15 min US bath B: 1. 15 sec Vortex + 5 min US bath, 2. diluted to 0.014 g/l, 3. 1 min US treatment C: 1. 15 sec Vortex + 5 min US bath, 2. diluted to 0.014 g/l, 3. 10 min US treatment US treatment: 3 4 ml Suspension, IKASONIC U 50, Amplitude 100 %, Cycle 1, Sonotrode 600 W/cm The Next STEP in Dispersion Analysis www.lum-gmbh.com, www.dispersion-letters.com 2012 LUM GmbH

19 HSP of Carbon black (HSPiP) (C. Hansen) The Next STEP in Dispersion Analysis & Materials Testingwww.lum-gmbh.com www.dispersionletters.com 20 2014 LUM GmbH Validation of HSP regarding chosen IE and CA for RST determination Int. Extinction for tsed D [MPa0.5] P [MPa0.5] H [MPa0.5] R [MPa0.5] 0.175 17.21 8.26 11.51

6.1 0.2 17.29 8.08 11.50 6.2 0.215 17.29 8.08 11.50 6.2 Rotational speed [rpm] D [MPa0.5] P [MPa0.5] H [MPa0.5]

R [MPa0.5] 1500 17.21 8.26 11.51 6.1 4000 17.21 8.26 11.51 6.1 The Next STEP in Dispersion Analysis & Materials Testingwww.lum-gmbh.com www.dispersionletters.com 21 2014 LUM GmbH Validation of HSP approach by dispersing into a good liquid

Printex L dispersed into Diethylene Glycol Butylether Expected based on Liquid HSPs to be good Solvent is ranked as good solvent The Next STEP in Dispersion Analysis & Materials Testingwww.lum-gmbh.com www.dispersionletters.com 2014 LUM GmbH Validation of HSP approach by mixing good and bad liquids 100% Ethylacetat 100% 1.4-Dioxane Tailoring continuous phases regarding dispersibility The Next STEP in Dispersion Analysis & Materials Testingwww.lum-gmbh.com www.dispersionletters.com 2014 LUM GmbH Validation by targeted surface decoration of ZnO quantum dots Synthesis of QD: Acetate molecules on ZnO surface ZnAc + LiOH Coordinated acetate

Ligand exchange: Catechol (CAT) molecules on ZnO surface O ZnO O O O Reduction of polar contribution by larger carbon content + benzene ring O ZnO O Increase of disperse contribution by carbon backbone Dispersing procedure for ZnO - preparation of 0.1 wt.-% ZnO dispersion in different solvents - 15 minutes sonication (30 W) - solvents: n-hexane, Toluene, NMP, 1.4-Dioxane, Ethyl acetate, Acetone, Diacetone alcohol, THF, IPA, DMSO, Propylene-1,2-carbonate, MeOH, H 2O

EtOH The Next STEP in Dispersion Analysis www.lum-gmbh.com, www.dispersion-letters.com 2012 LUM GmbH ZnO quantum dots (QD): Influence of surface molecules D / MPa0.5 P / MPa0.5 H / MPa0.5 R / MPa0.5 ZnO 20h 2ML 15.46 23.31 15.45 15.4 ZnO + Cat1 20h 2ML 14.61 3.17 14.51 7.9 ZnO + Cat2 20h 2ML 21.05 7.9 15.09 11.2 Score by rounding Decreased PP for ZnO+CAT1 as expected Increased PD for ZnO+CAT2 as expected

The Next STEP in Dispersion Analysis www.lum-gmbh.com, www.dispersion-letters.com 2012 LUM GmbH Summary I 1. Sedimentometer equipped with STEP-Technology allows for instrumental in-situ visualization and quantification of particle settling behavior in different liquids. 2. High flexibility due to different wavelengths, light factors, acceleration factors and optical path of sample cells. 3. HTP due to centrifugal acceleration and multisample approach (n = 12). 4. Determination of experimental sedimentation time (STi) based on integral extinction (SEPView). 5. Calculation of the dimensionless relative sedimentation time (RSTi) and normalization by RSTi/RSTmax The Next STEP in Dispersion Analysis www.lum-gmbh.com, www.dispersion-letters.com 2012 LUM GmbH 26 Summary II 6. Automatic scoring: a) Scoring simply by rounding RSTnorm (< 0.5 good, > 0.5 bad) (treshold has to be changed to have at least 2, better 3 continuous phases in each score, or use additional liquids) b) Automatic determination of number of good liquids by determining the minimum of change of the distance of HSP

sphere adding consecutively another liquid ranked as good. 7. Entering the automatically good bad liquids into HSPiP-Software and calculate HSPs by HSPiP-Software 8. Applicability of the instrumental and automatic scoring shown for pigments, Carbon Black and ZnO-QD and validation by mixing good and bad liquids or surface alterations. 9. Attention: HSPs may be altered by dispersion process (type, energy, time). Stay close to the real processing. The Next STEP in Dispersion Analysis www.lum-gmbh.com, www.dispersion-letters.com 2012 LUM GmbH 27 Proposal to discuss: HSP traditional Hansen Solubility Parameter In case of particles engineers and scientists are mostly interested in particle dispersibility, not so much in particle solubility. To avoid confusion, would it be better to call the parameters HDP Hansen Dispersibility Parameters ?

The Next STEP in Dispersion Analysis www.lum-gmbh.com, www.dispersion-letters.com 2012 LUM GmbH 28 Thank you for your attention!!! Questions?? Thanks for funding: hanks to Prof. Abbott or HSPiP and help hanks to S. van Loon or Finn Calc M15 More Information: See our booth (Adaptive Systems) [email protected], [email protected] www.LUM-GmbH.com, www.Dispersion-Letters.com The Next STEP in Dispersion Analysis www.lum-gmbh.com, www.dispersion-letters.com 2012 LUM GmbH

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