BOSTON UNIVERSITY

SCHOOL OF MEDICINE

Thesis

EFFECTS OF NaCl CONCENTRATION AND TEMPERATURE ON

CORROSION: UNDERSTANDING MATERIAL INTERACTIONS IN

AQUEOUS ENVIRONMENTS

by

KATIE SUE WEBSTER

B.S., Grand Valley State University, 2008

Submitted in partial fulfillment of the

requirements for the degree of

Master of Science

2010
 Approved by

First Reader _______________________________________________

Catherine Grgicak, Ph.D.
Instructor, Biomedical Forensic Sciences

Second Reader _______________________________________________

Robin Cotton, Ph.D.
Associate Professor, Biomedical Forensic Science

2
 ACKNOWLEDGEMENTS

To my amazing parents, who have always encouraged me to reach for

my goals. Words cannot express my appreciation for all of your support and

love throughout my life. Thank you to my loving husband, who has always

stood by my side, for giving me confidence and support everyday.

Thank you Catherine Grgicak for your patience and excellence in

teaching me about all about electrochemistry. Most importantly, thank you

for challenging me and setting high expectations, which has truly provided

me with one of the best learning experiences in my life.

Lastly, thank you Sgt. Gilmore of the Massachusetts State Police

Underwater Recovery Team for your inspiration behind this research project

and providing me with your input on such an interesting topic.

iii
 EFFECTS OF NaCl CONCENTRATION AND TEMPERATURE ON

CORROSION: UNDERSTANDING MATERIAL INTERACTIONS IN

AQUEOUS ENVIRONMENTS

KATIE SUE WEBSTER

Boston University School of Medicine, 2010

Catherine Grgicak, Ph.D., Instructor, Biomedical Forensic Sciences

ABSTRACT

The analysis of ballistics evidence is commonly performed in forensic

laboratories due to the high number of crimes committed with the use of a

firearm. When possible, ballistics evidence analysis will include the

examination of the firearm, projectiles and gunshot residue. However, further

analysis on corrosion products present on items of metallic evidence exposed

to the environment for a period of time may be beneficial in determining the

time since placement.

Understanding the metal composition and environmental factors is

necessary in determining the rate of corrosion. Each metal species, will

exhibit its own rate of corrosion. Environmental factors such as oxygen

iv
concentration, pH, chloride ion concentration and temperature are also

known to influence the rate of corrosion.

In this study, the rate of corrosion of stainless steel (SS) and handguns

in solution was assessed to determine whether a relationship between the

level of corrosion and the time since immersion exists. This was

accomplished by analyzing corrosion rate through the mass-loss method.

Specifically SS416 rods and four handguns were immersed in solution at

varying concentrations of NaCl and at two temperatures, over a 180-day

period. Results showed that in the presence of NaCl the corrosion rate of

SS416 and handguns increased. However, the rate did not significantly

increase within a 15 PSU to 35 PSU NaCl range. The variation in

temperature from 5C to 25C showed minimal changes in the corrosion rate

of SS416. Despite minimal corrosion rate variations between 15 PSU to 35

PSU and 5C to 25C, significant differences in the rates and corrosion

products were observed between the handguns which vary in metallic

composition. The variations in the rate of corrosion observed in the handgun

slides were associated with the differences in metal composition and/or

surface coatings.

Although corrosion of SS416 and the handguns was affected by the

presence of NaCl, prior knowledge of the attributes of the material was

required (i.e. the original mass) before a time since immersion could be

v
reported. It was established that items of equivalent metal composition

within similar environmental conditions of temperature and salinity exhibit

indistinguishable rates of corrosion. However, determination of the corrosion

rate of a variety of metallic evidence over a 180-day period cannot be

determined accurately without knowing the original mass, condition,

composition of the alloy and the corresponding mechanism of corrosion.

vi
TABLE OF CONTENTS

Title Page (i)

Readers Approval Page (ii)

Acknowledgements (iii)

Abstract (iv)

Table of Contents (vii)

List of Tables (ix)

List of Figures (x)

Abbreviations (xii)

1. Introduction (1)

1.1 Background (1)

1.2 Electrode Reactions (4)

1.3 Electrochemistry of Aqueous Corrosion (8)

1.4 Environmental Factors (10)

1.4.1. Oxygen Concentration (11)

1.4.2. pH (12)

1.4.3. Chloride Ion Concentration (14)

1.4.4. Temperature (15)

1.5 Metal Composition and Applications (16)

1.5.1. Pitting (18)

vii
 1.5.2. Types of Stainless Steel (19)

1.5.2. Handgun Metal Composition (21)

2. Materials and Methods (22)

2.1 Sample Descriptions and Preparations (22)

2.2 Experimental Procedures (27)

2.3 Data Analysis (28)

3. Results and Discussion (29)

3.1 Stainless Steel 416 Quantitative and Qualitative (30)

Results

3.1.1. Stainless Steel 416 at Room Temperature (30)

3.1.2. Stainless Steel 416 at 5C (35)

3.1.3. Stainless Steel 416 Temperature Differences (38)

3.1.4. Effect of Nick Formations (40)

3.1.5. XRD Analysis of Stainless Steel 416 (41)

3.2 Handgun Slides Quantitative and Qualitative (44)

Results

3.2.1. Handgun Slides Quantitative Data (44)

3.2.2. XRD of Handgun Slides (52)

4. Conclusion (57)

5. References (59)

6. Curriculum Vitae (63)

viii
LIST OF TABLES

Table 1. List of Samples (22)

Table 2. Elemental Composition of SS416 Control Samples (23)

Table 3. Initial Mass, Surface Area and Surface Area Density of (26)
Handgun Slides

Table 4: Parameters Maintained for Solutions Prepared (28)

Table 5. Mass Loss and Corrosion Current of SS416 at 25C (32)

Table 6. Mass Loss and Corrosion Current of SS416 at 5C (36)

Table 7. Comparison of Mass Loss between Solution (38)

Temperatures of 5C and 25C

Table 8. Daily Mass Loss of Each Gun Slides over 180 Days (44)

Table 9. Total Weight Loss Percentage of Handgun Slides (46)

ix
LIST OF FIGURES

Figure 1: Typical Electrochemical Set-up (4)

Figure 2: Evans Diagram (8)

Figure 3: Llama Handgun Slide P1 and P2 (23)

Figure 4: Jennings Handgun Slide P1 and P2 (24)

Figure 5: Ruger Handgun Slide P1 and P2 (24)

Figure 6: Raven Handgun Slide P1 and P2 (24)

Figure 7. SS416 Control Sample with nick in center and centimeter (26)
scale.

Figure 8. Mass Loss of Stainless Steel 416 at Room Temperature (30)

Figure 9. Mass Loss of Stainless Steel 416 at 25C with error bars. (31)

Figure 10. Comparison of Corrosion Products in Varying Salinity (34)

Levels at 25C at Day 180

Figure 11. Mass Loss of Stainless Steel 416 Samples at 5C (35)

Figure 12. Comparison of Corrosion Products in Varying Salinity (37)

Levels at 5C at Day 180

Figure 13. Side by Side Comparison of SS416 Corrosion Products at (38)

25C and 5C on Day 180

Figure 14. Localized Corrosion on SS416 Nick in 25 PSU Solution (40)

Figure 15. XRD Patterns of SS416 at Room Temperature (42)

Figure 16. White residue buildup on inner portion of Jennings P2 (47)

and Raven P2 at day 180

Figure 17. Comparison of Slides in 0 PSU and 25 PSU Solutions (48)

x
 at Day 180

Figure 18. Non-Adherent Rust Formations on Llama in 25 PSU (49)

Figure 19. Rust Formations Initiated on Screw of Raven Handgun in (50)

0 PSU Solution at Day 24

Figure 20. Ruger in 25 PSU Solution Progression of Rust on Site (51)

Figure 21. XRD Patterns of Llama Handgun Slide (52)

Figure 22. XRD Patterns of Jennings Handgun Slide (53)

Figure 23. XRD Patterns of Ruger Handgun Slide (54)

Figure 24. XRD Patterns of Raven Handgun Slide (55)

xi
ABBREVIATIONS

AISI American Iron and Steel Institute

AM AquaMend

C Carbon

cm centimeters

Cr Chromium

DO Dissolved oxygen

EDX Energy Dispersive X-ray spectroscopy

F Faradays Constant

Fe Iron

g Grams

ICP/MS Inductively Coupled Plasma/Mass Spectroscopy

L Liters

mg milligrams

MPS multiprobe system

MSP Massachusetts State Police

Mn Manganese

Mo Molybdenum

NaCl Sodium Chloride

n Number of electrons transferred

xii
OCV Open Circuit Potential

P Phosphorus

PPE Personal Protection Equipment

PSU Practical Salinity Units

r corrosion rate

R Universal Gas Constant

S Sulphur

SEM Scanning Electron Microscope

Si Silicon

SS stainless steel

SD Standard deviation

T Temperature

V Volts

XPS X-ray Photoelectron Spectroscopy

XRD X-ray Diffraction

xiii
 1. Introduction
_____________________________________________________________

1.1 Background

Forensic examinations and the subsequent conclusions drawn from

evidence retrieved during crime scene processing has become an important

component in crime scene analysis and forensic science. Within a given

investigation, a multitude of evidence types/items are examined, either for

comparison purposes or as investigative aids. Typical types of evidence

collected from crime scenes are biological, chemical or trace in nature. Each

type of item collected requires its own procedure for analysis within a specific

unit of a forensic laboratory. For the examination of firearms, bullets and

gunshot residue, the evidence would be analyzed in the ballistics unit.

In 2007, the Federal Bureau of Investigation estimated the total

number of reported crimes committed with the use of a firearm included 68

percent of all murders, 43 percent of all robberies and 21 percent of all

aggravated assaults [1]. With a significant number of criminal cases

involving firearms, the detailed characterization of ballistic or materials

evidence is commonly performed and necessary.

Ballistics examinations can be separated into three areas of analysis:

internal, external and terminal. Internal ballistics involves the examination

of the projectile and the rifling, striations and/or marks, which are created

upon the projectile while exiting the weapon. A part of the external ballistic

1
examination may include the analysis of gunshot residue and the patterns

created. These patterns may be used to determine the distance between the

weapon and the target. Lastly, terminal ballistics involves the effects the

projectile causes upon impact on the target. For example, the terminal

examination of a target surface can aid in determining the angle of impact of

a projectile and therefore the location of the shooter with respect to the

victim[2, 3]. All three areas of ballistic analysis aid in reconstructing the

crime scene and determining the facts of the crime. Such information can be

used to corroborate a story or for purposes of determining the sequence of

events. Although most forensic firearm analysis examines the projectile,

gunshot residue and angle of incidence; the length of time a particular article

has been exposed to the environment may also need to be elucidated within a

case.

An example of such a case is cited by Shanahan[4], where a 0.22

caliber brass cartridge case was found at the scene of a double murder 18

weeks after the crime occurred. At this time of the investigation the

prosecution assumed the cartridge case found at the scene was relevant to

the crime. There was no reason to believe that the cartridge was not in the

soil for 18 weeks and upon examination no specific observation of corrosion

products was recorded. In the appeal trial, the defense argued that the

cartridge case found was not relevant and presented six additional fired

2
cartridges recovered from the same location exposed for a period of 18 weeks.

These cartridges showed an accumulation of corrosion products due to the

environmental exposure differing from the prosecutions cartridge on exhibit.

The defense argued that the cartridge case on exhibit was not in the soil for

the 18 week period of time as suggested by the prosecution. The prosecution

claimed that the differences may have resulted for handling the evidence

unintentionally removing corrosion products that may have been present.

To better understand the corrosion process over this given time period,

a field study was conducted by Shanahan[4]. Similar cartridges were placed

in the soil near the scene to determine if corrosion products formed would

yield similar results to the cartridge found at the crime scene. The study

showed there is a significant amount of variability among corrosion products

formed within similar environments. Additionally, as suggested by the

prosecution, it was shown that corrosion products can be lost with

handling[4]. In this case, the rate by which rusting occurred would have a

significant role in determining the time since placement of the cartridge.

However, Shannahan showed that corrosion and the analysis thereof is

considerably complex and is influenced by a variety of factors including pH,

material chemistry, ion concentration, temperature and oxygen concentration

and soil composition.

3
 Although it was determined that corrosion rates are inconsistent

between cartridge cases and soils, determination of corrosion kinetics within

aqueous environments within a forensic context is needed. This work aims to

determine whether the rate of corrosion can be determined in forensic cases

involving the recovery of a handgun placed in a body of water for a period of

time. Since corrosion is an electrochemical process , knowledge of the

fundamentals of electrochemistry and factors influencing the process is

necessary.

1.2 Electrode Reactions

An electrochemical reaction is one where the redox reaction is

separated in space, whereby one half-reaction takes place at one electrode

compartment and the other takes place in another. Each reaction occurs at

an interface between an electrode substance and a conducting electrolyte

solution where a chemical change is accompanied by charge transfer across

the electrode/electrolyte interface. A general electrochemical set-up is as

follows;

4
 Figure 1. Typical Electrochemical Set-up

where the arrows represent the flow of electrons. During a spontaneous

reaction, species in solution are oxidized (loss of electrons) at the anode where

the electrons are deposited. These electrons travel through an external

circuit to the cathode where reduction (gain of electrons) of another species

occurs.

As Figure 1 shows, electrons produced in the half reaction

R1 O1 ne (1)

travel through an external circuit and re-enter the cell through the cathode.

O2 ne R2 (2)

In a galvanic cell, the anode withdraws electrons from the

electroactive species R1, giving the anode a relative negative charge. The

cathode will replenish the electroactive species R 2 with electrons giving the

cathode a relative positive charge[5].

5
 A cell in which the overall reaction has not reached equilibrium can do

electrical work. The efficiency of the given cell depends upon a number of

factors, which includes the maximum theoretical efficiency defined by

rGT
ET (3)
r HT

where ET is the maximum theoretical efficiency of the cell, rGT is the Gibbs

energy of reaction at temperature T and r HT is the standard enthalpy of

reaction. As demonstrated by Equation (3), the efficiency of the cell is related

to rGT, which is the maximum amount of electrical work a system can

perform.

A relationship between Gibbs free energy and the zero current cell

potential (OCV-open circuit potential) is given by the following equation

nFEcell rGT (4)

where n is the number of electrons transferred in the reaction, F is Faradays

constant and E is the potential of the cell[5]. Therefore, if Gibbs energy of a

reaction is known, Equation (4) can be used to determine the OCV of the cell.

Additionally, it should be noted that spontaneity of the reaction, given by

rGT where a negative value predicts the reaction will occur spontaneously,

may also be predicted in electrochemical terms (Ecell). For that reason, a

positive Ecell indicates the reaction will occur spontaneously. For example,

6
the expected Ecell of the oxidation of H2(g) to H2O(g) at standard temperature

and pressure can be calculated as follows:

H2(g) + O 2 H2 (5)

G298K = -nFEcell

-228.6 KJ/mol ((0)-0) = -nFEcell

-228.6 KJ/mol = -2FEcell

Ecell = 1.2 V

The negative rGT value and the corresponding positive Ecell suggests this

reaction will occur spontaneously. It should be noted however, that although

the aforementioned treatment predicts the reaction will occur spontaneously,

it gives no information regarding the kinetics or rate of the reaction.

Furthermore, a redox reaction can be expressed as two half reactions,

which show the loss and gain of electrons for the species of interest. For

example, Equation (5) can be expressed as two half reactions

1) The oxidation of hydrogen

2H+ + 2e- H2 E1/2 = 0V (6)

2) The reduction of oxygen

O2 + 4H+ + 4e- 2H2O E1/2 = 1.2V (7)

where E1/2 represents the reduction potentials verses the standard hydrogen
electrode. Therefore if,

7
 Ecell = Ecathode - Eanode (8)

= 1.2V 0V

= 1.2V

then Ecell can also be calculated using the electrochemical series[6]. The

standard reduction potential for each of the half reactions is a good measure

of the driving power of the cell. The larger the Ecell, the more negative the

rGT and the more electrical work can theoretically be performed. The Ecell

can also be considered a measure of the potential difference and provides

information on which species will be the one to undergo reduction. In this

example, E1/2 for the reduction of O2 is larger than that of H+, therefore the

O2 is expected to be the species to undergo reduction.

Understanding the basic fundamentals of redox equations is critical

when attempting to interpret corrosion processes. The potential exhibited by

each half-reaction will ultimately determine the driving power of the cell and

its energy requirements.

1.3 Electrochemistry of Aqueous Corrosion

For corrosion to take place, an oxidation reaction must occur

simultaneously with a reduction reaction. The kinetics of the corrosion

process is often displayed in an Evans Diagram. Figure 2 shows the anodic

and cathodic currents as a function of potential[7].

8
 Figure 2. Evans Diagram
The anodic reaction is due to the dissolution of metal (M), M Mn=+ne- and the cathodic
reaction is due to the reduction of a species, R + ne- O.

As displayed in Figure 2, as the current increases, the potential

becomes more positive for the anodic reaction. Therefore, the two curves will

eventually intersect at a point of equilibrium known as the corrosion

potential or mixed potential (Ecorr). The corresponding corrosion current (icorr)

is equal for both the anodic and cathodic reactions and, if known, can be used

to determine the Ecorr. An important consideration to remember is that the

potential values of each half reaction are species specific, where the E1/2

reflects the affinity for electrons between an element and its ions[6]. For

example, the corrosion of iron will exhibit its own potential and will be

different from that of zinc and its rate of corrosion. Therefore, with all else

9
being equal, the larger the potential difference between each half reaction,

the larger Ecorr is expected to be[7]. The corrosion current density (icorr)

signifies the rate of charge transfer at the corrosion potential. More

specifically, it is the number of electrons flowing per second between the

metal surface and solution[7, 8]. Typically, icorr is expressed in amperes per

square centimeter (A/cm2). If corrosion current is known, it can be converted

to the mass loss per surface area with the application of Faradays law. The

reverse is also true if the mass loss rate is known. For example by converting

the mass loss of a substance of known composition in mg/cm 2day to

mol/cm2s the following equation can be applied to calculate i corr

x( mol / cm2 s )
icorr (10)
nF

where F is Faradays constant (96,486 As/mol) and x is the loss of metal (in

mol) per square centimeter within a given time unit.

The Evans diagram displayed in Figure 2 is a schematic

representation of the anodic and cathodic current-potential relationship in

near neutral conditions. An alteration in the atmospheric conditions, such as

the availability of oxygen or pH can affect the rate at which reactions will

occur, resulting in a shift in the rate and a difference in potential-current

relationship. In turn, this shift would result in a change in the slope of the

anodic and cathodic curves, thereby affecting the rates of corrosion.

10
 The reaction and the rate at which metal dissolution occurs depends on

a number of factors including but not limited to oxygen concentration, salt

concentrations, pH and temperature.

1.4 Environmental Factors

Metals have a natural tendency to oxidize to reach a more stable

electrochemical state. The oxidation of metal results in the formation of solid

metal oxides on the surface, which serves as a barrier between the metal and

the surrounding environment. The metal oxide film is known as a passive

film. An intact passive film covering the surface of a metal with its protective

function will resist corrosion[9]. The corrosion current of a metal within a

passive state is small (nA/cm2) reflecting its resistance to corrosion[10, 11].

With environmental exposure of the passive film, the film will evolve to

eventually form both metal oxides and hydroxides[12]. Overtime, depending

on the harshness of the surrounding conditions, the film will deteriorate

losing its ability to self maintain and protect the metal resulting in

degradation or mass loss[13]. Each environmental factor will exhibit its own

affect on the rate of corrosion and dissolution of the metal.

1.4.1. Oxygen Concentration

At a given pH, temperature and ion concentration, the level of

dissolved oxygen plays a role in how iron dissolves, rusts and reacts. For

11
example, the mechanism by which corrosion may occur in an acidic

environment is[7]

Fe(s) + 2H+(aq) + O2 (g) Fe2+(aq) + H2O (l) (11)

where the two half reactions are

Fe2+ (aq) + 2e- Fe (s) E1/2 = -0.44V (12)

2H+(aq) + O 2 (g) + 2e- H2O(l) E1/2 = +1.23V (13)

According to the E1/2 values, the electrochemical reduction of O2 will occur

with the oxidation of Fe to Fe 2+. As the medium becomes saturated with O 2

the dissolution of iron is expected to increase. In this scenario, the metal will

be consumed and eventually lead to significant structural damage.

Previous work has shown that with an increase in O2 concentration,

the corrosion rate does increase as suggested. Melchers et al. showed that not

only did the O2 concentration increase the corrosion of mild stainless steels,

but there was a linear relationship between the mass-loss and dissolved

oxygen. However, the linearity was maintained only with a 0.5 year time

interval. At times greater than 0.5 years, corrosion was controlled by mass

transport or the ability of the oxygen to diffuse through the newly formed

oxide layer [14, 15].

The dissolved oxygen concentration within a body of water can also be

affected by the depth, temperature and pH. With an increase in water depth,

12
the dissolved oxygen levels will decrease[14, 16]. This increase can be

explained by less water circulation to replenish oxygen levels and/or the

consumption of oxygen by organic matter in deep waters[17]. As temperature

increases, the dissolved oxygen concentration of the of solution will decrease

due to the change in solubility of the oxygen allowing the oxygen to leave

solution[18].

Overall, the oxygen concentration of an environment in which an item

of metal has oxidized is a crucial factor in determining the rate of corrosion

over a period of time. Knowing the oxygen concentration of a body of water

would be a key factor to observe within the field to determine if the

concentration was a limiting factor in the corrosion process.

1.4.2 pH

The pH of a solution not only alters the rate of corrosion, but the

mechanism by which iron dissolves. In acidic solutions, it has been

suggested that -OH absorbs onto Fe to produce FeOH ads and it is the FeOHads

which will undergo further oxidation to eventually form Fe 2+ and H2O

products. Alternatively, in alkaline solutions, the FeOHads reacts with H2O

and -OH in a series of steps to eventually form Fe(OH) 2 + -OH [19].

Not only is the pathway affected by whether the solution is alkaline or

acidic, the pH value has a significant impact on the rate. In the simplest

scenario, iron dissolution via the two half reactions is as follows

13
 Fe Fe2+ +2e- E1/2= 0.44V (15)

2H+ + 2e- H2 (g) E1/2= 0V (16)

As pH becomes more acidic, Ecorr will become more positive due to the

increase in rate of hydrogen evolution. Subsequently the increase in iron

dissolution will result in a larger icorr. As explained by Gileadi, the resulting

corrosion current when iron is in concentrated acid (pH 0) equals 27mA/cm 2

verses 0.14 mA/cm2 which is the resultant icorr when iron corrodes in dilute

acid[8].

The corrosion of stainless steel in acidic conditions may also result in

an overall increase in the thickness of the passive film. However, a mass loss

of the stainless steel still occurs due to the selective dissolution of iron and

the deterioration of the passive film[11]. In contrast, corrosion processes

occurring in alkaline solutions is known to result in a lower rate of iron

dissolution and a thicker passive film due to the greater stability of iron

oxides in basic conditions[11, 20, 21].

In practice there is little interest in the corrosion of iron at low pH, as

most natural bodies of water have near neutral pH values ranging from 5 to 9

[18]. For example, the pH of the sea surface ranges from 8 to 8.3 and

remains consistent due to the natural buffering capacity of the sea[22]. Deep

seawater generally has a lower pH range from 7.5 to 7.7[16]. The slight

14
variations that occur in the surface pH of the ocean has minimal direct effects

on the corrosion process[23], especially for austenitic iron-base, ferritic alloys

and duplex alloys [8, 24].

Although pH does have an impact on corrosion rates and mechanisms,

the moderate variations in pH within natural bodies of water are expected to

have minimal effect.

1.4.3. Chloride Ion Concentration

Unlike pH, chloride ion concentrations can significantly vary between

bodies of water and effects of chloride ion concentration on corrosion

processes are of importance due to the abundance of salt present in the

environment. The average salinity level of the sea is 3.5 w/w%. Although

Sodium chloride (NaCl) is found in abundance, other salts are also present

whereby the composition includes a variety of ions listed from highest to

lowest concentrations: chloride, sodium, sulphates, magnesium, calcium,

potassium, carbonate and bromide [23, 25, 26].

The rate of corrosion is usually higher in salt verses fresh water [27].

This can be explained by the presence of chloride ions, which are known to

substantially decrease the ability of the passive film to negate metal

oxidation and/or dissolution. The small size and negative charge of the

chloride ion penetrates through the passive layer to the positively charged

metal cation destroying the protective function of the passive film[28].

15
Metals heavily affected by the breakdown of the passive film are stainless

steels and aluminum[16, 26]. With the breakdown of the passive film, pitting

corrosion of stainless steels is commonly observed, particularly in seawater.

For items of metallic evidence, which are retrieved from bodies of

water, the presence of chloride ions is expected to increase the rate of

corrosion. This factor is important for forensic investigators to characterize-

especially for crime laboratories located along ocean coastlines- in order to

appropriately assess the rate of corrosion.

1.4.4. Temperature

Temperature is known to affect the rate of a reaction and therefore will

have an effect on the rate of corrosion. The Arrhenius expression describes

the relationship between reaction rate and temperature:

r = Ae -Ea/RT (17)

where r equals the reaction rate, A is a pre-exponential factor, E a is the

activation energy, R is the gas constant and T is the temperature[18]. The

equation shows that, an increase in temperature will result in an increase in

the rate of corrosion when the process is solely governed by metal oxidation.

The effects of temperature become more complex with varying pH and oxygen

concentrations. As described by Malik et al., the increase in temperature

from 25-90C on a variety of commercial grade stainless steels resulted in a

positive linear relationship between the increase in corrosion rate and

16
temperatures up to 65C. After 65C, the increased solubility of oxygen

caused a decrease in the oxygen concentration resulting in a stabilization of

the corrosion potential[26].

Within the field, effects governed by temperature may cause

complexity in assessing the rate especially due to the variations in

temperature throughout climate seasons. Therefore, a detailed analysis of

the influence temperature has on corrosion rates and mechanisms is

necessary to determine whether the length of time ballistic evidence has been

immersed can be appropriately assessed.

1.5 Metal Composition and Applications

The composition of metal is also known to directly impact the rate of

corrosion. Each metal exhibits a specific potential and therefore corrosion

potential upon oxidation within the environment. Alloyed metals, which

contain two or more metals in a solid solution, will also reveal a specific

corrosion potential and rate of corrosion. This concept was demonstrated by

Zheng et al. who assessed the corrosion rate of low alloy steel and two

different stainless steels in solutions of 0.5 mol/L NaCl. Each steel in the

same environment resulted in a different rate of corrosion, with chromium

containing stainless steels exhibiting the lowest rate of corrosion by an order

of magnitude[29].

17
 Stainless steel is an iron-based alloy containing a minimum of 12%

chromium, the second most abundant metal within stainless steel. It may

also contain small amounts of other alloying elements such as nickel,

manganese and molybdenum[20, 23, 30]. It is the varying amounts of other

metals, which differentiate the types of stainless steels. For example SS416-

commonly used for the manufacturing of handguns- is composed of a mixture

of 0.15% carbon, 13% chromium, 84% iron, 1.25% manganese, 0.6%

molybdenum and 0.06% phosphorus, 0.15% sulphur and 1% silicon[31].

Small changes in metallic content change the physical properties of the steel

to such an extent that different types of stainless steels are used for specific

applications.

The addition of chromium to iron promotes passivation and therefore

offers corrosion resistance as discussed in the beginning of Section 1.4. Iron-

chromium based alloys must contain a minimum of 12% chromium in order to

promote passivation or self-passivate whereby a thin layer of chromium oxide

(Cr2O3) forms across the surface of the stainless steel[12, 32]. The stability of

the passive film depends on the presence of chromium. The mass loss of the

stainless steel is attributed to the selective dissolution of iron through the

passive film. The chromium oxide formed remains within the inner layer of

the film and it is the formation of chromium oxide, which deters further

18
corrosion and therefore mass loss[20, 32, 33]. With higher levels of chromium

present within stainless steel, lower rates of corrosion are expected[11].

1.5.1 Pitting

Although stainless steels are known for their corrosion resistance,

pitting is especially common among corrosion resistant alloys in

environments containing chloride ions[10, 26]. Pitting is a form of localized

corrosion and can be the most destructive form of corrosion[23]. The

initiation of pitting begins through a combination of variables such as

chemical or physical heterogeneities on the metal surface, material geometry

and environmental conditions[7, 10]. A disruption in the cathodic protection

of the passive film exposes a potential anodic site on the metal. Due to the

small area of the exposed anodic site verses the large area of the cathodic

passive film, the corrosion current density inside the anodic site is

significantly higher[7, 8]. The high corrosion current density localized on a

small area on the metal surface results in a pit. The use of a scanning

electron microscope (SEM) is often employed to examine the presence of

pitting on a metal surface due to their microscopic size.

Understanding the metal compositions ability to withstand

environmental conditions overtime is important when attempting to establish

a time since immersion. For example, the use of high alloy stainless steels

containing large levels of chromium (i.e. above 20 %) is recommended for long

19
term applications in seawater due to the ability to resist localized

corrosion[26].

1.5.2 Types of Stainless Steel

The families of stainless steel are broken up into five groups:

austenitic, ferritic, martenistic and duplex. These groups are classified by

their structural content while the precipitation-hardening steels are

classified by the heating process applied [20, 34]. More specifically, a series

identification (200, 300 and 400) was established by the American Institute of

Steel and Iron (AISI) for a universal understanding of the components and

the percentage of the components within stainless steel[30].

The most common of the stainless steel families, the austenitic family,

includes 200 and 300 series metals. These series contain a minimum of 18%

chromium and low carbon content. The austenitic family is known for high

corrosion resistance and strength[35, 36]. The 300 series contains nickel as

an austenite stabilizer while the 200 series contains manganese and nitrogen

stabilizers[36]. The austenitic metals cannot be hardened by heat treatment

and must be cold-worked[23]. Cold working can be described as the

application of hammering, rolling and stretching at room temperature to

change the shape and structure of the metal, the process allows for an

increase in strength and hardness[37].

20
 The ferritic family includes the 400 series metals ranging in 12% to

30% chromium with minimal nickel content offering moderate corrosion

resistance. The stability of the ferrite structure increases with an increase

in chromium content[35]. The ferrite metals do not harden with heat

treatment and are moderately hardened with cold working.

The martenistic stainless steel family contains grades of stainless steel

AISI 400, more specifically SS416 and SS420, commonly used for the

manufacturing of cutlery, medical instruments, bearings and barrels of

firearms[38, 39]. The heating process applied to the metal, above the critical

temperature of 1600F and the rapid cooling process, gives this type of

stainless steel its name because of the martensite structure that is formed[9].

The heating and cooling process produces a stainless steel product with high

strength, hardness and is the least corrosion resistant of all the families.

The duplex family consists of a equal proportion of ferrite and

austenite structures offering a high strength metal with approximately 28%

chromium and 6% nickel equivalent[35, 36]. The benefits of duplex steels are

the resistance to stress cracking and pitting in chloride solutions[36].

The precipitation-hardening steels are classified by the hardening

treatment entailing a solution quenching process followed by heating the

metal to 800-1000F. The steel may contain all three austenitic, martenistic

21
and ferritic structures. The steels produced are classified as the AISI 600

series and exhibit high strength and hardness [23, 37] .

1.5.3. Handgun Metal composition

The metal composition of handguns today consist of stainless steels

from the 400 series or precipitation-hardening steels, offering strength and

corrosion resistance[39, 40]. A variety of chemical treatments or coatings can

be applied to the firearm to offer more protection from corrosion such as:

chrome plating, browning or bluing processes, phosphate treatments,

passivating components and case hardening [40].

Further implications of the metal composition of handguns affecting

the corrosion process may result from handguns referred to as the Saturday

Night Special or the Ring of Fire. These handguns are made with a

melting pot of inexpensive metals available at a low price[41]. The high

variability in the metal composition of handguns produced from these

manufacturers adds to the complexity in establishing a rate of corrosion

within the field of forensics.

22
 2. Materials and Methods

___________________________________________________________

2.1 Sample Descriptions and Preparations

Table 1. List of Samples

Materials Source Description/Usage
Stainless Steel 416 OnlineMetals Control sample of
known composition
Jennings handgun Massachusetts State Byrco Arms, 9mm
slide Police
Llama handgun slide Massachusetts State Gabilondo Y CIA Vitoria
Police
Raven handgun slide Massachusetts State Raven Arms, MP-25
Police Auto
Ruger handgun slide Massachusetts State Sturm, Ruger and Co.
Police Inc., P93 DC

Stainless Steel 416 (SS416) rods and four handgun slides from

different manufacturers Jennings, Llama, Raven and Ruger were immersed

in aqueous solutions of varying NaCl concentration for a period of 180 days.

All SS416 samples were cut into approximately 1-inch long rods and all

handgun slides were cut in half across the width.

The SS416 elemental composition is similar to the composition of the

400-grade Ruger slide. Listed in Table 2 is the percent composition (by

weight?) of SS416 purchased from OnlineMetals.

23
Table 2. Elemental Composition of SS416 Control Samples
Element Percent Composition (%)
C 0.15 Max
Cr 13
Fe 84
Mn 1.25 Max
Mo 0.6 Max
P 0.06 Max
S 0.15 Max
Si 1 Max
*Composition listed from OnlineMetals [31].

Figure 3: Llama Handgun Slide P1 and P2

Displayed in Figure 3 is the Llama slide with a black colored coating

prior to being submerged in water. The slide is inscribed with Gabilonda Y

Cia Vitoria (Espana) on one side and Llama Max-I 45 C/F on the other

side.

Figure 4. Jennings Handgun Slide P1 and P2

Displayed in Figure 4, is the Jennings slide manufactured by Bryco

Arms prior to being submerged in water. The Jennings slide is made of a

24
silver colored metal and is manufactured by Bryco Arms known as a Ring of

Fire handgun[42]. The slide is inscribed with Bryco Arms, Costa Mesa, CA

USA on one side and Jennings Nine-ca 9mm on the other side.

Figure 5. Ruger Handgun Slides P1 and P2

Displayed in Figure 5 is the Ruger slide composed of a 400-grade

stainless steel[39]. The Ruger slide was inscribed with RUGER P93DC on

one side and Sturm, Ruger and Co, inc. Southport, CONN, USA on the

other side.

Figure 6. Raven Handgun Slide P1 and P2

Displayed in Figure 6 is the Raven Arms slide made of a silver colored

metal prior to being submerged in water. Raven Arms also known as Phoenix

Arms is also part of the Ring of Fire handgun group[42]. The other side is

inscribed with the Raven logo of a bird in the mid center and a SAFE

25
inscription with an arrow towards the rear on one side. The other side has an

inscription Raven Arms Industry California, Model MP-25 Cal. 25 AUTO.

Made in the USA.

Prior to placement within the aqueous environments, the approximate

surface area and average mass of all samples was obtained. The surface area

of the rods was calculated by measuring the height and radius of the exposed

surface. Due to the irregular shape of the handgun slides, the slides were

measured and drawn on graphing paper to calculate the approximate surface

area of each exposed surface. The average mass of each sample was

determined using an analytical scale with measurements taken in triplicate

and then averaged. The surface area density was determined by dividing the

mass (g) by the surface area (cm2). Table 3 displays the initial mass, surface

area and surface area density of each handgun slides.

Table 3. Initial Mass, Surface Area and Surface Area Density of

Handgun Slides
Gun Slide Mass (grams) Surface Area (cm 2) Surface Area
Density (grams/cm2)
Llama P1 198.8 94.4 2.11
Llama P2 148.5 126.5 1.17
Jennings P1 208.9 122.7 1.70
Jennings P2 176.7 119.8 1.48
Ruger P1 226.3 116.9 1.94
Ruger P2 143.4 126.4 1.13
Raven P1 101.6 91.2 1.11
Raven P2 57.3 60.2 .95
*For each gun slide the rear portion is referred to as Piece 1 (P1) and the front portion or
muzzle end is referred to as Piece 2 (P2).

26
 Prior to submersion of the handguns, a trial run was performed on

SS416 samples, which resulted in corrosion on the cut end surfaces. To

minimize influence of the cut end surfaces on the corrosion process,

waterproof AquaMend was applied to the ends of the rods and slides.

AquaMend is an epoxy putty stick made of a fiberglass-reinforced polymer

used to repair numerous surfaces including metal[43].

Figure 7. SS416 Control Sample with nick in center with centimeter scale.

The Swagelok tube cutter for stainless steel with a cutting diameter

of 3/16 inch to 1 inch was used to make controlled nicks on SS416 samples.

As displayed in Figure 5, a single nick was made in the center of each SS416

sample measuring approximately 18mm x 6 mm x 4mm.

2.2. Experimental Procedure

The SS416 rods were placed into twenty polyethylene containers with

prepared solutions with 0 PSU, 15 PSU, 25 PSU and 35 PSU of NaCl (1

Practical Salinity Unit (PSU) is equal to 1 g NaCl per 1 L deionized water).

For samples at room temperature, four SS416 rods were contained

individually for each prepared solution. SS416 rods in 0 PSU and 25 PSU

27
were in solution with a handgun slide, with one portion of the slide in 0 PSU

and its counterpart in 25 PSU solution. For samples at 5C, one SS416 rod

was contained individually for each prepared solution.

The solutions were changed weekly to ensure the rates of corrosion

would not be influenced by the changes in concentrations of the solubilized

corrosion products, a variable which is not expected if a small piece of

metallic evidence is immersed in a large body of water. The YSI Multiprobe

System (MPS) was used to measure the pH, salinity, conductance and level of

dissolved oxygen (DO) from weekly. This was performed to ensure the

parameters remained consistent over the 180-day experiment. The average

measured values are listed in Table 4.

Table 4: Parameters Maintained for Solutions Prepared

Solution pH Salinity Conductance DO (mg/l)
(mS/cm) Min-Max
0 PSU 7.51.4 0.010.03 0.030.06 8-11
15 PSU 6.11.0 15.51.0 24.12.1 7-10
25 PSU 6.11.3 25.91.2 37.82.7 7-10
35 PSU 5.90.7 35.21.0 51.33.7 7-10
*Standard deviation listed as 2SD

An Olympus camera was used to photograph and document the

accumulation of corrosion products overtime. Stereoscopic images were

captured with a Nikon SMZ100 stereoscope and SPOT InsightTM camera

implemented with SPOT Basic computer software.

28
2.3 Data Analysis

The bi-weekly average surface area density of each sample was

recorded and used to calculate the mass loss per day (grams/cm2/day).

Subsequently, the mass loss per day of SS416 samples was used to calculate

the icorr expressed in mA/cm 2 assuming the mass loss was due only to the

dissolution of iron (Equation 10). Descriptive statistics (i.e. averages and

standard deviations) and linear regression analysis was performed using

Microsoft Office Data Analysis ToolPak.

After 180 days the sample was removed from the solution and the

adherent rust present on the metal surfaces was removed with a blade.

Additionally, a metal file was used to collect filings from the metal surfaces,

which did not exhibit passive film formation. The adhering rust and metal

filings were analyzed by means of X-ray diffraction (XRD) in order to

determine the crystalline phases. Phase analysis was obtained using a

Rigaku MiniflexTM X-ray diffractometer using CuK radiation with a

wavelength of 1.54 . The scan ranges was 10-70 2 with a 0.04 step and a

rate of 0.7 s/step. The presence of a NaCl crystalline phase was confirmed

using JADE (Materials Data Incorporate) powder XRD analysis software and

Powder Diffraction Database files.

3. Results and Discussion

29
 ___________________________________________________________

3.1 Stainless Steel 416 Quantitative and Qualitative Results

3.1.1 Stainless Steel 416 at Room Temperature

Figure 8. Mass Loss of Stainless Steel 416 at Room Temperature

The mass loss of SS416 over time is represented in Figure 8 where () is the mass loss in 0
PSU, () 15 PSU, () 25 PSU, () 35 PSU solution. The 25 PSU slope does not the fit the
correlation and was excluded from analysis.

30
 Mass Loss of Stainless Steel 416 in 0 PSU Mass Loss of Stainless Steel 416 in 15 PSU

1.57 1.6

1.565 1.58
(grams/cm2)
Mass Loss

Mass Loss (grams/cm2)

1.56 1.56

1.555 1.54
0 PSU 15 PSU
1.55 1.52

1.545 1.5

1.54
1.48

1.535
1.46
0 50 100 150 200
0 50 100 150 200
Days Days

Mass Loss of Stainless Steel 416 in 25 PSU Mass Loss of Stainless Steel 416 in 35 PSU
1.59
1.59
1.58
1.58
Mass Loss (grams/cm2)

1.57

Mass Loss (grams/cm2)

1.57
1.56
1.56
1.55
1.55
25PSU 35 PSU
1.54
1.54
1.53
1.53
1.52
1.52
1.51
1.51

1.5
1.5
0 20 40 60 80 100 120 140 160 180 200
0 20 40 60 80 100 120 140 160 180 200
Days Days

Figure 9. Mass Loss of Stainless Steel 416 at 25C with error bars.
The mass loss of SS416 over time is represented in Figure 9 where () is the mass loss in 0
PSU, () 15 PSU, () 25 PSU and () 35 PSU solution. Error bars are displayed as 2SD
with a sample size of four SS rods for each solution. The trend line for 25 PSU samples were
excluded from analysis.

Figure 8 represents the linear mass loss per day of SS416 at 25C,

room temperature, in solutions of 0 PSU, 15 PSU, 25 PSU and 35 PSU from

days 15 to 180. Days 0 to 14 were excluded as part of the regression because

of the plateau in mass loss at the beginning stages of aqueous corrosion. The

figure is displayed without errors bars for clarity. As shown in Figure 8, the

slope for 0 PSU is nearly 0, while the rates of mass loss (i.e. slope) of 15 PSU

and 35 PSU were -0.26.01 and -0.25.01 mg/cm2/day respectively. The mass

loss for the 25 PSU was not included in the analysis since it did not follow the

31
trend of mass loss per day. This may have been due to the fact that it was in

the same solution as the Llama slide thereby influencing the rate of corrosion

through the solubilized products in solution. The SS416 samples in 25 PSU

were in the same solution as the slides, this appears to have had an effect on

the rate of corrosion.

Figure 9 displays the data from Figure 8 with error bars. The mass

loss for each sample is separated for presentation. The rate of mass loss for

samples in 0, 15 and 35 PSU solutions demonstrates that the presence of salt

(NaCl) had a significant impact on the corrosion rate of SS416. The

corrosion current density was calculated using Equation (10) and the

observed mass loss per day of SS416 samples. Results are shown in Table 5.

Table 5. Mass Loss and Corrosion Current of SS416 at 25C

Practical Salinity Mass Loss per Day R2 Corrosion Current
Unit (PSU) (mg/cm2/day) Density (mA/cm 2)
0 .02.004 0.677 6.71.3x10-4
15 .26.01 0.984 8.70.3x10-3
35 .25.01 0.977 8.40.3x10-3

The corrosion current density (icorr) is directly proportional to mass loss

and was calculated assuming the selective dissolution of iron[11, 32, 33]. The

corrosion current increases by an order of magnitude between 0 and 15 PSU,

while remaining constant between 15 and 35 PSU, indicating that the

presence of NaCl has a significant impact on corrosion rates of SS416, while

mild variations in NaCl concentration do not. Ibrahim et al. also showed the

32
presence of chloride ions concentration have a significant impact on corrosion

rates of stainless steel, however their work also indicated a correlation

between chloride ion concentrations and corrosion rates. In their work, the

NaCl concentration ranged from 0.5 M to 3.0 M (~30 to 145 PSU), resulting in

an increase in corrosion rate with an increase in NaCl concentration[28]. It

should be noted, the increase in corrosion rate observed by Ibrahim et. al.

was observed in concentrations significantly higher (~30 to 145 PSU) than

the NaCl concentrations used in this experiment (15 35 PSU).

As displayed in Figure 10 below, the presence of adhering rust at day

180 does not vary significantly between solutions of 15 PSU, 25 PSU and 35

PSU. With controlled settings of metal composition, temperature and pH, the

small variations in salt content does not seem to significantly impact

formation of rust. Therefore, the results demonstrate that mild changes in

salt concentrations are not expected to significantly affect the ability of an

investigator to determine time since immersion. The only sample which was

significantly different from the others was that of the SS416 in 0 PSU (i.e. DI

water) (Figure 10a and Figure 8). Although this suggests the presence of salt

plays a role in rust formation, natural bodies of water are not expected to be

free of ions (particularly SO 4-, Cl- and CO3- [44]) and therefore .small changes

is Cl-, Na+, and other ion concentrations are not expected to significantly

33
impact the ability to determine the length of time a handgun has been

immersed in a large natural body of water.

Figure 10. Comparison of Corrosion Products in Varying Salinity Levels at

25C at Day 180
SS416 samples from solutions (a) 0 PSU (b) 15 PSU (c) 25 PSU (d) 35 PSU

34
3.1.2. Stainless Steel 416 at 5C

Figure 11. Mass Loss of SS416 Samples at 5C

The mass loss of SS416 over time is represented in Figure 12 where () is the mass loss in 0
PSU, () 15 PSU, () 25 PSU and () 35 PSU solutions. The error bars are displayed as
2SD with a sample size of 1 SS rod for each solution.

Figure 11 represents the mass loss of samples at 5C in solutions of 0

PSU, 15 PSU, 25 PSU and 35 PSU. The slope of 0 PSU, which represents the

rate of mass loss per day, is 0.005 .006, while the slopes for 15 PSU, 25 PSU

and 35 PSU were 0.18.01, 0.19.01, 0.23.01 mg/cm2/day respectively. Since

the slope is representative of the mass loss of SS416 per day, the data shows

a significant difference between the mass loss in the 0 PSU solution verses

the salt solutions.

35
Table 6. Mass Loss and Corrosion Current of SS416 at 5C
Practical Salinity Mass Loss per R2 Corrosion Current
Unit (PSU) Day (mg/cm /day)
2 Density (mA/cm2)
0 +.005 .006 0.0766 1.72.0x10-4
15 .18 .01 0.952 6.00.3x10-3
25 .19 .01 0.982 6.40.3x10-3
35 .23 .01 0.986 7.70.3x10-3

As displayed in Table 6, the mass loss per day increased in the

presence of the salt. The SS416 sample at 0 PSU did not exhibit an

appreciable loss. The corrosion current of the samples, displayed in Table 6,

was also determined showing a correlation in the presence of NaCl resulting

an increase in the corrosion current.

Figure 12 displays the corrosion products present on day 180 in

varying levels of salinity at 5C. The rust present on SS416 in solutions of 15

PSU, 25 PSU and 35 PSU does not visually seem to vary significantly as

suggested by the mass loss data presented in Table 6. However, a significant

difference is observed in the corrosion products present in 0 PSU solutions

verses all other solutions which contain NaCl. The presence of corrosion

products in 0 PSU is minimal. This is similar to the results shown in Table 5

and Figure 8, whereby it was only the SS416 samples immersed in 0 PSU

solution, which showed a significant difference in rust formation. Although

visual inspection of rust formation would not be a sufficient analysis

technique to determine the differences in corrosion rates, a comparison of the

36
corrosion currents at 5C and room temperature suggests there may be a

difference between the two temperatures.

Figure 12. Comparison of Corrosion Products in Varying Salinity Levels at

5C at Day 180
SS416 samples from solutions (a) 0 PSU (b) 15 PSU (c) 25 PSU (d) 35 PSU

37
3.1.3 Stainless Steel 416 Temperature Differences

Table 7. Comparison of Mass Loss between Solution Temperatures of 5C and

25C
Practical Salinity Unit Mass Loss at 5C Mass Loss at 25C
(PSU) (mg/cm /day)
2 (mg/cm2/day)
0 +.005 .006 .02 .004
15 .18 .01 .26 .01
25 .19 .01 N/A
35 .23 .01 .25 .01
* Errors are via linear regression and are calculated from the standard error of the slope.

Figure 13. Side by side Comparison of SS416 Corrosion Products at 5C and

25C on Day 180
Column (a) represents SS416 at 5C and (b) represents SS416 at 25C. The salinity levels
increase from top to bottom: 0PSU, 15 PSU, 25 PSU and 35PSU.

38
 As displayed in Table 7, the comparison of the mass loss differences of

SS416 samples at temperatures 5C and 25C are minimal. Figure 13

displays a side-by-side comparison of the corrosion products present on SS416

at temperatures of 5C and 25C in varying levels of salinity. The visual

comparison of samples between different temperatures shows there are

indistinguishable differences between samples at each temperature.

Temperature is known to have an effect on the rate of corrosion[26], however

between 5C and 25C the results did not exhibit significant variation in

corrosion rate or among visual comparison of SS416 samples, particularly in

the 35 PSU solution. However, at low concentrations of NaCl notable

differences in the corrosion rate were observed, where the corrosion currents

decreased from 0.26 to 0.18 mg/cm2/day with a decrease in temperature of the

15 PSU solution. Further experimentation is required to elucidate whether

the difference is significant and reproducible at 5C.

Minimal differences, in rate of mass loss and oxide coverage, between

the SS416 within salinity levels from 15 to 35 PSU and temperatures 5C

and 25C demonstrate that within the same metal composition, small

variations in NaCl concentration and temperature resulted in

indistinguishable mass loss, corrosion current and the accumulation of visible

corrosion products over time. This finding may be important in forensic

investigations if a case involves locating items of metallic evidence of equal

39
composition exposed to similar aqueous environments over equivalent time

periods. Based on the experimental findings, the items of metallic evidence

should exhibit similar formations of rust. However, the findings do not

establish a method of determining the rate of corrosion within the field, as a

whole. A determination of the effect of gun type and composition has on

corrosion is necessary.

3.1.4. Effect of Nick Formation

The disruption of the SS416 surface of the metal rods by forming a

nick on did not show a definitive correlation in the location of initial rust

formation. It was originally hypothesized, that disturbances within the metal

surface would allow for a source of localized corrosion. Of the twenty SS416

samples submerged in varying levels of salinity, only one sample exhibited

localized corrosion on the nick.

Figure 14. Localized Corrosion on SS416 Nick in 25 PSU Solution

*SS416 sample submerged in 25 PSU solution with Llama P2. Stereoscope photograph with
millimeter scale at Day 180.

40
 Figure 14 displays the localized corrosion on the SS416 sample on day

180, which was submerged in 25 PSU solution along with the Llama P2

handgun slide. The corrosion process of the Llama P2 slide may have had an

effect on the SS416 corrosion process. It was noted the corrosion product

formation began on the side of the rod and eventually covered the entire side,

including the nick with even distribution. Overtime, the corrosion process

became localized at the site of the nick. Further microscopic analysis is

necessary to determine the effects of disturbances within the surface of

stainless steel as well as the formation of pitting over time.

3.1.5. XRD Analysis of Stainless Steel 416

XRD analysis was performed on SS416 samples to provide an

assessment of the phases present prior to and after the 180 days of

submersion. The term, phase, is used to describe materials without internal

bonding composed of atoms, ions or molecules organized in a particular

fashion. Most corrosion products of interest have a solid crystalline

structure[36].

41
 Figure 15. XRD Patterns of SS416 at Room Temperature
XRD patterns of SS416 where (a) represents the original metal (b) adherent rust present on
day 180 in 35 PSU solution.

As displayed in Figure 15(a), the diffractogram of the original metal

scrapings from SS416 displayed one prominent peak. Figure 15(b), shows the

diffractogram of the adherent rust on the SS416 sample immersed in 35 PSU

solution for 180 days. No crystalline phases above the background were

detected, despite the formation of rust observed in Figure 10. This may be

due to the small sample size of adherent rust obtained for analysis. Analysis

of rust formed on SS416 in the 0 PSU solution was not possible due to

42
 inadequate amount of sample available for analysis. Identification of

adherent phases present on the SS416 sample in 35 PSU solution would

require the use of analysis with SEM/EDX, XPS or ICP/MS to confirm the

composition of rust.

Although the XRD analysis performed on SS416 did not provide

identification of phases, research describing the iron and metal-oxide phases

present during the corrosion of steel has previously been performed. Research

conducted by Garcia on the adherent rust formation of carbon steels in the

atmosphere with low concentrations of chloride ions found lepidocrocite

( Fe 3O(OH )) to be the dominant corrosion product while also containing

magnetite (Fe2+Fe 23+O 2), goethite ( Fe 3O(OH )) and akaganeite

( Fe 3O(OH ,Cl ))[45]. However, corrosion which occurred at high

concentrations of chloride ions showed that akaganeite ( Fe 3O(OH ,Cl ))

was the dominant corrosion product formed[44, 46]. Previous research on the

corrosion process overtime also demonstrates the transformation in phases

and changes in phase concentration, which depends on the metal content and

environmental factors, adds to the complexity of interpreting the corrosion

process. The variation in iron phases were demonstrated by Garcia et al.,

who found that with the increase in time, the abundance of lepidocrocite

increased at the expense of goethite in carbon steels in 0.1 M NaCl

solutions[45].

43
 Therefore, previous research suggests phase changes between different

levels of salt concentration and over time is expected. This suggests that over

an extended period of time (>180 days) corrosion rates may also change,

adding to the complexity of establishing a time interval for forensic

investigators, particularly over a 6 month period.

3.2 Handgun Slides Quantitative and Qualitative Results

3.2.1 Handgun Slides Quantitative Data

Table 8. Daily Mass Loss of Each Gun Slides over 180 Days
Gun Slide Name Practical Salinity Mass Loss at 25C R2
Unit (PSU) (mg/cm2/day)
Llama P1 0 0.04.01 .481
Llama P2 25 0.13.01 .988
Jennings P1 0 0.02.004 .649
Jennings P2 25 0.04.01 .847
Ruger P1 0 0.05.01 .786
Ruger P2 25 0.09.01 .903
Raven P1 0 0.004.004 .108
Raven P2 25 0.02.01 .247
* Errors are via linear regression and are calculated from the standard error of the slope.

As displayed in Table 8, the mass loss per day on handgun slides is

minimal, with a range in mass loss from 0.004.004 to 0.05.004 mg/cm2/day

for 0 PSU solutions and 0.02.01 to 0.13.01 within 25 PSU solutions. In all

cases, each handgun slide submerged in the 25 PSU solution exhibited a

higher level of mass loss per day than its matching counterpart in 0 PSU

solution. The comparison of the mass loss of the Ruger slide (made of a 400

series SS) to SS416 mass loss within the same 25 PSU solution resulted in

44
different rates of corrosion, 0.09.01 and .18.01 mg/cm2/day respectively.

Although, the metal composition of the SS416 and the Ruger slide are

similar, the rates of corrosion are not expected to be equal due to the

application of protective coatings and/or surface differences, which can

influence the rate of corrosion. However, the mass loss of the handgun slides

indicate that the presence of NaCl plays an important role in establishing

corrosion rates regardless of metal composition and/or the presence of surface

coatings. The mass loss of the handgun slides correlates with the

experimental results of SS416, demonstrating that in the presence of NaCl

the rate of corrosion will increase. Since the exact metal composition of the

handgun slides is unknown, the corrosion current density of the slides cannot

be accurately calculated.

After the 180-day period, the adherent rust was scrapped off of the

slides and the final mass was obtained. The total mass loss percentage of

each handgun slide was determined using the equation:

Total Mass Loss % = Final Mass-Initial Mass x 100% (20)

Initial Mass

As displayed in Table 9, the total mass loss of the handgun slides after

removal of adherent rust in 25 PSU solutions (slides labeled P2) resulted in

significantly larger percentages of mass loss than handgun slides in 0 PSU

solutions again this emphasizes that the corrosion rates are affected by the

presence of NaCl.

45
Table 9. Total Mass Loss Percentage of Handgun Slides
Slide Name PSU Total Mass % Loss
Llama P1 0 0.45
Llama P2 25 2.09
Jennings P1 0 0.05
Jennings P2 25 1.25
Ruger P1 0 0.04
Ruger P2 25 1.46
Raven P1 0 0.10
Raven P2 25 2.44

The Jennings P2 and Raven P2, exhibited a weight loss percentage of

1.25 w/w% and 2.44 w/w% respectively. However, these samples also showed

a low mass loss per day before rust removal. This occurrence could be

explained by a heavy buildup of white residue on the inner portion of the

handgun slides. The heavy, white residue was not present on any of the

other samples and further analysis using XRD was performed. Results

indicated that the layer was composed of NaCl along with other phases

formed through metal oxidation. The presence of the NaCl phase was also

present in other samples, except for the Llama handgun, which exhibited the

typical reddish brown colored rust. The XRD spectra for the Jennings and

Raven rust formations within 25 PSU solution are displayed in Figures 22(c)

and 24(c). Photographs of the heavy white residue are displayed in Figure 16

below.

46
 Jennings P2

Raven P2

Figure 16. White residue buildup on inner portion of Jennings P2 and Raven
P2 at day 180

47
 Figure 17. Comparison of Slides in 0 PSU and 25 PSU Solutions on Day 180
* Slides in left column are in 0 PSU solution and slides in right column are in 25 PSU
Solution where (a) indicates the Llama slide, (b) Jennings slide, (c) Ruger slide and (d) Raven
slide.

Figure 17 represents a side-by-side comparison of the corrosion on the

gun slides in the 0 PSU and 25 PSU solutions on day 180. Each slide

exhibits a unique formation of corrosion from 0 PSU to 25 PSU, whether it

entails the source of rust initiation, rust color or residues and/or rust

adherence. For each handgun submerged in the same environmental

condition, the differences in rust between slides can be attributed to the

48
variations among metal composition and is supported by Zheng[29]. The

variation of the rust progression between each handgun submerged in the 0

PSU solution verses the 25 PSU solution can attributed to the presence of

NaCl causing an increase in the mass loss of each slide.

Each handgun displayed a unique process of corrosion between

solutions. For example, when comparing the visual differences of the Llama

handgun in the 0 PSU verses the 25 PSU solution, it should be noted that the

rust formed in the 25 PSU solution was non-adherent to the metal surface.

The non-adherent rust formation on the Llama slide in 25 PSU correlates

with the significantly larger mass loss compared to other the slides displayed

in Table 8. The rust formed on the Llama in the 0 PSU was adherent and

can be seen in Figure 17. Non-adherent rust is loosely bound to the metal

surface and is rarely collected in field analysis[45]. In the laboratory the

loosely bound rust, which usually covered the entire surface, was visible on

the Llama handgun prior to removal from solution.

Figure 18. Non-adherent Rust Formations of Llama in 25 PSU

49
 The photograph from day 24 in Figure 18, displays a typical

representation of the non-adherent rust layer present on the surface of the

Llama handgun. This observation, would present challenges within a field

analysis, due to the water velocity and constant water replenishment, which

would carry away the non-adherent rust.

It should also be noted that several handgun slides had metal screws

and/or sites, which may be composed of a different type of metal. This was

often the location where the rust formations initiated.

Figure 19. Rust Formations Initiated on Screw of Raven Handgun in 0 PSU

solution at Day 24

As displayed in Figure 18 the rust formed on the screw while the rust

formations on the remaining surface was minimal. Similar findings occurred

on the Jennings in the 0 PSU solution and on other screws present on the

Raven handgun in the 0 PSU solution.

50
 Day 3 Day 180

Figure 20. Ruger in 25 PSU Solution Progression of Rust on Site

As displayed in Figure 20, the beginning of rust formation occurred on

the metal site on the top of the muzzle end of the slide. The rust located on

the site occurred rapidly and eventually consumed the entire metal portion of

the site by day 180.

This data demonstrates that although mild changes in NaCl

concentrations and temperature do not seem to impact the rate of corrosion

on SS in a 180 day period, the metal composition and therefore type of gun is

expected to have a significant impact. Since knowledge of the metal

composition and the initial state of the gun is required to characterize the

corrosion rate, a time since immersion within the context of a forensic case

without detailed knowledge of the corrosion processes would be difficult to

establish.

51
3.2.2. XRD Analysis of Handgun Slides

Figure 21. XRD Patterns of Llama Handgun Slide

XRD patterns of Llama handgun where (a) represents the original metal (b) adherent rust
present on day 180 in 0 PSU solution and (c) adherent rust in 25 PSU solution.

52
 Figure 22. XRD Patterns of Jennings Handgun Slide
XRD patterns of Jennings handgun where (a) represents the original metal (b) adherent rust
present on day 180 in 0 PSU solution and (c) adherent rust in 25 PSU solution. () in Figure
22(c) represents the NaCl phase.

53
 Figure 23. XRD Patterns of Ruger Handgun Slide
XRD patterns of Ruger handgun where (a) represents the original metal (b) adherent rust
present on day 180 in 0 PSU solution and (c) adherent rust in 25 PSU solution.

54
 Figure 24. XRD Patterns of Raven Handgun Slide
XRD patterns of Llama handgun where (a) represents the original metal (b) adherent rust
present on day 180 in 0 PSU solution and (c) adherent rust in 25 PSU solution. () in Figure
24(c) represents the NaCl phase.

55
 As displayed in Figures 21(a) through 24(a), the pattern analysis of all

four handgun slide metal resulted in a unique diffractogram for each sample.

The diffractogram of each sample exhibits the presence of different metal

phases, therefore indicating differences in metal composition. The metal

composition is known to affect the rate of corrosion[26, 29]. Given the

significant differences in mass loss and adherent rust phases between guns it

is suggested that it is differences in metal content of the handgun slides

which dictate, to a large degree, the corrosion process and rate.

Additionally, the phases present in the adherent rust are not

equivalent between 0 PSU and 25 PSU solutions. The results signify that the

environmental conditions influence the formation of metal oxides and

hydroxides. For each handgun slide, the XRD pattern of adherent rust in the

0 PSU solution verses the 25 PSU solution differs indicating differences in

phases present on day 180. Each handgun also exhibited differences in mass

loss per day between 0 PSU and 25 PSU solutions, demonstrating not only is

the rate of corrosion changed in the presence of NaCl, but the mechanism is

modified as well. This eludes to the very complex mechanism(s) corrosion

may undergo given a specific composition of metal and environmental

condition. Therefore, a detailed characterization of the corrosion mechanism

is necessary before forensic ballistics units will be able to accurately

56
determine the length of time a particular metal object has been immersed in

a natural body of water.

4. Conclusions
_____________________________________________________________

Overall, based on the 180-day laboratory study conducted with

controlled salinity, temperature and pH parameters the determination of

time since a handgun has been submerged in solution cannot be determined

without properly characterizing the corrosion mechanism/rate. The

mechanism/rate is mainly dependent upon the condition of the gun, the metal

composition and the environmental factors. The numerous factors affecting

the corrosion process and the necessary prior knowledge required makes the

determination of length of submersion within a 180-day period of time

uncertain.

The presence of sodium chloride increases the rate of corrosion of

SS416 and handguns, but rust will not necessarily be observed due to the

non-adhering nature of some of the films, making the time estimate difficult.

Although alterations between the salinity levels from 15 PSU to 35 PSU and

temperatures of 5C and 25C resulted in minimal variation in mass loss

between SS416 samples, the variation in metal composition and condition of

the guns would significantly impact the ability of a forensic examiner to

determine the length of time a metallic object has been submerged in an

aqueous environment. In order to accurately determine length of time since

57
immersion, metal composition, condition, phase determination (i.e. type of

alloy) and the mechanism of oxidation in a given environment need to be

elucidated for a given item of metallic evidence.

58
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 6. Curriculum Vitae
_____________________________________________________________
Katie S. Hoffmeyer (Webster)
21600 Bonz Beach Hwy. Onaway, MI 49765 (616) 634-5150
katiehoffmeyer86@gmail.com

EDUCATION
M.S. Biomedical Forensic Sciences September 2010
Boston University School of Medicine (BUSM), Boston, MA

B.S. Biomedical Science April 2008

Grand Valley State University (GVSU), Allendale MI
Minor: Chemistry

RESEARCH PROJECTS
Effects of Salinity and Temperature on Rates of Corrosion
Boston University School of Medicine, Boston, MA
Massachusetts State Police, Underwater Recovery Team, Boston, MA

In Vitro Analysis of Protective Compounds for Glaucoma

Grand Valley State University, Allendale, MI
Live/Dead Assessment of pig retinal cells in the presence of
Nicotine and Glutamate.
Research Presentations
Student Scholarship Day, Grand Valley State University 2007
Society for Neuroscience Meeting, University of Michigan 2007

RELATED EXPERIENCE
Trace Analysis Laboratory Student Intern Fall 2009
Massachusetts Department of State Police, Sudbury, MA
Independent research project implementing FTIR and py-GC/MS
instrumental analysis.

Student Lab Assistant 2009

Educational Media, BUSM, Boston MA
Preparations for medical student lab courses.

PROFESSIONAL MEMBERSHIP
Boston University Forensic Science Society 2009
Secretary
American Academy of Forensic Sciences February 2009-Present
Student Affiliate

64