Tiêu chuẩn iso 15901 1 2016

© ISO 2016 Evaluation of pore size distribution and porosity of solid materials by mercury porosimetry and gas adsorption — Part 1 Mercury porosimetry Evaluation de la distribution de taille des pores[.]

Evaluation ofpor e size distribution

Part 1:

Ev lu tio de la dis rib tio de tai e de s p re s e tla p rosité de s

matéria x solde s p r p rosimétrie à me rcur e t l’adsorptio de s g z —

Partie 1: Porosimétrie à me cur

COPYRIGHT PROTECTED DOCUMENT

© ISO 2016, P blshed in Sw itz rlan

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written permis ion Permis ion c n be req esed from either ISO at the ad r es below or ISO’s member bod y in the c u try of

F reword i v

Introduction v

1 Sc ope 1

2 Nor mati ve r eferenc es 1

3 Terms and definitio s 1

4 Symbols and abbreviated terms 4

5 Principles 5

6 A pparatus and mater ial 6

6.1 Sample holde

6 6.2 Por osimete 7

6.3 Mer cury 7

7 Proc ed res for cal bratio and performanc e 7

7.1 General 7

7.2 Pr es ur e sig nal calbr ation 7

7.3 Volume sig nal calbration 7

7.4 Vacu m tr ansd c r calbr ation 7

7.5 Ve ification of p r osimete pe formanc 8

8 Proc ed res 8

8.1 Sampl ng 8

8.1.1 Obtaining a tes sample 8

8.1.2 Q uantity ofsample 8

8.2 Method 9

8.2.1 Sample pr e-treatment 9

8.2.2 Fi ing of the sample holde an ev cuation 9

8.2.3 Fi ing the sample holde with mer cury 9

8.2.4 Measur ement 1

8.2.5 C mpletion of tes 1

8.2.6 Blan an sample compr es ion correction 1

9 Evaluatio 11

9.1 Dete mination of the p re siz distribution 1

9.2 Dete mination of the spe ific por e v lume 1

9.3 Dete mination of the spe ific surfac ar ea 1

9.4 Dete mination of the bulk an skeleton densities 1

9.5 Dete mination of the p rosity 1

10 Repor ting 13

A nne x A (informative)Mercur y porosimetry anal ysis r esults 14

A nne x B (informative)Rec ommendatio s for the safe handlng of mer cury 17

Biblog raphy 19

Forewor d

ISO (he Int ernational Org nization for Stan ardization) is a worldwide fede ation of national s an ards

b dies (ISO membe b dies) The work of pr p ring Int ernational Stan ards is normaly car ied out

through ISO t echnical committ ees Each membe b dy int er st ed in a subje t for w hich a t ech ical

committ ee has be n es a lshed has the right t o be r pr sented on that committ ee Int ernational

org nizations, g ove nmental an non-g ove nmental, in laison with ISO, also take part in the work

ISO cola orat es closely with the Int ernational Ele trot ech ical Commis ion (IEC) on al matt ers of

ele trot ech ical s an ardization

The proc d r s used t o develo this document an those int en ed for it furthe maint enanc ar

desc ibed in the ISO/IEC Dir ctives, Part 1 In p rticular the dife ent a pro al c it eria ne ded for the

dife ent ty es of ISO document should be not ed This document was draft ed in ac ordanc with the

edit orial rules of the ISO/IEC Dir ctives, Part 2 ( e www.iso.org dir ctives)

A tt ention is drawn t o the p s ibi ity that ome of the element of this document ma be the subje t of

p tent right ISO shal not be held r sp nsible for identifying any or al such p t ent right Detai s of

any p tent right identif ied d ring the develo ment of the document wi be in the Introd ction an / r

on the ISO ls of p t ent de larations r c ived ( e www.iso.org p t ent )

Any trade name used in this document is information given for the convenienc of use s an does not

cons itute an en orsement

For an ex lanation on the meaning ofISO spe ific terms an ex r s ions r lated to conformity as es ment,

as wel as information a out ISO’s adhe enc to the Wor ld Trade Org nization (WTO) principles in the

Te h ical Bar ie s to Trade (TBT) se the folowing URL: www.iso.org/ iso/for word.html

The committ ee r sponsible for this document is ISO/TC 24, Particle charac te i zatio includin s iev in ,

Subcommitt ee SC4, Particle charac teri zatio

This se on edition canc ls an r plac s the f irs edition (ISO 1 90 -1:2 0 ), w hich has be n t ech icaly

r vised It also incorp rat es the C r ig en um ISO 1 9 1-1:2 0 /Cor 1:2 0

ISO 1 9 1 consis s of the folowing p rt , u de the g ene al title Ev lu tio o p r s i ze di s trib tio a d

p ros it y o s old materials b me c ury p ros imetr y a d g s adsorptio :

— Part 1: Me rcury p rosime try

— Part 2: An lysis o mesop r s a d mac ro or s b g s adsorption

— Part 3 : An lys i s o mic ro or s b g s ads orptio

In g ene al, dife ent por s (mic o-, meso-, an mac o or s) ma be pictur d as eithe a e tur s,

channels or ca ities within a sold b dy or as sp c ( i.e int ers ic s or v ids) between sol d p rticles

in a bed, comp ct or a gr g t e Porosity is a t erm w hich is oft en used t o in icat e the porous natur of

sold mat erial an in this Int ernational Stan ard is mor pr cisely def ined as the ratio of the t otal p r

v lume of the ac es ible por s an v ids t o the volume of the particulat e a glome at e In ad ition t o

the ac es ible p r s, a sol d ma contain closed p r s w hich ar isolat ed from the ext ernal surfac an

int o w hich fluids ar not a le t o penetrat e The charact erization of closed por s is not co e ed in this

Int ernational Stan ard

Porous mat erials ma take the form of fine or co rse p wde s, comp ct , extru at es, she t or

monolths Their charact erization usualy inv lves the det ermination of the p r siz dis ribution as

wel as the t otal ac es ible p r v lume or p rosity F or some purp ses it is also ne es ary t o s u y the

p r sha e an int er on e tivity and t o det ermine the int ernal an ext ernal spe if ic surfac ar a

Porous mat erials ha e gr at t ech olo ical imp rtanc , for ex mple in the cont ext of the folowing:

— controled drug r lease;

— cataly sis;

— g s sep ration;

— f iltration inclu ing st eri zation;

— mat erials t echnolo y;

— environmental prot ection an p l ution control;

— natural r se v ir rocks;

— buiding mat erials;

— polyme san c ramic

It is wel es a l shed that the pe formanc of a p rous sold (e.g it s r ngth, r activity, pe mea i ty) is

dependent on it por s ructur Many dife ent methods ha ebe n develo ed for the charact erization

of por s ructur In view of the complexity of mos p rous sol ds, it is not surprising that the r sult

o tained ar not alway s in a r ement an that no single t ech iq e can be r l ed up n t o pro ide a

complet e pictur of the p r s ructur The choic of the mos a pro riat e method depen s on the

a plcation of the p rous sold, it chemical an phy sical natur an the rang eof por siz

The mos commonly used methods ar as fol ows:

a) Me cury p rosimetry, w he e the por s ar f il ed with me cury un e pr s ur This method is

suita le for many mat erials with por s in the a pro imat e diamet er rang e of 0,0 4 µm t o 40 µm

b) Meso- an mac o or analy sis b g s adsorption, w he e the por s ar charact eriz d b adsorbing

a g s, such as nitrog en at lq id nitrog en t empe atur The method is used for p r s in the

a pro imat e diamet er rang e of 0,0 2 µm t o 0,1 µm (2 nm t o 1 0 nm)

c) Mic o or analy sis b g s adsorption, w he e the p r s ar charact eriz d b adsorbing a g s,

such as nitrog en at lq id nitrog en t empe atur The method is used for p r s in the a pro imat e

diamet er rang e of 0,4 nm t o 2 nm

Evaluation ofpor e size distribution and por osity ofsolid

Part 1:

WARNING — The use of this Internatio al Standard may inv lve hazardo s materials,

o eratio s an equipment This Internatio al Standard d es n t purport to addres al of the

safety pro lems as ociated with its use It is the responsibi ity of the use of this Internatio al

Standard to establsh appropriate safety and he lth practices and determine the ap l cabi ity of

re ulatory l mitatio s prior to use

This Int ernational Stan ard desc ibes a method for the ev luation of the p r siz dis ribution an

the spe ific surfac ar a of p r s in solds b me cury p rosimetry ac ording t o the method of Ritt er

an Drake

[1][2]

It is a comparative t es , usualy des ructive d e t o me cury contamination, in w hich

the v lume of me cury penetrating a p r or v id is det ermined as a fu ction of an a pl ed hydros atic

pr s ur , w hich can be r lat ed t o a por diamet er

Practical conside ations pr sently l mit the ma imum a pled a solut e pr s ur t o a out 40 MPa

(6 00 psi) cor esp n ing t o a minimum eq iv lent por diamet er of a pro imat ely 4 nm The

ma imum diamet er islmit ed for samples ha ing a significant depth d e t o the dife enc in hydros atic

head of me cury from the t op t o the b tt om of the sample F or the mos purposes, this lmit can be

r g rded as 40 µm The measur ment co e int er-p rticle an intra-p rticle porosity In g ene al,

without ad itional information from othe methods it is difficult t o dis inguish betwe n theseporosities

w he e they co-exis The method is suita le for the s u y of mos porous mat erials non-wet a le b

me cury Samples that amalg mat e with me cury, such as c rtain metals, e.g g old, aluminium, co pe ,

nickel an sive , can be u suita le with this t ech iq e or can r q ir a pr lminary p s iv tion Un e

the a pled pr s ur some mat erials ar deformed, compact ed or des ro ed, w he eb o en p r s ma

becola sed an closed p r s o ened In some cases it ma be p s ible t o a ply sample compr s ibi ty

cor e tions an useful comp rative data ma s i l be o taina le F or these r asons, the me cury

porosimetry t ech iq e is conside ed t o be comp rative

2 Normati ve r eferences

The folowing document , in w hole or in p rt, ar normatively r fe enc d in this document an ar

in ispensa le for it a pl cation F or dat ed r fe enc s, only the edition cit ed a pl es F or u dat ed

r fe enc s, the lat es edition of the r fe enc d document ( inclu ing any amen ment )a pl es

ISO 3 6 , S mpln o chemic al produc ts fr indus trial use — S fet y in s ampln

ISO 1448 , Partic ulate mate ial s — Samplng an sample splt ing for the det ermination of particulat e

pro e ties

3 Terms and definitions

F or the purposes of this document, the folowing t ermsand definitions a ply

3.1

porosimeter

ins rument for measuring p r v lume an p r siz dis ribution

p rous or nonp rous sold comp sed of disc et e p rticles with ma imum dimension les than a out

1 mm, p wde swith a p rticle siz below a out 1 µm ar oft en r fe r d t o as f ine p wde s

p r not t otaly enclosed b it wal s an o en t o the surfac eithe dir ctly or b int er on e ting with

othe p r s an the efor ac es ible t o fluid

int ernal p r width (for ex mple, the diamet er of a cy lindrical por or the dis anc between the

o p sit e wals of a sl t) w hich is a r pr sentative v lue of v rious siz s of v cant sp c inside a p rous

pore diameter

diamet er of a por in a model in w hich the p r s ty icaly ar as umed t o be cy lin rical in sha e an

w hich is calculat ed from data o tained b a spe if ied proc d r

3.1

median pore diameter

diamet er that cor espon s t o the 5 th pe c ntie of p r volume, i.e the diamet er for w hich one half of

the p r v lume is fou d t o be in larg er p r s an one half is fou d t o be in smale p r s

hy raul c pore diameter

a e ag e p r diamet er, calculat ed as the ratio of p r v lume multipled b four t o por ar a

v lume of the sample inclu ing the volume of closed por s ( if pr sent) but ex clu ing the volumes of

o en p r s as wel as that of v id sp c s betwe n particles within the bulk sample

t otal volumeof the sold cons ituent ofthe sample inclu ing closed p r s an p r s inac es ible or not

det ecta le b thes at ed method;

interparticle porosity

ratio of the volume of void sp c between the in ivid al p rticles t o the bulk volume of the particles

or p wde

3.29

intraparticle porosity

ratio of the v lume of o en p r s inside the in ivid al p rticles of a p rticulat e or divided sold sample

t o thebulk volume oc upied b the sample

angle at w hich a lq id/ a our int erfac me t the surfac of a sold mat erial

4 Symbols and abbr eviated terms

F or the purposes of this document, the fol owing symb ls a ply

so-let e u it

C nve sion fact ors

cm3

, mm3

13

mm3

=1 cm3

= 1

−

m3

cm3

, mm3

cm3

, mm3

·g

−1

cm3

mas of sample holder with

sample an f iled with mer

-cury

Symb l Te m SI u it De ived an o

Me cury p rosimetry is a widely ac ept ed method for por siz analy sis of v rious mat erials such as

pharmac utical ta let , bui ding mat erials, cataly st an their sup ort , mainly be ause it alow s p r

size /porosity analy sis t o be u de taken o e a wide rang e of p r siz s from meso- t o mac o or s with

p r widths a out 0,0 4 µm t o a out 40 µm

[1]–[7]

In contras t o ca i lary condensation, w he e the

por fluid wet the p r wal s ( i.e the contact angle is smale than 90 degr es), me cury p rosimetry

desc ibes a non-wet ing situation ( i.e the contact angle is gr at er than 9 degr es) an the efor

pr s ur mus be a pled t o for e me cury int o the por s Th s, a pro r s ive inc ease in hydros atic

pr s ur is a pl ed t o ena le the me cury t o ent er the p r s in de r asing orde of width A ccordingly,

the e is an inve se r lationshipbetwe n the a pled pr s ur , p, an thep r diamet er, d

p, w hich in the

simples case of cy lin rical por sis given b the Washburn eq ation ( e 9.1)

In the a plcation of me cury porosimetry, the v lume of me cury ent ering the por s ructur is

measur d asthe a pled pr s ur is grad aly inc eased The v lue V

Hg

at he a pled pr s ur , p, gives

the cumulative v lumeof al a ai a le p r s of diamet er eq al t o, or gr at er than, d

p The det ermination

ma proc ed eithe with the pr s ur being raised in a st ep-wise manne an the v lume of me cury

intru ed measur d aft er an int erv l of time w hen eq i brium has be n achieved, or b raising the

pr s ur in a contin ous (pro r s ive) manne

Figur 1 show s two intrusion/extrusion cycles of me cury int o a p rous p wde as a function of

pr s ur R egion (a) cor esp n s t o a r -ar ang ement of p rticles within the p wde bed, folowed

b intrusion of the int erp rticle v ids (b) Fi lng of intra article p r s oc urs in the r gion (c) an

for some mat erials (r ve sible) compr s ion is then p s ible at highe pr s ur s (d) Hy st er sis (h)

is o se ved an extrusion (e) oc urs at dife ent pr s ur s than for the intrusion On completion of a

firs intrusion-extrusion cycle, usualy some me cury is r tained b the sample, the eb pr venting the

lo p from closing (f) Intrusion-extrusion cycles aft er the f irs cyclecontin e t o show hyst er sis(g) but

eventualy the lo p closes, showing that the e is no furthe entra ment of me cury On mos samples,

entra ment is not o se ved anymor aft er jus the se on cycle, w hich also in icat es that hy st er sis

an entra ment ar es entialy of dife ent origin

1 powder compr es ion

2 interparticle filing

3 intraparticle filing

Y intru ed mer cury, V

Hg

X h draulic pr es ur e, lg p

Figure 1 — Characteristic fe tures of mer ury porosimetry curves

Thehy st er sis an entra ment phenomena is u doubt edly imp rtant in orde t o o tain a compr hensive

por siz analy sis Me cury entra ment a pears t o be ca used b the ruptur of me cury bridg es in p r

cons rictions d ring extrusion from in -b t le por s Dife ent me hanisms ha e be n pro osed t o

ex lain intrusion/extrusion hy st er sis

[6]–[1 ]

The single p r me hanism impl es that hy st er sis can

be u de st ood as an intrinsic pro e ty of the intrusion/extrusion proc s d e t o n cleation b r ie s

as ociat ed with the formation of a v p ur-lq id int erfac d ring extrusion, or discus ed in t erms

of dife enc s in adv ncing an r c ding contact angles In contras , the network models take int o

ac ou t the ink-b t le an pe colation efe t in p r networks It is now g ene aly ac ept ed that p r

blocking efe t , w hich can oc ur on the intrusion branch, ar simi ar t o the pe colation efe t inv lved

in the desorption of g ses from p rous networks In e d, the sha e of a me cury intrusion/extrusion

hy st er sis lo p oft en a r es wel with that of the cor esp n ing g s adsorption lo p

[9][1 ]

Th s,

me cury intrusion an the ca i ary ev p ration a pear t o be based on simiar me hanisms The

por blocking pe colation efe t ar dominant in disorde ed por networks, an a r la le p r siz

dis ribution can only be calculat ed from the intrusion branch b a plying complex network models,

b sed on pe colation theory The a plcation of such models also alow s one t o o tain a l mit ed amou t

of s ructural information from the intrusion/extrusion hy st er sis lo p

[1 ][1 ]

6 A pparatus and material

WARNING — It is important that pro e precautions for the protection of laboratory per onnel

are taken w hen mer ury is used A ttentio is drawn to the relevant re ulatio s and guidance

documents w hich appertain for the protectio of per o nel in e ch of the membe co ntries

6.1 S mple holder

The sample holde ma consis of a ves el with a u iform b r ca i lary tube through w hich the sample

can be ev cuat ed an the ves el fil ed with me cury The ca i lary tube is at ached t o a wide b r

tube in w hich the t es sample is locat ed If pr cise measur ment ar r q ir d, the int ernal v lume of

the ca i lary tube should be between 2 % an 9 % of the ex e t ed p r an int erp rticle v lume of

the sample Sinc dife ent mat erials exhibit a wide rang e of o en p rosities a n mbe of sample ves el

holde s with dife ent tube diamet ers an ves el v lumes is r q ir d A spe ial design of sample holde

is oft en used with p wde ed samples t o a oid los of p wde d ring ev cuation

In orde t o ev luat e the p rosity an the bulk an skelet on densities, the v lume of the sample holde ,

inclu ing the ca i lary tube, mus bek own

6.2 P orosimeter

An ins rument ca a le of car ying out the t es at two seq ential measur ment , a low pr s ur t es

up t o at leas 0,2 MPa (3 psi) an a high-pr s ur t es up t o the ma imum o e ating pr s ur of the

p rosimet er [cir a 400 MPa (6 0 0 psi)]

The p rosimet er ma ha e seve al p rt for high an low pr s ur o e ation, or the low pr s ur t es

ma be car ied out on a sep rat e unit

Prior t o any p rosimetry measur ment it is ne es ary t o ev cuat e the sample using a ty ical rotary

v cu m pump, eq ip ed with a me cury r taine an then t o fil the sample holde with me cury t o a

given low pr s ur A means of g ene ating pr s ur is ne es ary t o cause intrusion of me cury

A means of det ecting the chang e in the v lume of me cury intru ed t o a r solution of 1 mm

3

or les is

desira le Thisis usualy done b measuring the chang e in ca acitanc betwe n the me cury column in

the ca i ary tube an a metal sle ve arou d the out ide of the sample holde

Sample pr paration an the fil ing of the sample holde with me cury r q ir a v cu m, the level of

w hich is usualy r corded using a transd c r F or the p rosity ev luation, two signals ar r q ir d t o

be measur d in a p rosimet er; the a pled pr s ur an the cor esp n ing v lume chang e of me cury

as it intru es int o the p r s in the sample The v lume of me cury displac d from a pr cision glas

ca i lary tube shal be pr fe a ly det ermined as a function of an ele trical ca acity chang e

7.2 Pres ur e sig nal cal bration

Pr s ur is usualy measur d with ele tronic pr s ur transd c rs w hich ar fact ory cal brat ed The

ac uracy of the pr s ur measur ment should be within ± % of the ful scale transd c r r ading

or ±2 % of the actual r ading, w hicheve is the lowe It is r commended that ve ification of calbration

an trac a i ity t o an ac r dit ed org nization, be r gularly pe formed

7.3 Volume sig nal cal bration

The ac uracy of the v lume measur ment should be within ± % of the t otal v lume t o be measur d

It is r commen ed that ve if ication of cal bration, an trac a i ty t o an ac r dit ed org nization, be

r gularly pe formed

7.4 Vacuum transduc er cal bration

The ac uracy of the indicat ed v cu m is g ene aly not c itical The v cu m manifold sy st em, without a

sample, should be ca a le of achieving at leas 7 Pa, an if pos ibleit hould be calbrat ed t o within 1 Pa

at this level