Material removal mechanism of ceria

particles with different sizes in glass

polishing

Wenqiang Peng
Chaoliang Guan
Shengyi Li

Downloaded From: http://opticalengineering.spiedigitallibrary.org/ on 05/16/2015 Terms of Use: http://spiedl.org/terms

 Optical Engineering 53(3), 035104 (March 2014)

Material removal mechanism of ceria particles with

different sizes in glass polishing
Wenqiang Peng,a,b Chaoliang Guan,a,b and Shengyi Lia,b,*
a
National University of Defense Technology, College of Mechatronics and Automation, Deya Road, Changsha, Hunan Province 410073, China
b
Hunan Key Laboratory of Ultra-precision Machining Technology, Hunan Province 410073, China

Abstract. A material removal mechanism of ceria particles with different sizes in a glass polishing process was
investigated in detail. Contrast polishing experiments were carried out using ceria slurries with two kinds of par-
ticle sizes and different amounts of hydrogen peroxide (H2 O2 ) added in the slurries. The Ce3þ ions on the surface
of the ceria particles were gradually oxidized to Ce4þ with increased H2 O2 concentration. It was found that the
material removal rate (MRR) decreased sharply with an increasing concentration of H2 O2 . There was no material
removal when the concentration reached 2.0% for nanoparticle slurry. Nevertheless, the application of micro-
particles made the MRR decrease to a constant value when excessive H2 O2 was added. By comparison, we
conclude that the material is removed by chemical reaction for ceria nanoparticles, while chemical reaction and
mechanical abrasion simultaneously take place for ceria particles with sizes at scale of micrometers in the glass
polishing process. It is clearly demonstrated from the experimental results that Ce3þ instead of Ce4þ ions play an
important role in chemically reacting with the glass surface. An ultrasmooth surface with root-square-mean
roughness of 0.272 nm was obtained after being polished by ceria nanoparticles. © 2014 Society of Photo-Optical
Instrumentation Engineers (SPIE) [DOI: 10.1117/1.OE.53.3.035104]

Keywords: ceria particles; chemical reaction; mechanical abrasion; material removal mechanism.
Paper 131685 received Nov. 4, 2013; revised manuscript received Jan. 16, 2014; accepted for publication Feb. 12, 2014; published
online Mar. 20, 2014.

1 Introduction rate was determined by the formation of the Ce─O─Si

Ceria particles have received wide application in the glass
polishing area for their excellent polishing performance.
The particle has a fast polishing rate and inflicts less surface
damage in the polishing process compared with other par-
ticles of Al2 O3 , TiO2 , SiO2 , etc.1 Although the material
removal mechanism has been studied in the field of optical
glass, the major question is whether the chemical contribu-
tion is dominant in the polishing process. The ceria is softer
than the glass, and it is in conflict with the fact that the soft
particles should give a lower polishing rate if mechanical
polishing is dominant. Hence, the chemical contribution
should be larger in the polishing process. Gilliss et al.2 and
Wang et al.3 found that the Ce elements exist in the forms of
Ce3þ and Ce4þ on ceria particles in the slurry. Sabia and
Stevens4 claimed that the ceria was unstable in aqueous
solution from the point of view in thermodynamics for
the Ce4þ can be easily transformed to Ce3þ . The autologous
oxidation–reduction accelerates the chemical reaction with
the glass surface to increase the material removal rate
(MRR). Kelsall5 considered that the chemical bond formed
between Ce3þ and Si atoms restrained the hydroxylation of
Si─O, and the Si atom was removed by the Ce─O─Si bond
between the particle and the surface. In the view of Cook,6
the glass was first hydrolyzed to form SiðOHÞ4 on the
surface, and then the siloxane reacted with ceria, forming
a Si─O─Ce linkage at the interface between the surface and
particle. Then, a SiO2 or SiðOHÞ4 monomer was removed
when the particle moved away from the bonding site.
However, Hoshino et al.1 found that the material was removed
as a lump instead of SiðOHÞ4 monomer, and the removal
bond and the abruption of the Si─O─Si bond.
Generally, the processed surface has a better roughness
and lower surface damage polished by ceria particles with
small sizes. To the best knowledge of the authors, reports
that explain this phenomenon in glass polishing are very lim-
ited. In this article, the removal mechanism of ceria particles
with different sizes is experimentally investigated.
2 Experiment
To study the polishing behavior of ceria particles, experi-
ments were carried out on two-spool lap polishing equip-
ment, as shown in Fig. 1. A pith lap with diameter of
25 mm was selected as the polishing tool. A constant load
on the workpiece was realized by controlling the supply pres-
sure of the low-friction air cylinder on the lap. The off-center
distance was 5 mm, and the revolution and rotational speed
were set to 100 and 105 rpm, respectively. Two types of
slurry with a concentration of 1.0 wt.% were prepared. One
contained ceria particles with an average diameter of 100 nm,
and the other contained ceria particles of a normal diameter
1 μm. Both types of the slurry were the mixture of particles,
deionized water, and some dispersants. The nanoparticle
slurry was divided into five parts with the same amount
labeled as I, II, III, IV, and V. H2 O2 was added in the slurries,
and the concentration was controlled with H2 O2 of 0.0 vol.%
in part I, 0.2 vol.% in part II, 0.6 vol.% in part III, 1.0 vol.%
in part IV, and 2.0 vol.% in part V. Meanwhile, the other type
of slurry was divided into three parts labeled as VI, VII, and
VIII with H2 O2 of 0.0 vol.% in part VI, 2.0 vol.% in part VII,
and 10.0 vol.% in part VIII. Fixed-point polishing

*Address all correspondence to: Shengyi Li, E-mail: syli@nudt.edu.cn 0091-3286/2014/$25.00 © 2014 SPIE

Optical Engineering 035104-1 March 2014 • Vol. 53(3)

Downloaded From: http://opticalengineering.spiedigitallibrary.org/ on 05/16/2015 Terms of Use: http://spiedl.org/terms

 Peng, Guan, and Li: Material removal mechanism of ceria particles with different sizes in glass polishing
Fig. 1 Schematic of the two-spool lap polishing process.
experiments were conducted on a quartz glass sample to get
the material removal profile for different kinds of slurries,
and the polishing time was 5 min for each point. Before
and after polishing, the surface was measured by a Zygo
GPI XP/D 1000 to calculate the MRR.
3 Results and Discussion
Figure 2 describes the variation of MRR for different polish-
ing slurries. It clearly demonstrates that the increase of the
H2 O2 concentration depressed the polishing rate, regardless
of the types of the particles. For nanoparticle slurries, there
was almost no material removal when the concentration of
H2 O2 reached 2.0 vol.%. However, the MRR decreased to
a constant value in the slurry with particle size of 1 μm when
the H2 O2 concentration exceeded 2.0 vol.%. The color of
both types of the slurry was gradually changed from
white to yellowish when the H2 O2 concentration increased,
and when the concentration exceed 2.0 vol.%, the color did
not alter significantly, as shown in Fig. 3. H2 O2 is a strong
oxidizer and can easily oxidize the Ce3þ into Ce4þ . When the
oxidizer is added to the ceria particle slurry, the following
chemical reaction occurs:
1 CeðOHÞ3 þ SiðOHÞ4 → Ce2 O3 · SiO2 þ H2 O:
Ce3þ ðwhiteÞ þ H2 O2 → Ce4þ ðyellowishÞ þ H2 O þ O2− :
2
As the CeO2 is unstable in aqueous solution, the Ce4þ on
the particle surface can easily transform to Ce3þ , forming
a CeðOHÞ3 layer on the particle surface.3,4 The intrinsic color
Fig. 2 Material removal rate (MRR) of different kinds of slurries. (a) 100 nm, and (b) 1 μm.
Optical Engineering
Downloaded From: http://opticalengineering.spiedigitallibrary.org/ on 05/16/2015 Terms of Use: http://spiedl.org/terms
of CeðOHÞ3 presents as white, while that of CeO2 ·H2 O
appears yellowish.7 With the increasing concentration of
H2 O2 , the Ce3þ on the particle surface was gradually oxi-
dized to Ce4þ , and that is why the color of the slurries
changed from white to yellowish when excessive oxidizer
was added. On the other hand, Wang et al.3 and Greenhaus
et al.8 have found that the adsorptions of Ce3þ and Ce4þ ions
are substantially different in ultraviolet spectrum analysis
and lie in the regions around 340 and 360 nm, respectively.
When the ceria slurry with different H2 O2 concentrations
was applied to polish silicon wafers, Wang et al.9 have
proved that the Ce3þ ions have been completely oxidized to
Ce4þ in the ceria slurry when the 1.0% or 2.0% H2 O2 was
added, as shown in Fig. 4. According to their work, we can
also conclude that the Ce3þ ions have completely oxidized to
Ce4þ in V, VII, and VIII with 2.0% and 10.0% H2 O2 .
Figure 5 shows the size distribution of the nanoparticles in
I and V slurries, from which we can see that the nanoparticle
was lightly agglomerate for its high adsorption due to the
large specific area. By comparison, we can conclude that
the addition of H2 O2 did not affect the stability of the slurry.
Wang et al.9 have found that the amount of Ce3þ is dom-
inant in ceria particle slurries. Fig. 2(a) shows that the MRR
decreased as the reduction of the Ce3þ in the nanoparticle
slurry and the MRR disappeared when Ce3þ ions were com-
pletely oxidized to Ce4þ by H2 O2. Hence, we can conclude
that the material removal in ceria nanoparticles slurry is com-
pletely caused by chemical reaction. Meanwhile, the chemi-
cal reaction with the glass surface completely relies on
the Ce3þ other than Ce4þ on the ceria nanoparticle surface.
According to previous studies,5,6,10–12 we can conclude that
the following reactions take place in the polishing process:
SiO2 þ 2H2 O → SiðOHÞ4 ;
1
CeO2 þ 2H2 O ↔ CeðOHÞ3 þ H2 O2 ;
2
Many defect sites exist on the glass surface where the sur-
face electrostatic field is strong enough to exert a significant
attractive force on polar water molecules, forming a layer
containing SiðOHÞ4 on the surface.13,14 The hydroxyls on
035104-2 March 2014 • Vol. 53(3)
 Peng, Guan, and Li: Material removal mechanism of ceria particles with different sizes in glass polishing

Fig. 3 Color of ceria slurry. (a) With 0% H2 O2 , and (b) with 2% H2 O2 .

the surface possess strong reacting capacity to other atoms.15
When CeðOHÞ3 on the particle comes close to the hydroxyl-
ated surface, a chemical bonding reaction can easily occur.
Chemical reactions convert strongly bonded surface atoms to
weakly bonded ones, and material removal is primarily due
to the overcoming of the binding energy of the weakly
bonded atoms.16 To separate from the glass surface dragged
Fig. 4 Spectrum analysis of ceria slurry with different H2 O2 concen-
trations at pH ¼ 7 (Ref. 9).
away when particles are transported to separate, removed
with the product with a kind of amorphous of Ce─O─Si.
Previous work shows the functional groups of Ce─O─Si pre-
sented on the surface of ceria nanoparticles after polishing.12
Figure 6 shows the scanning electron microscopy images
of ceria particles. The images indicate that the nanoparticles
have an approximately spherical shape with truncated edges,
whereas the microparticles have an irregular shape with
sharp edges. The rule of how particle shape is affected by
the size is that smaller particles have rounder shapes.17
Mechanical abrasion can easily take place for the sharp
indenters, so the glass surface undergoes mechanical wear
with the microparticles. By comparison, the MRR of the
nanoparticles is much lower than that of the microparticles
with the same concentration when no oxidization was added,
as shown in Fig. 2. Under the polishing pressure, large par-
ticles are deeply depressed into the workpiece surface, and
the material is removed by mechanical plough effect in plas-
tic mode. However, material is removed by chemical reaction
in elastic mode for nanoparticles.18 Chemical reaction only
occurs at the top surface atoms, so the MRR is very low
at the atom scale. The MRR of the microparticles still
existed when excessive H2 O2 was added, which means
that only mechanical abrasion occurred in the polishing proc-
ess with microparticle slurry. We introduce a factor k to
evaluate the chemical contribution of ceria particles in the
polishing process.

Fig. 5 Size distribution in nanoparticle slurry. (a) I slurry, and (b) V slurry.

Optical Engineering 035104-3 March 2014 • Vol. 53(3)

Downloaded From: http://opticalengineering.spiedigitallibrary.org/ on 05/16/2015 Terms of Use: http://spiedl.org/terms

 Peng, Guan, and Li: Material removal mechanism of ceria particles with different sizes in glass polishing

Fig. 6 Scanning electron microscopy images of ceria particles. (a) 100 nm, and (b) 1 μm.

Fig. 7 Surface roughness. (a) The initial surface, (b) polished by VI slurry, and (c) polished by I slurry.

MRRC MRRT − MRRM
k¼ × 100% ¼ × 100%:
MRRT MRRT
Here, MRRC denotes the chemical contribution, MRRM
represents the mechanical contribution, and MRRT is the
combined contribution of chemical reaction and mechanical
abrasion. The value of k ranges from 0% to 100%, and the
larger value means higher chemical contribution. Hence, k
equals to 100% means that the MRR is completely caused
by chemical reaction and 0% means that the material is com-
pletely removed by mechanical abrasion. Material removal is
caused by the combined action of the chemical reaction and
mechanical abrasion with no oxidizer, while the material is
completely removed by mechanical abrasion with excessive
oxidizer. Hence, according to Eq. (1), the factor k is equal to
100% in the nanoparticle slurry, and that is to say the
material removal is completely caused by chemical reaction
for ceria nanoparticle. MRRT and MRRM are 26.51 × 10−3
and 8.37 × 10−3 mm3 ∕ min, respectively, for the micropar-
ticles slurry, so the chemical contribution of the micropar-
ticles is 68.3% according to Eq. (1). On the other hand,
mechanical abrasion greatly relies on the sharp edges of the
particle; if the particle becomes more irregular, such as
spherical, then the mechanical contribution is much lower.19
This demonstrates that the chemical reaction is still dominant
in the traditional large particle polishing process and also
explains why the ceria particle is softer than other types of
particles (SiO2 , Al2 O3 , ZrO2 , etc.) and has a higher MRR
and better processed surface.
Figure 7 shows the surface roughness measured by Zygo
New View 700 (Middlefield, Connecticut) with vertical
resolution of 0.1 nm before and after polishing. By compari-
(1)
son, we can see that the surface roughness has become
slightly worse when polished by microparticles slurry,
whereas the surface roughness has improved to 0.272 nm
when polished by the nanoparticle slurry. With the action
of mechanical abrasion, plastic scratches and pits can easily
be generated. Nanoparticles are too small and easily
embedded in the lap, and the contact with the glass surface
is so weak that only elastic deformation occurs on the sur-
face. Within elastic deformation, the arrangement of each
atom can be recovered back to its original position with
no mechanical damage generated in the polishing process.
On the other hand, the removal rate of top atoms is larger
than other surface atoms if only chemical reaction takes
place in the polishing process due to their weaker connection
to the bulk material and higher chemisorption.20 So, the proc-
essed surface becomes much smoother when the ceria nano-
particle was applied to polish.
4 Conclusions
In this study, we investigated the chemical contribution of
ceria particles with different sizes in glass polishing process.
Material removal for ceria nanoparticle completely relies on
the chemical reaction, and the chemical reaction rate is com-
pletely determined by the amount of Ce3þ in the slurry. The
MRR decreased rapidly as the reduction of Ce3þ , and the
material removal disappeared when the Ce3þ ions were com-
pletely oxidized to Ce4þ . For microparticles, the chemical
reaction and mechanical abrasion simultaneously take place
in the polishing process, and the chemical contribution plays
the dominant role in the process. It explained why the softer

Optical Engineering 035104-4 March 2014 • Vol. 53(3)

Downloaded From: http://opticalengineering.spiedigitallibrary.org/ on 05/16/2015 Terms of Use: http://spiedl.org/terms

 Peng, Guan, and Li: Material removal mechanism of ceria particles with different sizes in glass polishing
ceria particles have a higher MRR and better processed sur-
face than other polishing particles. For chemical reaction
occurring in elastic mode using ceria nanoparticles, an
ultrasmooth surface with roughness of subnanometers was
obtained.
Acknowledgments
This work is partially supported by the National Natural
Science Foundation of China (Nos. 51305450 and
91023042).
References
1. T. Hoshino et al., “Mechanism of polishing of SiO2 films by CeO2
particles,” J. Non-Cryst. Solids 283(1–3), 129–136 (2001).
2. S. R. Gilliss, J. Bentley, and C. B. Carter, “Nanochemistry of ceria
abrasive particles,” Mater. Res. Soc. 818, 9–14 (2004).
3. L. Y. Wang et al., “Ceria concentration effect on chemical mechanical
polishing of optical glass,” Appl. Surf. Sci. 253(11), 4951–4954
(2007).
4. R. Sabia and H. J. Stevens, “Performance characterization of cerium
oxide abrasives for chemical-mechanical polishing of glass,” Mach.
Sci. Technol. 4(2), 235–251 (2000).
5. A. Kelsall, “Cerium oxide as a route to acid free polishing,” Glass
Technol. 39(1), 6–9 (1998).
6. L. Cook, “Chemical processes in glass polishing,” J. Non-Cryst. Solids
120(1–3), 152–171 (1990).
7. Q. Yuan et al., “Controlled synthesis and assembly of ceria-based
nanomaterials,” J. Colloid Interface Sci. 335(2), 151–167 (2009).
8. H. L. Greenhaus, A. M. Feibush, and L. Gordon, “Ultraviolet spectropho-
tometric determination of cerium,” Anal. Chem. 29(10), 1531–1534
(1957).
9. Y. G. Wang, L. C. Zhang, and A. Biddut, “Chemical effect on the
material removal rate in the CMP of silicon wafers,” Wear 270(3–
4), 312–316 (2011).
10. L. B. Zhou et al., “Research on chemo-mechanical grinding of large
size quartz glass substrate,” Precis. Eng. 33(4), 499–504 (2009).
11. V. K. Jain et al., “Chemo-mechanical magneto-rheological finishing
(CMMRF) of silicon for microelectronics applications,” CIRP Ann.
Manuf. Technol. 59(1), 323–328 (2010).
12. W. Q. Peng et al., “Improvement of magnetorheological finishing surface
quality by nanoparticle jet polishing,” Opt. Eng. 52(4), 043401 (2013).
Optical Engineering 035104-5
Downloaded From: http://opticalengineering.spiedigitallibrary.org/ on 05/16/2015 Terms of Use: http://spiedl.org/terms
13. T. A. Michalske and S. W. Freiman, “A molecular interpretation of
stress corrosion in silica,” Nature 295, 511–512 (1982).
14. E. A. Leed and C. G. Pantano, “Computer modeling of water adsorp-
tion on silica and silicate glass fracture surfaces,” J. Non-Cryst. Solids
325(1–3), 48–60 (2003).
15. F. H. Zhang et al., “Figuring of an ultra-smooth surface in nanoparticle
colloid jet machining,” J. Micromech. Microeng. 19(5), 054009
(2009).
16. Y. Zhao, L. Chang, and S. H. Kim, “A mathematical model for chemi-
cal-mechanical polishing based on formation and removal of weakly
bonded molecular species,” Wear 254(3–4), 332–339 (2003).
17. Y. Xie and B. Bhushan, “Effects of particle size, polishing pad and
contact pressure in free abrasive polishing,” Wear 200(1–2), 281–
295 (1996).
18. W. Q. Peng, C. L. Guan, and S. Y. Li, “Material removal mode affected
by the particle size in fluid jet polishing,” Appl. Opt. 52(33), 7927–
7933 (2013).
19. M. A. Moore and P. A. Swanson, “The effect of particle shape on abra-
sive wear: a comparison of theory and experiment,” in Proc. the 1983
Int. Conf. Wear of Materials, pp. 1–11, ASME, New York (1983).
20. W. Q. Peng, C. L. Guan, and S. Y. Li, “Ultrasmooth surface polishing
based on the hydrodynamic effect,” Appl. Opt. 52(25), 6411–6416
(2013).
Wenqiang Peng received his BS degree in mechanical design,
manufacturing, and automation from Huazhong University of
Science and Technology, in 2008, an MS degree in mechanical engi-
neering from National University of Defense Technology, in 2010, and
expects to receive his PhD degree in mechanical engineering from
the same university in 2014.
Chaoliang Guan received his BS and PhD degrees in mechanical
engineering from National University of Defense Technology in 2005
and 2010, respectively. He is a lecturer of College of Mechatronics
and Automation at the National University of Defense Technology.
The area of his primary research is focused on ultraprecision optical
polishing and defects-free surface fabrication.
Shengyi Li is a professor of National University of Defense Technol-
ogy. In recent years, his group has focused on optical elements manu-
facturing and equipment research, such as diamond cutting, grinding,
lapping, and polishing processes and equipment in CCOS, magneto-
rheological finishing (MRF), ion beam figuring (IBF), and fluid jet
polishing (FJP).
March 2014 • Vol. 53(3)