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The Effect of Hydrofluoric Etching of Glass

Surface of Glass Laminates

Technical Report August 2013

DOI: 10.13140/RG.2.1.4414.6404

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 The Effect of Hydrofluoric Etching of Glass Surface of
Glass Laminates

by Parimal J. Patel, Steve Kilczewski, Terrence Taylor, Jared Wright,

and Jeffrey Swab

ARL-TR-6565 August 2013

WarningThis document contains technical data whose export is restricted by the Arms Export Control Act (Title 22,
U.S.C., Sec. 2751 et seq.) or the Export Administration Act of 1979 (Title 50, U.S.C. App 2401 et seq.), as amended.
Violations of these export laws are subject to severe criminal penalties. Disseminate in accordance with provisions of DOD
Directive 5230.25.

Distribution authorized to the Department of Defense and U.S. DOD contractors only; critical technology; export
limitations (August 2013). Other requests for this document shall be referred to Director, U.S. Army Research
Laboratory, ATTN: RDRL-WMM-E, Aberdeen Proving Ground, MD 21005-5069.
 NOTICES

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Army Research Laboratory
Aberdeen Proving Ground, MD 21005-5069

ARL-TR-6565 August 2013

The Effect of Hydrofluoric Etching of Glass Surface of

Glass Laminates

Parimal J. Patel, Terrence Taylor, and Jeffrey Swab

Weapons and Materials Research Directorate, ARL

Steve Kilczewski and Jared Wright

Bowhead Science and Technology, Belcamp, MD

WarningThis document contains technical data whose export is restricted by the Arms Export Control Act (Title 22,
U.S.C., Sec. 2751 et seq.) or the Export Administration Act of 1979 (Title 50, U.S.C. App 2401 et seq.), as amended.
Violations of these export laws are subject to severe criminal penalties. Disseminate in accordance with provisions of DOD
Directive 5230.25.

Distribution authorized to the Department of Defense and U.S. DOD contractors only; critical technology; export
limitations (August 2013). Other requests for this document shall be referred to Director, U.S. Army Research
Laboratory, ATTN: RDRL-WMM-E, Aberdeen Proving Ground, MD 21005-5069.
 REPORT DOCUMENTATION PAGE Form Approved
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1. REPORT DATE (DD-MM-YYYY) 2. REPORT TYPE 3. DATES COVERED (From - To)
August 2013 Final 1 January 201130 September 2012
4. TITLE AND SUBTITLE 5a. CONTRACT NUMBER
The Effect of Hydrofluoric Etching of Glass Surface of Glass Laminates
5b. GRANT NUMBER

5c. PROGRAM ELEMENT NUMBER

6. AUTHOR(S) 5d. PROJECT NUMBER

Parimal J. Patel, Steve Kilczewski,* Terrence Taylor, Jared Wright,* and Jeffrey
Swab 5e. TASK NUMBER

5f. WORK UNIT NUMBER

7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) 8. PERFORMING ORGANIZATION

REPORT NUMBER
U.S. Army Research Laboratory
ATTN: RDRL-WMM-E ARL-TR-6565
Aberdeen Proving Ground, MD 21005-5069
9. SPONSORING/MONITORING AGENCY NAME(S) AND ADDRESS(ES) 10. SPONSOR/MONITORS ACRONYM(S)
U.S. Office of Naval Research
ATTN: CODE 822, One Liberty Center, 875 N. Randolph St, Suite 1425, 11. SPONSOR/MONITOR'S REPORT
Arlington, VA, 22203-1995 NUMBER(S)
12. DISTRIBUTION/AVAILABILITY STATEMENT
Distribution authorized to the Department of Defense and U.S. DOD contractors only; critical technology; export limitations
(August 2013). Other requests for this document shall be referred to Director, U.S. Army Research Laboratory, ATTN: RDRL-
WMM-E, Aberdeen Proving Ground, MD 21005-5069.
13. SUPPLEMENTARY NOTES
* Bowhead Science and Technology, Belcamp, MD
14. ABSTRACT
The U.S. Army Research Laboratory (ARL) has been conducting investigations to understand the role of surface flaws on the
ballistic performance of glass based laminates. Previous investigations studied the effect of surface flaws initiated during the
float process. One conclusion from the previous study is that the surface strength does influence the ballistic performance. This
investigation studied the effect of reduced flaws via improved surfaces on the quasi-static and ballistic performance. Glass
plates were subjected to a hydrofluoric (HF) acid treatment to remove the surface layer. All processing conditions were held
constant with the exception of soak time. Mechanical properties were measured immediately after the etching process and
found to increase as a result of the etching process, though the scatter was very high with numerous invalid fractures. Glass
laminates were produced immediately after the etching process and subsequently tested for ballistic performance. The
performance increased for all conditions with 4.4% being the highest-performance improvement. These values indicate promise
into etching as a method for achieving ballistic improvement but will require further research to optimize processing conditions.
15. SUBJECT TERMS
transparent, armor, strength, hydrofluoric etching
17. LIMITATION 18. NUMBER 19a. NAME OF RESPONSIBLE PERSON
16. SECURITY CLASSIFICATION OF: OF ABSTRACT OF PAGES
Parimal J. Patel
a. REPORT b. ABSTRACT c. THIS PAGE 19b. TELEPHONE NUMBER (Include area code)
Unclassified Unclassified Unclassified SAR 16 410-306-0744
Standard Form 298 (Rev. 8/98)
Prescribed by ANSI Std. Z39.18

ii
Contents

List of Figures iv

List of Tables iv

1. Introduction 1

2. Armor Development 2

3. Effect of Strength 3

4. Experimental Procedure 4
4.1 Materials ..........................................................................................................................4
4.2 Hydrofluoric (HF) Acid Treatment .................................................................................4

5. Strength Characterization 6

6. Results 6
6.1 Ballistic Testing...............................................................................................................7

7. Conclusions 8

8. References 9

Distribution List 10

iii
List of Figures

Figure 1. Schematic of a transparent armor system. ........................................................................2

Figure 2. HF treatment and lamination process used in this study. .................................................5
Figure 3. Strength as a function of Soak Time for Comparative Purposes. Please note this
includes invalid ASTM data that fractured outside the load ring. .............................................7

List of Tables

Table 1. Calculated weight loss after the etching process. ..............................................................5

Table 2. Summary chart of strength and ballistic performance. ......................................................7

iv
1. Introduction

Transparent armor is a system constructed of different materials that are designed to defeat a
particular threat or range of threats. The threats targeted are dependent on the envisioned combat
or non-combat scenarios. Though a system is designed for a particular threat and multi-hit
performance, there are general requirements common to most transparent armor systems. The
paramount requirements for a transparent armor system are visibility for situational awareness
and the defeat of a designated threat. The system must also provide a multi-hit capability with
minimized distortion of surrounding areas of the first hit. For future land and air platforms,
weight is a critical parameter that must be minimized. Space efficiency can also be quite
important for certain applications. Other requirements for transparent armor windows are that
they are night vision compatible and they are affordable based on cost-performance models.
ATPD 2352 * details the government requirements for ground vehicle transparent armors. These
requirements include ballistic and environmental requirements. The armor must be both durable
and resistant to nonballistic threats such as rocks, bottles, and hand-tossed objects. At the time of
the report, ATPD does not include specifications for low-velocity impacts such as rocks or
bottles. This is due to the challenge of selecting the threat materials, and relevant velocities from
a range of available options that have been observed in operations.

Figure 1 is a drawing of a general transparent armor configuration. As can be seen, the system is
comprised of many layers, separated by polymer interlayers. Figure 1 does not include the casing
and support framing that is also critical to the overall performance of the transparent armor. The
front face (leftmost ply) is usually a hard face material that is designed to break up or deform the
projectile upon impact. The sequential plys are added to provide additional resistance to
penetration. These materials can be the same or different as the front ply material. An interlayer
to join the two plates separates the plys and provides a transition between two materials that may
have thermal expansion mismatches. The final plate is usually a polymer (polycarbonate [PC] or
polyurethane [PU]) with a thicker interlayer. The purpose of this interlayer is to mitigate the
stresses from thermal expansion mismatches of the different materials, as well as to stop crack
propagation from ceramic to polymer.

* Transparent Armor Purchase Document.

1
2. Armor Development

The armor system can be engineered to provide different levels of protection. In addition to
defeating the threat with multi-hit capability, the mass and space efficiency should be optimized
to a given application. The variables that can be changed are plate material, thickness of plys,
interlayer hardness, interlayer thickness, number of plys, and the order of constituent materials.

Figure 1. Schematic of a transparent armor system.

A simple solution that increases the ballistic performance of a window is increasing the thickness
of the window; thus, the material and design costs are increased incrementally. For many
applications, very thick armor systems are not practical solutions, even if they defeat the threat.
Thick windows may be impractical for several reasons. One is due to the increased weight
associated with thicker materials. Another reason is the space limitations in many vehicles.
Finally, thick sections of transparent armor have greater optical distortion than thinner sections,
thus reducing the transparency. Therefore, new materials that are thinner, lightweight, and offer

2
better ballistic performance are sought. Affordability is a key need given the large volume of
transparent armor used on current Army systems. Affordability can be achieved via reduced cost
of materials, reduced processing costs, increased competition, and the increased lifetime of
transparent armor.

The baseline transparent armor system widely used is a laminate system consisting of layers of
soda-lime-silica (float) glass backed by a PC spall layer. The motivation for the use of these
systems is effectiveness, low cost, and widely available materials on a global scale. As
previously described, the limitation of these systems is the excessive thickness and weight that
has logistical and operational human factor burdens.

There are several methods to improve ballistic performance of transparent armor. Material
substitution is a primary method to improve efficiencies. The use of a transparent ceramic has
been shown to significantly improve by 50%60% the performance over glass based laminates.
Similarly, the use of transparent glass-ceramic has shown 15%20% improvement over soda-
lime-silica laminates. These systems are typically more expensive than the baseline soda-lime-
silica/PC systems that have limited their use. Substitution of glass with polymers such as poly
methyl methacrylate (PMMA), PC, or PU has also shown improvement of 20%30%. The
limiting factor for application of these systems is a higher-thermal stress that must be managed
for long term durability.

Recently, considerable resources have been allocated for the development of higher-performing
armors. The limiting factors for use of advance materials and concepts has typically been cost
and availability. The U.S. Army Research Laboratory (ARL) is currently conducting a
challenging program to improve commercial glasses such as soda-lime-silica and borosilicate
glasses. The objective is to improve ballistic performance with treatments, both surface and bulk,
that would be scalable and utilize the global supply of commercial glasses while incurring an
incremental increase in cost. This report discusses the finding of the first segment of the overall
study.

3. Effect of Strength

The effect of surface flaws on the strength of glass has been widely studied and it is generally
accepted that the existence or introduction of surface flaws reduce the glass quasi-static strength.
There are several known methods to improve the strength of glass. They include removing
surface flaws, surface compression, and surface crystallization (1, 2, 3). Chemical and thermal
tempering mechanisms are widely used techniques to increase the glass strength. Surface
crystallization techniques improve strength by pinning cracks. Efforts to reduce this surface flaw
population using polishing, etching, and coating techniques have shown an improvement in
strength (49). These studies have been focused on rod or fiber type geometries where

3
considerable strength improvements were measured. James et al. (4) found strength
improvements of 77% while Fabes et al. (5) developed glasses with a 220% improvement in
strength for rods and plates.

The strength of glass under dynamic loading has been reported to be very high. This strength
represents the interior strength of the material. Investigations into the effect of strength on the
ballistic performance have been studied and have shown some promise against several threats
(10, 11). This current investigation explores techniques to reduce the surface flaw population of
glasses as a means to improve the ballistic performance. The initial effort, discussed in this
report, focuses on the use of etching methodologies to remove material from the surface as a
means of reducing surface flaws.

4. Experimental Procedure

4.1 Materials
The materials for this study are Starphire * Glass, Huntsman 399 interlayer, and Bayer Makrolon
polycarbonate (PC). These materials are widely available and used in current transparent armors.
The glass chosen for this study was Starphire, a low iron soda-lime-silica glass produced by PPG
Industries. The interlayer is Hunstman 399, an aliphatic polyurethane (PU) used for bonding the
layers of glass and PC. Makrolon PC was used as a spall layer for this study.

4.2 Hydrofluoric (HF) Acid Treatment

Starphire Glass was pre-screened to obtain material that was 9.82 mm thick 0.01 mm. This was
done to ensure comparable data that is not influenced by thickness variations that can influence
the areal density. Figure 2 is a schematic of the process used in this study. The glass was etched
(30 mole percent HF solution) in polymer trays with appropriate rinses to ensure the resulting
material was safe to handle. The soak times used were 4 and 25 min with no heating of the
solution. Immediately after drying, the parts were used for either strength testing or for ballistic
testing. The samples for strength were immediately tested after the final rinse and drying. The
parts processed for ballistic evaluation were immediately stacked onto a PU interlayer in less
than 5 min. The parts were bagged in less than 120 min and laminated in an autoclave the same
day. It is believed that the surface is protected once the interlayer material is in place and the
laminated structure is placed inside an envelope bag.

* Starphire is a registered trademark of PPG Industries, Inc.

4
The parts were weighed and measured prior to the etching process. The glass was not measured
after etching in order to prevent introduction of surface flaws from the measurement process.
The parts were weighed after lamination and the weight loss of the glass was calculated from the
initial weights and the final weights. Table 1 details the weight loss for the different soak times.
The 4-min soak lead to a 2.36% weight loss while the 25-min soak had a 2.56% weight loss.

Figure 2. HF treatment and lamination process used in this study.

Table 1. Calculated weight loss after the etching process.

Part Soak Time AVG% Weight Loss

972 4 min 2.36

971 25 min 2.56

5
5. Strength Characterization

Equibiaxial flexure testing was conducted on all sets on a universal test frame following the
procedures outlined in ASTM * C1499 (12). A semi-articulating fixture with support and load
ring diameters of 85 and 42.5 mm respectively was used. The crosshead displacement rate was
2.2 mm/min, which is equivalent to a stressing rate of approximately 50 MPa/s. A piece of
graphite foil, nominally 0.005 in thick, was placed between each ring of the fixture and both
100 100 mm surfaces to reduce stress concentrations and friction affects. All specimens were
tested with the tin side subjected to tensile loading.

The etched specimens were tested immediately after etching and the strength calculated using
equation 1:
3 2 2
= 22 (1 ) + (1 + ) , (1)
2 2

where is the equibiaxial flexure strength, F is the break load, h is the specimen thickness, is
the Poissons ratio =0.2 and DS and DL are the support and load ring diameters. D is the diameter
of the circle represented by the characteristic size of the rectangular plate and it is calculated
using equation 2:

= 1 , (2)
0.90961+0.12652 +0.00168 ln

where is the average length of the two sides of the rectangular plate.

6. Results

Strength Testing: The strength test results are shown in figure 3 for illustration purposes. It is
important to note that these tests do not fall under ASTM standards since many of the fractures
occurred outside the load area. While the strength data is invalid, the load required to fracture the
treated plates was significantly higher than for the untreated (baseline) plates. The fracture load
for the etched materials was up to 75% higher than the fracture load of the baseline materials. It
is believed strengthening occurred in this etching process but the test methodologies were not
adequate to ascertain the actual influence of the treatment on the strength.

*ASTM International, formerly known as the American Society for Testing and Materials (ASTM).

6
 Figure 3. Strength as a function of Soak Time for Comparative Purposes. Please
note this includes invalid ASTM data that fractured outside the load
ring.

6.1 Ballistic Testing

The laminates produced were tested against the 7.62 39 M1943 PS Ball. The baseline parts
represent glass that was laminated in the as-received condition and had a V50 of 1952 ft/s,
which matches historical data. ARL 971/989 used glass soaked for 4 min. The apparent strength
for this material was 166.5 14.1 MPa. The V50 for this laminate was found to be
2010 ft/s. ARL 990 used glass soaked for 15 min and had a V50 of 2004 ft/s. ARL 972 used glass
soaked for 25 min with an associated strength of 168 67.9 and a V50 2037 ft/s, respectively.
This represents a ballistic improvement of 4.4% with a slightly reduced areal density. There is an
incremental observed benefit in the use of HF etching though the process has not been optimized.

Table 2. Summary chart of strength and ballistic performance.

Soak Time Average AD Est V50

Part Strength MPa Spread Em
(min) (psf) (ft/s)

Baseline 0 153.4 15.1 6.32 1952 1 0.90

971/989 4 166.5 14.1 6.25 2010 15 0.95

990 15 165.1 97.1 6.28 2004 1 0.94

972 25 168.4 67.8 6.28 2037 32 1.0

7
7. Conclusions

ARL has been conducting investigations to understand the role of surface flaws on the ballistic
performance of glass based laminates. Previous investigations studied the effect of surface flaws
initiated during the float process. One conclusion from the previous study is that the surface
strength does influence the ballistic performance. This investigation studied the effect of reduced
flaws via improved surfaces on the quasi-static and ballistic performance. Glass plates were
subjected to a HF acid treatment to remove the surface layer. All processing conditions were held
constant with the exception of soak time. Mechanical properties were measured immediately
after the etching process and found to increase as a result of the etching process, though the
scatter was very high with numerous invalid fractures. Glass laminates were produced
immediately after the etching process and subsequently tested for ballistic performance. The
performance increased for all conditions with 4.4% being the highest-performance improvement.
These values indicate promise into etching as a method for achieving ballistic improvement but
will require further research to optimize processing conditions.

8
8. References

1. Varshneya, A. K. Fundamentals of Inorganic Glasses, The Society of Glass Technology:

Sheffield, 2006, pg 51352.

2. Vlasov A. S.; Zilberbrand, E. L.; Kozhushko, A. A.; Kozachuk, A. I.; Sinan, A. B, Behavior
of Strengthened Glass Under High Velocity Impact, Strength of Materials, Vol. 34, No.3,
2002, pp 266268.

3. Nie, X. Chen, W.W.M Templeton, D.W., Dynamic Ring-on Ring Equibiaxial Flexural
Strength of Boroslicate Glass. Int. J. Appl. Ceram. Technol. 2010, 7 (5), 616624.
4. James, P. F.; Chem, M.; Jones F. R. Strengthening of Soda Lime Silica Glass by Sol Gel and
Melt-Derived Coatings. J. of Non-Crystalline Solids 1993, 155, 99109.

5. Fabes, B. D.; Doyle, W. F.; Zelinski, B. J. J.; Silverman, L. A.; Uhlmann, D. R.

Strengthening of Silica Glass By Gel-Derived Coatings. J. of Non-Crystalline Solids 1985,
82, 349355.

6. Wu, L. Y. L.; Tan, G. H.; Qian, M.; Li, T. H. Formulation of Transparent Hydrophobic Sol-
Gel Hard Coatings; SIMTech Technical Reports, Vol. 6, n.2, pg 14, JulySeptember 2005.

7. Greene, C. H. Flaw Distribution and the Variation of Glass Strength with Dimensions of the
Sample, J. of American Ceramic Society 1956, 39, 6672.

8. Greene, C. H. Surface Flaws in Glass and the Statistics of Flaw Distribution, Glass
Technology 1966, 7, 5465.

9. Proctor, B. A. The Effect of Hydrofluric Acid Etching on the Strength of Glasses, Phys.
Chem. Glass 1962, 3, 1, 727.

10. Vlasov A. S.; Zilberbrand, E. L.; Kozhushko, A. A.; Kozachuk, A. I.; Sinan, A. B.;
Stepanov, M. I. Ballistic Behavior of Strengthened Silicate Class. 20th International
Symposium on Ballistics, Orlando, FL, 2002.

11. Wilkins, M.; Cline, C.; Honodell, C. Light Armor Program Fourth Progress Report; UCRL
50694; Lawrence Radiation Lab: Livernore, CA, 1969.

12. Standard Test Method for Monotonic Equibiaxial Flexure Strength of Advanced Ceramics at
Ambient Temperatures. ASTM C 1499, Vol. 15.01, ASTM: West Conshohocken, PA, 2008.

9
 NO. OF
COPIES ORGANIZATION

1 DEFENSE TECHNICAL
(PDF) INFORMATION CTR
DTIC OCA

1 DIRECTOR
(PDF) US ARMY RESEARCH LAB
IMAL HRA

1 DIRECTOR
(PDF) US ARMY RESEARCH LAB
RDRL CIO LL

ABERDEEN PROVING GROUND

5 DIR USARL
(PDF) RDRL WMM E
P J PATEL
S M KILCZEWSKI
J WRIGHT
T M TAYLOR
J J SWAB

10

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