Laboratory 2: Griffith Flaws and 

Surface Treatment of Glass Slides 
 
 
Prepared for 
 
Dr. Xueyuan Nie 
 
 

 
 
 
 
 
 

Faisal SIDDIQUI 
Student ID 101963673 
th
4  year Candidate for BASc. Mechanical Engineering 
Department of Mechanical Automotive and Materials Engineering
 Table of Contents
Abstract: ............................................................................................................................. 2
Summary: ........................................................................................................................... 2
Survey of literature: ............................................................................................................ 3
Experimental Procedures:................................................................................................... 4
Experimental Results:......................................................................................................... 6
Part A:............................................................................................................................. 6
Part B: ............................................................................................................................. 6
Questions: ........................................................................................................................... 7
Part A:............................................................................................................................. 7
Part B: ............................................................................................................................. 9
Discussion: ....................................................................................................................... 10
Conclusion:....................................................................................................................... 12
Recommendations: ........................................................................................................... 13
References: ....................................................................................................................... 13
Appendix: ......................................................................................................................... 13
Calculations: ................................................................................................................. 13
Figures: ......................................................................................................................... 14

List of Figures
Figure 1: Griffith Flaw (Elliptical Crack)............................................................................... 3
Figure 2: Etching time with HF acid vs. Fracture Load (lb) .................................................. 7
Figure A 1: Unetched Glass Slide Microstructure................................................................ 14
Figure A 2: Glass Slide with 15 Minutes of Etching with HF Acid..................................... 14
Figure A 3: Glass Slide with 30 Minutes of Etching with HF Acid..................................... 14
Figure A 4: Glass Slide with 45 Minutes of Etching with HF Acid..................................... 15

List of Tables

Table 1: Fracture Loads at different Surface Etching Duration ............................................. 6

Abstract:
The objective of this experiment is to study Griffith flaws in glass and to evaluate the
mechanical properties of glass slide such as to study the effect of a surface etch on the
strength of glass. This experiment was conducted to firstly, compare the crack patterns of
the spots treated with the eutectic mixture and the KNO3 on the unetched slide. Secondly,
compare the crack patterns of the spots treated with the eutectic mixture on the four slides
surface etched with HF acid. Thirdly, to investigate the fracture load of glass that was not
surface etched with HF acid slides using three point bend test. Fourthly, to investigate the
fracture load of glass that was not surface etched with HF acid slides using a three point
bend test and therefore find a relationship between the fracture loads vs. the etching time.
And finally, to examine the microstructure of the glass slides both etched and unetched and
compare the two.

Summary:
The purpose of doing the experiment was to become familiar with Griffith flaws in glass
and examining the mechanical properties and finally to analyze its microstructure. This is
an important experiment due to the fact that this experiment meets all of the necessary
objectives. In the study of materials engineering it is very important to become familiar
with Griffith flaws and its various properties due to the fact that almost all brittle ceramic
materials contain a large number of such flaws and such flaws are one of the main
contributors to the fracture of brittle materials.

Firstly a glass microscope slide (and its constituents) was treated with lithium nitrate
(LiNO3) salt. This is a method of ion exchange. This method of ion exchange is
advantageous because the smaller lithium ions produce a tendency to crack all over the
glass slide and enable microscopic analysis of cracks. The crack patterns from addition of
the lithium salt was used as a basis for comparison between itself and the crack pattern
resulting from the eutectic mixture of lithium nitrate (LiNO3) and Potassium Nitrate
(KNO3).

Secondly this experiment helps us determine level of surface fractures and Griffith flaws,
the amount of cracking and severity during the ion exchange and etching and correlate the
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level of surface fractures and Griffith flaws with etching time. This helps us understand the
effect of etching time of Griffith flaws and effect of different sized ion exchanges on tensile
strength

Finally with the aid of this experiment we can examine the fracture strength and the
microstructure of the glass slides which were both unetched and etched for different
duration, to understand the relationship between the microstructure characteristics and
fracture strength and etching time.

Survey of literature:
The theoretical strength for glass is of the order of 106 lb/in2, but in practice, tensile
strength values of the order of 5,000 lb/in2 are common. This is due to “theoretical”
strength of a material is estimated on the assumption that it contains no imperfections.
While freshly drawn fine glass fibers approach the theoretical value, with time as they get
exposed to the atmosphere they start to lose strength.

According to the Griffith theory, there are many fine elliptical cracks, as shown in Figure 1,
and there are high concentrations of stress at the tips of such cracks. With such a stress
concentration, the theoretical cohesive strength can be obtained in this localized region
when the body of the material is under a fairly low applied tensile stress.

Figure 1: Griffith Flaw (Elliptical Crack)

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When glass microscope slide is treated with LiNO3 an ion exchange takes place between
relatively large Na+ ions in the glass and relatively smaller ion Li+. This creates biaxial
tension on the slide surface and it tends to crack all over. When an eutectic mixture of
LiNO3 and KNO3 is added the relatively larger K+ ions exchange with relatively smaller
Na+ ions. This offsets the tensile stress created by LiNO3 addition in the first place and as a
result cracking is reduced. The amount of cracking is also reduced by addition of
hydrofluoric HF acid by etching the glass slide surface and removing surface containing
Griffith flaws.

Griffith crack model can explain strength of different samples as a distribution in the
lengths of the cracks as well as their orientation relative to the tensile axis. The biggest and
most favourably oriented crack determines the critical stresses for different test pieces of
the same material.

As the surface cracks are twice as effective as the interior ones they usually become critical
and propagate first as the load on the specimen is increased. Hence, it is expected that any
surface treatment which affects the cracks on it will also affect the strength. A surface
newly exposed is more perfect immediately on exposure than after some time. With time,
atmospheric corrosion tends to introduce defects on the surface. Another contributing
factor for defect introduction on the surface is accidental mechanical abrasion by other
objects.

General References
Ceramics laboratory 2 handout:
Chapter 6 Lecture Slides: Mechanical Properties & Linear Elastic Fracture.

Experimental Procedures:
¾ Clean four glass slides with soap and water. Dry them with alcohol. Handle the
clean slides by their edges only to prevent leaving finger prints on them.
¾ Place one of the slides in the glass petri dish. Place a few milligrams of the eutectic
mixture near on one spot on the slide. Put an approximately equal amount of KNO3
on a different spot on the slide.

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¾ Place the petri dish in the furnace.
¾ Remove the petri dish from the furnace after twenty minutes. Do this slowly to
avoid shattering the glass slide.
¾ After the slide has cooled, wash the excess salt from it with warm water. Make sure
that the salt is removed. There should be no bulge on the slide surface.
¾ Dry the slide with alcohol.
¾ Use the light microscope to observe the two spots on the slide where the salts were
placed.
¾ Immerse the other three clean slides in the five percent HF solution.
¾ Take out one of the slides after fifteen minutes, rinse it with water, and dry it with
alcohol. Subject this slide to steps 2 to 7 above.
¾ Remove the second slide from the HF solution after thirty minutes and the third
after forty-five minutes. Repeat step 9 with each of these slides.
¾ Clean seven glass microscope slides with soap and water. Handle the clean slides
by the edges only.
¾ Dry the slides with alcohol.
¾ Place one of the clean and dry slides in the three point bend test fixture and slowly
load the specimen.
¾ Record the fracture load of the slide.
¾ Repeat the experiment with two more clean slides to obtain an average value for the
fracture load.
¾ Immerse the remaining four clean slides in 5 percent HF solution.
¾ Take one of the slides out of the HF solution after 15 minutes. Thoroughly rinse it
with water and dry it with alcohol.
¾ Repeat steps 3 and 4 with this slide.
¾ Remove other slides from the HF solution after 25, 35, and 45 minutes.
¾ Repeat steps 3 and 4 with each of these slides.
¾ Record the data in a table.
¾ Plot a graph of fracture load versus length of time in the HF solution.

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Experimental Results:
Part A:
¾ Severities of the cracks were found to be less with KNO3 when compared to that of
Eutectic Mixture.
¾ The crack amount was reduced with the increase of HF etching time.
¾ The size of the undivided portions (grains) found in the microscopic analysis was
found to be increasing with the increase in etching time, indicating a reduction in
cracking amount.
¾ LiNO3 surface treatment results in ion exchange between the sodium ions in the
glass and the lithium ions in the salt, this puts the surface of the glass into biaxial
tension and as a result the slide has a tendency to crack all over.
¾ The addition of HF solution and etching the glass slide with HF solution resulted in
a decrease in the amount of Griffith flaws.
¾ It was shown that with increasing etching times the density of the crack patterns
decreased and a greater number of Griffith flaws disappear.
¾ See Appendix Figure A1 – A4, for the reduction of Griffith flaws and surface
fractures resulting from surface etching.

Part B:
¾ See table 1 for tabulated fracture loads for different duration of surface etching.
Table 1: Fracture Loads at different Surface Etching Duration
Etching Time (minutes) Fracture Load (lb)
0 6, 5, 5, 5, 5, 5, 4, 5, 6, 5Î Avg. 5.1
15 20
25 9
35 24
45 12

¾ See figure 2 for fracture loads for different duration of surface etching.

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 Etching time with HF in minutes vs. Fracture Load (lb)

30

25

20
Fracture Load (lb)

R2 = 0.1663
15

10

0
0 5 10 15 20 25 30 35 40 45 50

Etching Time with HF (minutes)

Etching time vs Fracture Load

Figure 2: Etching time with HF acid vs. Fracture Load (lb)

Questions:
Part A:
1. Is there any difference in the two treated areas of the unetched slide as seen on the
microscope? If so, what is the difference and what is a possible explanation for the
difference?

Ans: The severity of the crack is found to have decreased with the addition of the
eutectic mixture of KNO3 and LiNO3. Treating the slide with lithium nitrate salt
(LiNO3) at elevated temperatures, results in ion exchange between the sodium ions
in the glass and the lithium ions in the salt. The smaller size (ionic radii of Li+ and
Na+ are 0.068 and 0.098 nm respectively) of the lithium ions puts the surface of the
glass into biaxial tension and as a result the slide has a tendency to crack all over.

But when the slide is treated with eutectic mixture of KNO3 and LiNO3, since the
potassium ion is bigger (ionic radius 0.133nm) it subjects the glass to biaxial

7
 compression when exchanged with sodium ions in the glass slide. This cancels
some of the tensile stress generated by the lithium ion exchange.

This results in reduction of the severity of the crack in the glass slide.

2. Make sketches of the crack patterns on both the unetched and etched slides. Bring
out the differences in the crack patterns, if any.

Ans: See the crack pattern in Appendix Figure A1 - A4.

When compared between the etched and unetched slides, it was found that the slides
which were etched with HF in general showed a reduction in the amount of crack
indicated by larger undivided portions (grains). Also it is found that the crack
amount was reduced with the increase of HF etching time. The size of the undivided
portions (grains) found in the microscopic analysis was found to be increasing with
the increase in etching time, indicating a reduction in cracking amount.

3. From the crack patterns what can you conclude regarding the effect of the HF
solution on the Griffith flaws?

Ans: The addition of HF solution and etching the glass slide with HF solution resulted in
a decrease in the amount of Griffith flaws. Etching glass is known to increase the
tensile strength of glass presumably by removing the surface layers that contain the
flaws.

4. What is the effect of etching time on the Griffith flaws?

Ans: It was shown that with increasing etching times the density of the crack patterns
decreased and a greater number of Griffith flaws disappear. When sufficient glass
was removed by etching, it would impossible to obtain any crack pattern at all
regardless of how long the ion exchange treatment was continued.

5. How will the tensile strength of the glass be affected if potassium ions are
exchanged for sodium ions in the glass surface?
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Ans: If an ion exchange takes place between the sodium ions in the glass and the
potassium ions in the salt. The larger size (ionic radii of K+ and Na+ are 0.133 and
0.098 nm respectively) of the potassium ions puts the surface of the glass into
compression. This cancels some of the tensile stress generated by the lithium ion
exchange and as a result the slide will have a reduction in the tendency to crack.

6. How will the tensile strength of the etched glass slides compare with that of the
unetched one?

Ans: Etching glass is known to increase the tensile strength of glass presumably by
removing the surface layers that contain the flaws. It was shown in this experiment
that with increasing etching times the density of the crack patterns decreased. When
sufficient glass was removed by etching, it would be impossible to obtain any crack
pattern at all regardless of how long the ion exchange treatment was continued.

Part B:
1. What is the average value of the fracture load for an unetched glass slide?

6+5+5+5+5+5+ 4+5+ 6+5

Ans: Average Fracture Load (lb)= = 5.1lb
10

2. Has the strength of the glass increased or decreased after etching? What is the
reason for this change?

Ans: The strength of the glass fluctuated for the different time of etching with HF, but
the fracture strength was found to have increased after etching. The addition of HF
solution and etching the glass slide with HF solution resulted in a decrease in the
amount of Griffith flaws. Etching glass is known to increase the tensile strength of
glass presumably by removing the surface layers that contain the flaws.

9
 As the surface cracks are twice as effective as the interior ones they usually become
critical and propagate first as the load on the specimen is increased. Hence, as a
result of a surface treatment such as etching the surface strength is greatly altered.
A newly exposed surface has fewer Griffith flaws immediately on exposure than
after some time. This caused the increase in the fracture strength after etching. With
time, atmospheric corrosion tends to introduce defects on the surface.

3. Why is it not possible to use this method in practice for improving the strength of
glass?

Ans: Etching the glass slide with HF, is the process which removes the surface layers that
contain the Griffith flaws. More and more amount of the glass material is removed
with the increase in length of the etching time. As a result less glass material will
remain intact in the glass slide and this will cause a decrease in surface area. This
will result in a reduction in the glass fracture load.

4. Suggest a method of improving glass strength.

Ans: One method to improve glass strength is to coat a glass with poly(siloxane). The
introduction of a poly(siloxane) in a coating composition for a glass substrate, and
in particular an optical fiber, acts to delay the rate of deterioration of the glass or
optical fiber due to moisture, and improves adhesion between the glass substrate
and the coating composition.
(Reference: http://www.freepatentsonline.com/5502145.html)

Discussion:
From the experiment it was found that when a glass microscope slide is treated with lithium
nitrate salt (LiNO3) at elevated temperatures, an ion exchange takes place between the
sodium ions in the glass and the lithium ions in the salt. The smaller size (ionic radii of Li+
and Na+ are 0.068 and 0.098 nm respectively) of the lithium ions puts the surface of the
glass into biaxial tension and as a result the slide has a tendency to crack all over. The level

10
of the cracking is decreased by using a eutectic mixture of KNO3 and LiNO3, since the
potassium ion is bigger (ionic radius 0.133nm) it subjects the glass to biaxial compression
when exchanged with sodium ions in the glass slide. This cancels some of the tensile stress
generated by the lithium ion exchange.

Secondly it was found that with the increase in the duration of etching with HF acid, a
greater amount of surface containing Griffith flaws were removed and the crack density
was reduced. The undivided portions (grains), visible in the slide were found to be
increasing in size with the increase in duration of surface etching.

Thirdly it was also found that the fracture load of the unetched glass slide was found to
have an average of 5.1 lb for 10 slides. The relatively smaller fracture load is due to
presence of surfaces containing Griffith flaws.

Fourthly, while comparing the etched glass slides with the unetched slides, the etched slides
were found to have a greater fracture load. The fracture load of the etched slides were
found to fluctuate between 9 lb to 24 lb but showed a general increase in fracture load. This
method of strengthening glass slides was not found to be effective as some slides which
were etched for a longer duration showed a lower fracture load. This could be attributed to
loss of glass material from etching and hence the loss of cross sectional area.

Finally, after examining the microstructure of the etched surfaces (can be seen in Appendix
Figure A1-A4) it was found that the amount of cracks were the greatest in the unetched
surfaces and the amount of crack decreased with the greater duration of etching. It can be
said that with sufficient etching, the cracks on the surface can be found to have completely
disappeared. The undivided portions (grain) sizes visible from the microstructure indicate
an increase in size. This is an indication of the lower level of cracks at longer duration of
etching.

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Conclusion:
The purpose of this experiment was to study Griffith flaws in glass and to the effect of a
surface etch on the strength of glass. From this experiment we learned a several important
characteristics of Griffith flaws, crack growth by ion substitution, difference between
etched and unetched surfaces, relationship between etching duration and level of cracks.

It was found that the addition of LiNO3 caused a biaxial surface tension which caused the
tendency to crack all over. This was due to the relatively smaller Li+ ions (0.068nm radii)
exchanging relatively larger Na+ ions (0.098nm radii) in the glass and hence introducing a
biaxial tensile stress in the slide. A large amount of cracks was found while examining the
microstructure.

Also it was found that the addition of eutectic mixture of LiNO3 and KNO3 reduced the
severity of cracks in the glass slides. This happened due to the relatively larger K+ ions
(0.133nm radii) exchanged with the relatively smaller Na+ ions (0.098nm radii) and hence
introduced a biaxial compressive stress in the slide. This in turn cancelled some of the
biaxial tensile stress created previously by addition of Li+ ions.

Another finding from the experiment was the observation that etching with HF acid tends to
reduce the amount of cracks. This happens because the HF etches and removes the surfaces
containing the flaws and the newly exposed surface tends to have fewer cracks. It was
found that with etching for longer periods of time the surface cracks became fewer.
It can be said that with sufficient amount of etching the surface cracks will almost
disappear.

One of the other findings was while comparing the etched surfaces to the unetched surfaces
it was found that the etched surfaces had a greater fracture strength than the unetched slides
due to lower amounts of cracks. However the strength of the etched surfaces fluctuated
while in general showing an increase in strength due to crack locations and the amount of
glass material being removed from the surface and change in cross sectional area due to
etching. Changes in cross sectional area due to etching are a major cause of why some
slides failed at a lower fracture load than predicted.

12
While examining the microstructure of the unetched and etched surfaces, the amount of
cracks were found to be greater in unetched slides. The cracks became less and less as
slides were etched for longer periods of time. In other words the crack density of the
surface decreased. This was due to surfaces containing flaws were removed due to etching
and new surface containing fewer cracks were exposed.

Recommendations:
In our results we found that the fracture strength of the slides were not always as predicted
based on their surface etching time duration. This could be because of accidental
mechanical abrasion on the surface, or reduction of the cross sectional area due to removal
of glass material by etching, or critical crack locations at places where load was applied.
Also it was found that etching the surface to strengthen the glass material due to reduction
in cross sectional area.

In the future therefore, it is recommended that the party conducting experiment avoid
accidental mechanical abrasion on the surface and test slides which have been exposed to
the atmosphere for similar amount of time. Also it is recommended that some other
effective form of strengthening glass material is used such as coating with poly(siloxane)
which delays the rate of decomposition of glass.

References:
Ceramics laboratory 2 handout.
Chapter 6 Lecture Slides: Mechanical Properties & Linear Elastic Fracture.
Coating system for glass strength retention:
(http://www.freepatentsonline.com/5502145.html)
Griffith Flaws In Brittle Materials:
(http://www.matsci.ucdavis.edu/MatSciLT/Other/Files/GriffithFlaws.pdf)

Appendix:

Calculations:

Average Fracture Load (P) for Unetched Glass Slides

6+5+5+5+5+5+ 4+5+6+5
P= = 5.1lb
10

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Figures:

Figure A 1: Unetched Glass Slide Microstructure

Figure A 2: Glass Slide with 15 Minutes of Etching with HF Acid

Figure A 3: Glass Slide with 30 Minutes of Etching with HF Acid

14
Figure A 4: Glass Slide with 45 Minutes of Etching with HF Acid

15