12/02/2023

Microscopy techniques: resolution

In order to understand the engineering properties of materials, it is
necessary to examine them over a range of scales, which necessitates
MM9819 (CIVE5026M/5926M) the use of a number of microscopy techniques.
The working ranges of various techniques that are used for viewing
solids is shown below:
Structure of hardened
cement paste

Prof. I.G. Richardson

SEM = scanning electron microscopy. For cements, the SEM
micrographs that you see will be either secondary electron images of
fracture surfaces or backscattered electron images of flat polished surfaces.
CTEM = conventional transmission electron microscopy
HRTEM = high resolution transmission electron microscopy

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I have told you about cement hydration The next diagram shows White = steel rebar Light grey = CH
reactions and the formation of microstructure. the most important
I have shown you some images of signals:
microstructures that were taken using the secondary electrons (SE);
transmission electron microscope (TEM) or backscattered electrons
scanning electron microscope (SEM).
(BSE); and
Electron microscopy images can be formed
characteristic X-rays.
using any of the signals that result from the
interaction of the primary electron beam (PE) of
the microscope with the specimen. This is a backscattered electron (BSE) image of polished steel-reinforced concrete.
Backscattered electrons give average atomic number information. 240 µm
Transmitted electrons (TEM); Backscattered electrons Medium grey = aggregate
thin specimen (SEM); flat polished surface
Black =
‘large’ pores

Secondary electrons
(SEM); fracture surface

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Structure of hardened cement paste, hcp Structure of hardened cement paste, hcp
The last image showed the 100 µm 100 µm
binary mask for ‘large’ pores. So, at any stage of
hydration hcp is made up
In the lectures that you will
of different proportions of:

100μm
100μm
have on ‘Durability’, you will
be told about porosity and why • unhydrated cement
it is important. • hydration products
This BSE image is just of • Voids (porosity) Three types of porosity:
hardened cement paste, hcp,
rather than concrete.
The relative proportions of • Capillary Pores
Backscattered electron image
of polished hcp. these depends on the
degree of hydration & the • Gel Pores
Light = unreacted cement
Pale grey = CH i.e. Ca(OH)2 water : cement ratio (W/C).
Darker grey = other products • Entrapped air voids
Black = ‘large’ pores

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Structure of hardened cement paste, hcp Reference microstructure: location of pores

Typical sizes: A few micrometres
Component Size nm (1 nm = Component Size nm (1 nm =
10−6 mm) 10−6 mm) Ca(OH)2
Water molecule 0.28 Water molecule 0.28
Gel pore 1.5 Gel pore 1.5
Gel solid 3.0 Gel solid 3.0
Capillary pore 50 (0.05 µm) Capillary pore 50 (0.05 µm)
Cement grain 20,000 (20 µm) Cement grain 20,000 (20 µm)

Typical pore size range:

Capillary pores: 10 – 100 nm (0.01 – 0.1 µm) Inner product Outer
(Ip) C-S-H product (Op)
Gel pores: 1 – 10 nm
C-S-H
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C-S-H in a hardened C3S paste hydrated for 8 years at 20°C Structure of hardened cement paste, hcp
Pore diameter (nm)
1 10 100 1000
Ip C-S-H Mercury 0. 5
Capillary pores:

Cumulative pore volume

0. 45
Intrusion
Porosimetry 0. 4 The pore size
The gel pores are 0. 3
MIP
0. 35
0. 4 distribution is finer
between particles 0. 3
0. 25
0. 5
with lower W/C
of C-S-H, Op or Ip The capillary pores 0. 6
0. 2
0. 7 and with greater
are between the 0. 15
0. 8 degrees of
0. 1
fibres of Op C-S-H 0. 05 hydration.
0

Gel Capillary
porosity porosity

Op C-S-H
Gel pores: 1 – 10 nm; No impact on strength and permeability

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Structure of hardened cement paste, hcp

So, to summarize: voids that remain as a result of the originally
water-filled spaces not being filled by hydration products are
known as capillary pores.
More capillary pores
Higher W/C More original voids for given % hydration

Capillary porosity controls strength and permeability.

As porosity increases, strength decreases.
So higher W/C = lower strength.
On continued hydration:
• capillary pores are progressively filled by hydration products
(volume of capillary pores reduces; volume of gel pores
increases)
• strength increases, permeability reduces.

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