The City University of Hong Kong

Department of Physics
Analysis of harmful substances in oil paints through
Scanning Electron Microscopy (SEM) and Mass Spectrometer

PHY3231 Proposal
 Table of contents

No. Content Page

1 Time and budget 1

2 Abstract 2

3 Scientific Background 3-5

4 Research Plan 6-8

5 Equipment and materials required 9

6 Impact 10

7 Time and budget 11

8 Bibliography 12

1
Abstract
Oil paint is a material that forms a solid film on the surface of an objec
t. It is always used in modern buildings. There are two main reasons that o
il paint is commonly used on the walls of buildings. One reason is to prote
ct the wood from damaging and exposed metal structures from erosion in buil
dings, since oil paint is useful to avoid damage from humidity, temperatur
e, etc. Another reason is for decoration, people like to use different colo
rs of oil paint to match the style of their house. Therefore, paint is wide
ly used in indoor environments, whether in residence or public buildings.

According to the National Human Activity Pattern Survey [4], Klepeis et.al
(2001) found that people In America spend more than 86% of their time indoo
rs. With an assumption that people in developed cities have similar behavio
r on staying location, the survey can be explained as modern people used to
stay indoors in their lifetime, which is an environment full of oil paint i
n the surrounding. Therefore, it is of great importance for us to examine w
hether oil paint contains harmful substances.

Generally, Oil paint contains two main types of harmful substances, heavy m
etals and Volatile Organic Compounds (VOCs), which may bring serious diseas
es to the human body. If air does not circulate in the indoor environment,
VOCs become more concentrated, people may over inhale to cause jeopardy; he
avy metals will also cause hazards as oil paint is used on walls, which som
e people may always have physical contact with. Thus, it is crucial for peo
ple to use oil paint with low VOCs and heavy metal concentration in their r
esidence, to avoid damage from these substances of oil paint.

In this research, the samples would be picked from the top 10 best-selling
oil paint brands, which is listed on “Top 10 Coatings Enterprises In The W
orld” [14], on purpose to distinguish and make a comparison on the degree
of danger of the most commonly used brand paints over the world. Specifical
ly, in the experiment, Scanning Electron Microscopy (SEM) and Mass spectrom
eter are recommended to be used on analyzing the amount of heavy metal and
VOCs respectively in this proposal.

2
Scientific Background
Scanning Electron Microscopy equipped with an Energy Dispersive X-ray Analy
sis detector and Mass Spectrometer are required instruments in our project.
The scientific background information will be discussed below.

Scanning Electron Microscopy (SEM)

Electron Gun is used to generate high-speed electrons. The accelerated elec
tron will pass the condenser and the electromagnetic lens will help the con
densed electron focus on the sample. When the electron bombards the specime
n, various types of by-product electrons will be formed, ranging from Auger
Electron, Backscattered Electron, Secondary Electron, Inelastically Scatter
ed Electron and Elastically Scattered Electron. However, these are not usef
ul in the experiment, since one wants to obtain the information of the elem
ents in the specimen.

Besides electrons, two kinds of X-ray may also be generated, including Brem
sstrahlung X-ray and Characteristic X-ray. The latter one is the signal tha
t one wants to collect since it possesses the information of the type of th
e element. Hence, one requires the analysis of the Energy-Dispersive X-ray.

Energy-Dispersive X-Ray Analysis (EDX)

When the primary electron hits the inner shell electron, it will be knocked
off from the atom. Thus, there will exist a vacancy of the electron in the
inner shell orbital, leaving a hole. Nevertheless, Nature tends to minimize
the potential energy, the outer shell electron will jump to the hole. This
phenomenon is known as the relaxation of an atom [1]. An X-ray will be rele
ased during this process, in particular, the Characteristic X-ray. This X-r
ay is unique corresponding to different elements due to specific energy lev
el differences between the two orbitals. Hence, by observing the X-ray ener
gy, we can identify the element type. With the internet, one can easily fin
d the database of different elements relating to different Characteristic X
-rays. In the heavy metal part, a series of characteristic X-rays of three
heavy metals are listed for reference. However, when the experiment is carr
ied out by using EDX analysis, it is not needed to compare every heavy elem
ent by observing directly with bare eyes, since EDX analysis will automatic

3
ally print out a report that has the description
of the existence of the element and the quantity.

4
- Mass Spectrometer
The working principle of mass spectrometer consists of 4 main stages [8],
[16]:

Stage 1: Ionisation of the sample

Putting the sample into the entry and heat
ing it up with the heater, the vaporized s
ample will bombard with a bunch of electro
ns emitted by the electron gun. The electr
ons in the sample are then knocked off so
that the sample can be ionized into differ
ent ions.

Stage 2: Acceleration
To ensure the ions all have the same velocity, they are accelerated by an e
lectric field. Only the undeflected ions with the selected velocity can pas
s the velocity selector [6]. Utilizing the electric plates, we can acceler
ate the ions as ions have charges. The selected velocity equation is listed
below,
𝐸
=𝐸
𝐸
Stage 3: Deflection
The accelerated ions are deflected by a magnetic field in the separation ch
amber. Different deflections of the ions will occur as they have different
mass to charge ratios, and the related equation is listed below,
𝐸𝐸
=𝐸
𝐸𝐸
Where m is the mass of the ion, v is the velocity of the ion, B is the magn
etic field strength and r is the radius of the ion’s path. We can ensure t
hat the ion has the same velocity, magnetic field strength and charge. Thu
s, we can know the relationship between the radius and the mass [6]. More d
eflection will happen if the mass to charge ratio is smaller, vice versa.

Stage 4: Detection

5
When the number of ions arrives at the detector, we can use the current rec
eived by the chart recorder to analyze the type of volatile molecules and t
heir amount.

6
- Volatile Organic Compounds (VOCs)
Volatile Organic Compounds (VOCs) are organic compounds that have relativel
y low boiling points and are easy to vaporize, i.e.having an initial boilin
g point less than or equal to 250°C measured at a standard atmospheric pre
ssure of 101.3 kPa [12]. Benzene, formaldehyde, dichloromethane and 1,1,1-t
richloroethane are the common VOCs in the oil paint. Over inhaling of VOCs
may cause nervous system, organ damage and cancer.

In the VOCs analysis experiment with the Mass Spectrometer, the properties
of characteristic mass to charge ratios spectrum will be used in the analys
is. This will be discussed in the research plan part in detail.

- Heavy metal
Heavy metals are defined as metals with a particular density of greater tha
n 5g/cm³. Lead (Pb), Mercury (Mg) and Cadmium (Cd) are the common heavy met
als that exist in oil paint, and these heavy metals will cause disease when
humans have physical contact with them, for example, affecting sensory-moto
r function, reducing the quantity and quality of sperm [2] and destroying k
idney epithelial cells [3].

In the heavy metal-related experiment with SEM, these three elements will e
mit the following characteristic energy of X-ray when the electron jumps fr
om the outer shell to the lower shell. Here are some of the examples of the
transitions.

Types of He 𝐸𝐸1 𝐸𝐸2 𝐸𝐸 𝐸𝐸1 𝐸𝐸2 𝐸𝐸1

avy Metal (keV) (keV) (keV) (keV) (keV) (keV)

Pb 70.82 72.80 84.94 10.55 10.45 12.61

Hg 74.97 68.90 80.25 9.99 9.90 11.82

Cd 23.17 22.98 26.10 3.13 3.13 3.32

The meanings of these transitions are shown in the picture above. For examp
le, 𝐸𝐸1 represents the transition from 𝐸𝐸𝐸𝐸 to 𝐸𝐸 .

7
If the characteristic energy appeared on the outcoming diagram of EDX, the
appearance of that element was confirmed and we can get the quantity inform
ation of the element from EDX.

8
Research Plan
- Sample selection
To broaden the range of influence of this research, the samples of oil woul
d be purchased from the top 10 oil paint companies on the global market sha
re, which is listed on “Top 10 Coatings Enterprises In The World“ [14] an
d covered around 43% of the oil paints sales in 2021 in total. In case ther
e are three main types of paint used indoors, i.e. latex paint, enamel pain
t and wood paint, 3 types of oil paint are targeted to be purchased for eac
h brand of oil paint. Thus, there are 30 samples that have to be analyzed f
or each experiment.

- Sample preparation SEM

First, we have to separate the oil paint with 0.25mL from each bucket of oi
l paint. As SEM only works with a conductive sample, we have to make the oi
l paint be conductive. Before the experiment, we have to mix the oil paint
samples with 0.2mL silver glue and stir it regularly. Then, the sample will
be heated for about one hour to ensure the sample becomes solid.

- Preparation before the experiment of Mass Spectrometer

For the Mass Spectrometer, unlike SEM, Mass Spectrometer does not have a pr
oblem with the conductivity of samples. To do the preparation for the Mass
Spectrometer experiment, we just have to Separate the oil paint with 0.25ml
from each bucket of oil paint.

As it is critical that the ions created in the ionization chamber pass thro
ugh the machine without colliding with air molecules, Vacuum is required fo
r the experimental environment [16]. Thus, we have to make sure the experim
ental environment is high vacuum before the experiment by opening the pump.

9
- Heavy metal analysis with SEM
After sufficient preparation mentioned above, it is crucial to notice that
one requires that there exists minimum energy, or minimum voltage, to produ
ce characteristic X-rays, which is known as Critical Excitation Energy. It
is calculated as follows [11]:

𝐸𝐸(𝐸) = 𝐸𝐸𝐸 + 𝐸𝐸𝐸 + 𝐸𝐸𝐸

where 𝐸𝐸𝐸 =𝐸𝐸(𝐸𝐸) − 𝐸𝐸(𝐸𝐸𝐸+𝐸𝐸𝐸 ) , 𝐸𝐸𝐸 =𝐸𝐸(𝐸𝐸) − 𝐸𝐸(𝐸𝐸𝐸𝐸 ) , 𝐸𝐸𝐸 =

𝐸𝐸(𝐸𝐸) − 𝐸𝐸(𝐸𝐸𝐸𝐸 )

In this experiment, the voltage for the electron gun would be set to 30keV.

After the processing of SEM, an EDX diagram will be obtained, similar to th

e example diagram above. From the diagram, the kind of elements present in
the particular oil paint can be observed. Furthermore, one can also know wh
at kind of heavy metal elements have larger portions in the oil paint. Howe
ver, for the quantity information of certain elements, EDX analysis will au
tomatically give us the precise amount of the particular heavy metal, no fu
rther calculations are required for us.

Limitation: As silver glue is added into the sample to make it be conductiv

e for SEM analysis, silver should be excluded from the analysis result. Ref
erring to the article from Dartmouth Toxic Metals Superfund Research Progra
m [13] “silver is almost completely biologically inert, and even if ingest
ed, would pass through the human body without being absorbed into tissue
s”. Therefore, even though silver cannot be analyzed, it does not affect o

10
ur objective of research in case that silver is not harmful to the human bo
dy.

11
- VOCs analysis with Mass Spectrometer
In the experiment for VOCs, we have to put the sample into the Mass spectro
metry and start functioning the mass spectrometer. To vaporize VOCs in the
sample, the sample should be heated up to 250°C [12]. Also, an electron gu
n will be used to bombard the vaporized organic sample as it travels throug
h the ionization chamber of a mass spectrometer. These electrons have enoug
h energy to knock off one electron from an organic molecule, resulting in t
he formation of a charged ion. This ion is known as the molecular ion, and
it is frequently denoted by the letters M+•. M+• can be broken into charged
ions and radicals. [16]

However, not all the ions can reach the detector. Due to deflection, they m
ay collide with the wall in the chamber. After the collision, the ions will
be neutralized and removed by the vacuum pump. The magnetic field should be
adjusted for the repeated experiment till the whole common VOCs are discove
red in the result.

As a result, we can obtain a stick diagram of the intensity to mass-charge

ratio; the example diagram is on the right. Nevertheless, in a real experim
ent, the diagram will be more complicated. The diagram shown above indicate
s the amount of certain broken masses.

12
Notice that by observing which type of broken molecules are present in the
oil paint, we can deduct what kind of original molecules are present in the
oil paint, and also the total amount. Here is a table shown above, showing
different common broken molecules associated with their m/z value. [10] Hen
ce, we can easily deduct what types and amounts of molecules are in the oil
paint.

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Equipment and materials required
1. Mass Spectrometer with analyzing instrument
(available in State Key Laboratory of Marine Pollution, Cit

yU HK)

2. Scanning Electron Microscopy with analyzing instrument

(available in Physics Laboratory, CityU HK)

3. Sample of oil paints (30 buckets):

Types of paints latex paint, enamel paint and wood paint

Brands of paints Sherwin-Williams, Pittsburgh Plate Glass Comp

any, AkzoNobel, Nippon Paint, RPM Internation
al, Badische Anilin-und-Soda-Fabrik, Axalta,
Kansai Paint Co., Behr Process Corporation, A
sian Paints

4. Silver Glue

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Impact
Inductively coupled plasma optical emission spectroscopy (ICP-OES) is commo
nly used in analyzing heavy metals mixtures. However, ICP-OES requires the
aerosolization of the sample [9]. In this case, using SEM can reduce the co
st and increase the efficiency of sample preparation.

Besides, Fourier Transform Infrared Spectroscopy is currently used for anal

yzing organic substances as it is fast to get the result [7]. However, it i
s limited due to the existence of H2O from the water-based oil paint [5]. U
sing Mass spectrometer can determine both oil-based and water-based oil pai
nt which increases the feasibility of the experiment.

- Objectives

● List out the harmful matters contained in oil paint to raise the publ
ic’s attention to the danger of oil paints.

● Popularize the danger of harmful substances in oil paint in order to

avoid unintentionally suffering from toxicity and other diseases.

● Provide a comparison table on the safety level between different bran

ds of oil paint for the general public.

● Encourage the public to establish and emphasize the safety precaution

s of using oil paint.

● Stimulate oil paint companies to develop their product on safety, esp

ecially on reducing the amount of VOCs and heavy metals.

● Help to check the oil paint currently used in the CityU campus to pro
tect health among CityU’s students and faculty

● Determine the use of oil paint for further application, like the use
on the wall of the new building.

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Time and budget

Process Time

Ask for permission for instruments Depends on the booking situation

Oil paint procurement and transportation 2 weeks (day 1 - 14)

Experiment with SEM 2 days (day15 - 16)

Experiment with Mass Spectrometer 2 days (day 17 - 18)

Result analyzing and report writing 1 week (day 19 - 25)

On the expected processing time, Oil paint procurement and transportation r

equire nearly 2 weeks; the execution of the two experiments requires nearly
4 days; the result analyzing and report writing requires nearly 1 week. In
total, the whole experiment can be finished within a month.

Instruments and material Cost

Mass spectrometer for 10 hours 2680 HKD

Scanning Electron Microscopy (SEM) for 10 hours 1000 HKD

30 Buckets of oil paint 15000 HKD

Silver Glue 2000 HKD

Total Cost 20680HKD

On the expected cost, as both the mass spectrometer and Scanning Electron M
icroscopy are available at CityU, we can borrow the instruments for $268 HK
D and $100 HKD per hour respectively for Mass Spectrometer and SEM; For the
sample, we will prepare 30 buckets of oil paint for the experiment, with av

16
erage expenses of $500 HKD per bucket.

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