Neal Leddy CMA Postgraduate Analytical Workshop 2010

 Vital for many manufacturing and research processes.

Common Characterisation techniques - Optical and Scanning Electron Microscopy - Transmission and Scanning Probe Microscopy - Dynamic Light Scattering - X-ray Diffraction - Differential Scanning Calorimertry and Thermogravimetric Analysis

 Surface Area and Porosity measurement data important for many sectors:      Pharmaceuticals Paint & Surface Coating Ceramics Catalysts Gas Sensors & Filters etc.

 When a gas or vapour phase is brought into contact with a solid, part of it is taken up and remains on the outside attached to the surface.

 In physisorption (physical adsorption), there is a weak Van der Waals attraction between the adsorbate and the solid surface.

 Useful tool to characterise porous materials allowing for the determination of specific surface area, pore size distribution and porosity.

 1. Low heats of adsorption, no violent or disruptive structural changes.

 2. Can involve multiple layers of adsorbate, thus allowing for pore measurements.

 3. High temperatures tend to inhibit physical adsorption.

 4. Adsorption equilibrium is achieved quickly since no activation energy is generally required.

 5. Physical adsorption is fully reversible, allowing adsorbate to fully adsorb and desorb.

 An Adsorption Isotherm is obtained by measuring the amount of gas adsorbed across a wide range of relative pressures at a constant temperature (typically liquid N2, 77K). Conversely desorption Isotherms are achieved by measuring gas removed as pressure is reduced  5 Classical Iostherm types described by Brunauer, Deming, Deming and Teller.

Type I Pores are typically microporus with the exposed surface residing almost exclusively inside the micropores, which once filled with adsorbate, leave little or no external surface for further adsorption.

Type II Most frequently found when adsorption occurs on nonporous powders or powders with diameters exceeding micropores.

Inflection point occurs near the completion of the first adsorbed monolayer

Type III Characterised by heats of adsorption less than the adsorbate heat of liquification, adsorption proceeds as the adsorbate interaction with an adsorbed layer is greater than the interaction with the adsorbent surface

Type IV Occur on porous adsorbents with pores in the range of 1.5 – 100nm. At higher pressures the slope shows increased uptake of adsorbate as pores become filled, inflection point typically occurs near completion of the first monolayer

Type V Are observed where there is small adsorbate absorbent interaction potentials (similar to type III), and are also associated with pores in the 1.5 – 100nm range

 The most common adsorbate used is Nitrogen, however, other adsorbates are used in some circumstances.

GAS Ar Temp (˚C) α factor x10 5 (1/mm Hg) Cross Sectional Area (Å2/mol.) 14.2

Molecular weight (g/mol) 39.948

CO 2 CO N 2 -195.8

-183 -78 0 25 -183 -195.8

11.4

3.94

2.75

1.75

1.55

3.42

6.58

19.5

16.3

16.2

44.01

28.01

28.0134

-183 3.78

O 2 C 4 H 10 -183 0 25 4.17

14.2

4.21

46.9

58.12

 Surface area: Best described as the external surface area of a solid object including surface attributable to pores.

Gas adsorption provides a distinct advantage as many classical models for particle measurement and characterisation fail to consider porosity

 Brunauer, Emmett and Teller (BET), most common method used to describe specific surface area: The BET equation – W= weight of gas adsorbed P/P 0 =relative pressure Wm = weight of adsorbate as monolayer C = BET constant

BET equation requires a linear plot of 1/[W(

P/P

0 )-1] against

P/P

0  Slope (s) Intercept (i)  Wm (weight of monolayer)

 Total Surface area (S t ) can then be derived N = Avagadro’s number (6.023x10

23 ) M = Molecular weight of Adsorbate A cs = Adsorbate cross sectional area (16.2Å 2 for Nitrogen)  Specific Surface Area (S) is then determined by total Surface area by sample weight

 Single point BET: Involves determining specific surface area using a single on the isotherm  Multipoint BET: Minimum of three data points.

Plot: Summary: Relative Volume@STP 1 / [ W((Po/P) - 1) ] Pressure P/Po cc/g 1.10536e-01 7.5355 1.3195e+01 1.53021e-01 8.1192 1.7804e+01 1.99422e-01 8.7403 2.2803e+01 2.48028e-01 9.4102 2.8045e+01 2.97227e-01 10.1099 3.3472e+01 BET summary Slope = 108.451, Intercept = 1.195e+00, Correlation coefficient, r = 0.99999 C constant= 91.759

Surface Area = 31.762 m²/g

 Relative error between single and multipoint BET, (typically measured at

P/P

0

of 0.3)

 The Langmuir equation describes Microporus material exhibiting Type I Isotherms.

 Assumes adsorption limited to one monolayer.

Macroporous (>50nm) Mesoporus Microporus (2-50nm) (<2nm)

Pore Volume – Total pore volume is derived from the amount of vapour adsorbed at a relative temperature close to unity (assuming pores are filled with liquid adsorbate).

V ads V liq = volume of gas adsorbed = volume of liquid N 2 in pores V m P a = molar vol. of liquid adsorbate (N 2 =34.7cm

3 /mol) = ambient pressure T = ambient temperature

 Pore Radius The average pore size can be estimated from the pore volume.

Assuming cylindrical pore geometry (type A hysteresis) average pore radius (r p ) can be expressed as: Other pore geometry models may require further information on the isotherm hysteresis before applying appropriate model.

 Pore Volume Data Total pore volume for pores with Radius less than 15.93 Å at P/Po = 0.395090 5.787e-01 cc/g BJH method cumulative adsorption pore volume 2.103e+00 cc/g BJH method cumulative desorption pore volume 2.192e+00 cc/g DH method cumulative adsorption pore volume 2.054e+00 cc/g DH method cumulative desorption pore volume 2.146e+00 cc/g HK method cumulative pore volume 4.257e-01 cc/g SF method cumulative pore volume 4.358e-01 cc/g NLDFT method cumulative pore volume 1.904e+00 cc/g  Pore Size Data Average pore Radius 3.505e+01 Å BJH method adsorption pore Radius (Mode Dv(r)) 1.698e+01 Å BJH method desorption pore Radius (Mode Dv(r)) 1.710e+01 Å DH method adsorption pore Radius (Mode Dv(r)) 1.698e+01 Å DH method desorption pore Radius (Mode Dv(r)) 1.710e+01 Å HK method pore Radius (Mode) 1.838e+00 Å SF method pore Radius (Mode) NLDFT pore Radius (Mode) 2.261e+00 Å 2.376e+01 Å

           Barrett-Joyner-Halenda Method (BJH) Dollimore Heal Method (DH) Alpha S Method (αs) MP Method (MP) Dubinn-Radushkevic Method (DR) Dubinin-Astakhov Method (DA) Horvath-Kawazoe Method (HK) Saito-Foley Method (SF) Density Functional Theory Method (DFT) Frenkel-Halsey-Hill Method (FHH) Neimark-Kiselev Method (NK)

 Important step before measurement of surface area or pore size/volume  Surfaces are ‘cleaned’ of water/organic vapours in two ways: 1. With heating under a vacuum 2. Under a flow of dry, inert gas.

   Adsorbate is introduced in to the manifold The valve to the sample cell is opened allowing the adsorbate to interact with the sample material.

The pressure is repeatedly measured for the preset equilibration time, if the pressure drops dosing recurs and measurement proceeds until a stable reading is achieved.