Effect of temperature on rectifying Schottky barriers formed from fingerprint sweat corrosion of brass

Corrosive electrochemical processes of brass, including those resulting from fingerprint sweat, continue to be studied because of the widespread industrial use of brass. Here, we examine how increased temperature affects the relative abundance of fingerprint sweat corrosion products and the rectifying Schottky barrier formed between p-type copper (I) oxide corrosion and brass. X-ray photoelectron spectroscopy confirms increasing dezincification with increasing temperature. This leads to n-type zinc oxide replacing copper (I) oxide as the dominant corrosion product, which then forms a rectifying Schottky barrier with the brass, instead of copper oxide, when the temperature reaches c. 600°C. Using X-ray diffraction, resulting diodes show polycrystalline oxides embedded in amorphous oxidation products that have a lower relative abundance than the diode forming oxide. Conventional current/voltage (I/V) characteristics of these diodes show good rectifying qualities. At temperatures between c. 100 and c. 600°C, when neither oxide dominates, the semiconductor/brass contact displays an absence of rectification.     

Visualization of latent fingermark corrosion of brass, climatic influence in a comparison between the U.K. and Iraq

Through a comparison of fingermark sweat corrosion of α phase brass in both the U.K. and Iraq, we show how samples from Iraq have improved fingermark corrosion over U.K. samples that require no additional enhancement prior to visualization. Over 50% of Iraqi samples produced fingermark corrosion with full ridge detail compared with 0% from the U.K. X-ray photoelectron spectroscopy analysis of the fingermark corrosion products showed that Iraqi samples exhibit more dezincification with the Zn:Cu ratio averaging 1:1.82 compared with 1:3.07 for U.K. samples. Auger spectroscopy showed the presence of both zinc oxide and copper (I) oxide. No copper (II) was observed on the surface of the corroded brass. Opportunities to exploit the optical properties of these thin film oxides to enhance the visualization of fingermark corrosion are considered, and the potential to use fingermark corrosion of metal as a means of visualizing fingerprints in war zones is discussed.     

Visualization of Latent Fingerprint Corrosion of Brass

Abstract:  Visualization of latent fingerprint deposits on metals by enhancing the fingerprint-induced corrosion is now an established technique. However, the corrosion mechanism itself is less well understood. Here, we describe the apparatus constructed to measure the spatial variation (Δ V ) in applied potential ( V ) over the surface of brass disks corroded by latent fingerprint deposits. Measurement of Δ V for potential of 1400 V has enabled visualization of fingerprint ridges and characteristics in terms of this potential difference with Δ V typically of a few volts. This visualization is consistent with the formation of a Schottky barrier at the brass-corrosion product junction. Measurement of the work function of the corroded brass of up to 4.87 ± 0.03 eV supports previous results that suggested that the corrosion product is composed of p-type copper oxides. A model for the galvanic corrosion of brass by ionic salts present in fingerprint deposits is proposed that is consistent with these experimental results.     

A Comparison of Fingerprint Sweat Corrosion of Different Alloys of Brass

Fingerprint sweat from 40 donors was deposited onto samples of five α and α + β phase brasses, comprising five alloys with different copper and zinc concentrations, two of which also had the addition of small concentrations of lead. Visual grading of the visibility of the corrosion revealed that brasses with the least amount of zinc produced the most visible and fully formed fingerprints from the most donors. Consideration of previously reported mechanisms for the corrosion of brass suggests red copper (I) oxide as a likely corrosion product for low zinc brasses, and a consideration of the color, composition, and solubility of fingerprint sweat corrosion products suggests that copper (I) oxide produces good contrast and visibility with the brass substrate. Scanning electron microscope images of the corrosion of all five alloys confirmed the enhanced contrast between corroded and uncorroded areas for low zinc alloys.     

Effect of chloride ion concentration on the galvanic corrosion of α phase brass by eccrine sweat

Inductively coupled plasma mass spectrometry measurement of the relative concentration of sodium, chloride, calcium, and potassium ions in eccrine sweat deposits from 40 donors revealed positive correlations between chloride and sodium (ρ = 0.684, p < 0.01) and chloride and calcium ions (ρ = 0.91, p < 0.01). Correlations between ion concentration and the corrosion of α phase brass by the donated sweat were investigated by visual grading of the degree of corrosion, by measuring the copper/zinc ratio using energy-dispersive X-ray spectroscopy, and from a measurement of the potential difference between corroded and uncorroded brass when a large potential was applied to the uncorroded brass. An increasing copper/zinc ratio (indicative of dezincification) was found to correlate positively to both chloride ion concentration and visual grading of corrosion, while visual grading gave correlations with potential difference measurements that were indicative of the preferential surface oxidation of zinc rather than copper.     

Can the RUVIS Reflected UV Imaging System Visualize Fingerprint Corrosion on Brass Cartridge Casings Postfiring?

Comparisons are made between the visualization of fingerprint corrosion ridge detail on fired brass cartridge casings, where fingerprint sweat was deposited prefiring, using both ultraviolet (UV) and visible (natural daylight) light sources. A reflected ultraviolet imaging system (RUVIS), normally used for visualizing latent fingerprint sweat deposits, is compared with optical interference and digital color mapping of visible light, the latter using apparatus constructed to easily enable selection of the optimum viewing angle. Results show that reflected UV, with a monochromatic UV source of 254 nm, was unable to visualize fingerprint ridge detail on any of 12 casings analyzed, whereas optical interference and digital color mapping using natural daylight yielded ridge detail on three casings. Reasons for the lack of success with RUVIS are discussed in terms of the variation in thickness of the thin film of metal oxide corrosion and absorption wavelengths for the corrosion products of brass.     

Effect of Temperature on the Visualization by Digital Color Mapping of Latent Fingerprint Deposits on Metal

Visualization of fingerprint deposits by digital color mapping of light reflected from the surface of heated brass, copper, aluminum, and tin has been investigated using Adobe^® Photoshop^®. Metals were heated to a range of temperatures (T) between 50°C and 500°C in 50°C intervals with enhancement being optimal when the metals are heated to 250°C, 350°C, 50°C, and 300°C, respectively, and the hue values adjusted to 247°, 245°, 5°, and 34°, respectively. Fingerprint visualization after color mapping was not degraded by subsequent washing of the metals and color mapping did not compromise the visibility of the fingerprint for all values of T. The optimum value of T for fingerprint visibility is significantly dependent of the standard reduction potential of the metal with Kendall's Tau (τ) = 0.953 (p < 0.001). For brass, this correlation is obtained when considering the standard reduction potential of zinc rather than copper.     

Comparison of metal ions recovered during DNA analysis of brass ammunition and effects of copper and zinc ions on DNA profiling

Analyzing DNA from brass surfaces poses unique challenges that may result from DNA damage and/or PCR inhibition. To examine the relationship between the metal ions present in brass ammunition and the success of Short Tandem Repeat (STR) profiling, six recovery methods were tested to determine the identity and quantity of metal ions co-recovered during DNA sampling. In addition, DNA and metal ion solutions were created at varying concentrations to determine the threshold at which deleterious effects occur. The results of this study show that copper and zinc are recovered in the highest concentrations from both fired and unfired ammunition, but at substantially lower levels than previously published. Furthermore, most metal ions co-recovered with DNA were removed during DNA purification and complete STR profiles were generated when the concentrations of copper and zinc ions were less than 0.1 M and 0.03 M, respectively.     

Visualization of latent fingerprint corrosion of metallic surfaces

Abstract:  Chemical reactions between latent fingerprints and a variety of metal surfaces are investigated by heating the metal up to temperatures of ∼600°C after deposition of the fingerprint. Ionic salts present in the fingerprint residue corrode the metal surface to produce an image of the fingerprint that is both durable and resistant to cleaning of the metal. The degree of fingerprint enhancement appears independent of the elapsed time between deposition and heating but is very dependent on both the composition of the metal and the level of salt secretion by the fingerprint donor. Results are presented that show practical applications for the enhancement to fingerprints deposited in arson crime scenes, contaminated by spray painting, or deposited on brass cartridge cases prior to discharge. The corrosion of the metal surface is further exploited by the demonstration of a novel technique for fingerprint enhancement based on the electrostatic charging of the metal and then the preferential adherence of a metallic powder to the corroded part of the metal surface.     

甲醛溶液固定对ICP-MS检测电流损伤皮肤金属化的影响

目的探讨应用电感耦合等离子体质谱（inductively coupled plasma-mass spectrometry ICP-MS）技术检测甲醛溶液固定后电流损伤皮肤中金属元素。方法利用黄铜、铁电极材料以220V交流电电击兔子后肢,电损伤皮肤分别进行甲醛溶液固定1周、6个月后,应用ICP-MS对电流损伤皮肤中金属元素进行测定。结果与对照组皮肤比较,黄铜电击组皮肤中检测出Cr、Ni、Cu、Zn、Pb含量升高（P〈0.05）;固定1周、6个月后仍可检测出Cr、Ni、Cu、Zn、Pb成分,其中Cr、Cu、Zn、Pb含量电击组与固定组差异无统计学意义。与对照组比较,铁电击后皮肤中检测出Fe、Cr、Mn、Ni元素含量升高（P〈0.05）;固定组（1周和6个月）后Fe、Cr、Ni元素含量与电击组差异无统计学意义。结论 ICP-MS可作为检测电流损伤皮肤中金属元素的有效方法,甲醛溶液固定后触电皮肤仍可进行沉积的金属元素检测,且固定对皮肤金属元素的含量影响较小,该方法仍可为电流损伤诊断提供依据。     

A Comparison of Cleaning Regimes for the Effective Removal of Fingerprint Deposits from Brass

Abstract:  Effective removal of fingerprint deposits is crucial for experimentation related to the corrosion of metals by fingerprint deposits. Such removal is also necessary prior to deposition of test fingerprints. The effectiveness of four regimes in removing fingerprint deposits from brass is considered. Sustained wiping of the deposit with a tissue at applied pressures of up to c . 1430 Pa or rubbing while the brass was immersed in acetone both failed to remove completely all traces of fingerprint deposits. Heating the brass to 600°C was an effective remover; however, this also oxidized the surface of the metal except where inhibited by fingerprint deposits. The most effective regime, and the only one of the four that removed all traces of deposit without affecting the properties of the metal surface, was immersion in warm soapy water while rubbing with a tissue. We propose this as the preferred method for fingerprint removal.     

The thermodynamics of latent fingerprint corrosion of metal elements and alloys

Redox reactions taking place between the surface of a metal and fingerprint residue have been expressed thermodynamically in terms of both the Nernst equation for reduction potential and the complexation constant for the formation of complex metal halide ions in aqueous solution. These expressions are used to explain experimental results for the corrosion of 10 different metal elements by fingerprint residue in air at room temperature. Corrosion of noble metals, such as silver and gold, supports the proposition that the degree of metal corrosion is enhanced by the presence of chloride ions in eccrine sweat. Extending the experiments to include 10 metal alloys enabled the construction of a fingerprint corrosion series for 20 different metals. Fingerprint corrosion on metals alloyed with > approximately 40% copper was found to display third level fingerprint detail. A comparison of both conventional ink on paper and digital (Livescan) fingerprinting techniques with fingerprints deposited on 9 Karat gold alloy has shown that gold alloy depositions are least susceptible to third level detail obliteration by poor fingerprint capturing techniques.     

A Preliminary Study on Vacuum Metal Deposition as a Standalone Method for Enhancement of Fingermarks on Ballistic Brass Materials

In order to assess the efficacy of vacuum metal deposition (VMD) as a technique to develop fingermarks on ballistic metallic surfaces, a preliminary study using six donors (three male & three female) was conducted. Using a sequential metal deposition process, two metal combinations were studied—gold/zinc and silver/zinc. Results indicate the potential of this technique, by developing identifiable fingermarks on brass metal disks aged from a few days up to more than a month old. As the development of fingermarks on fired (brass) cartridge cases is an area of interest, a further study was conducted where a total of 20 fingermarks were deposited on cases. After firing, second level fingermark characteristics were successfully observed on cartridge cases highlighting its potential as a fingermark enhancement method for ballistic brass materials. Further work is required to fully evaluate the VMD process and its reliability as a fingermark enhancing method on ballistic surfaces.     

A sudden death with lung embolism after inadvertent infusion of zinc oxide shake lotion

A 74-year old woman in postoperative treatment after a colonic surgery died immediately after perfusion of about 1.5 mL of a white emulsion which was believed to contain 1% propofol via cardiac catheter into the right atrium. It was strongly suspected that a syringe with a zinc oxide shake lotion (consisting of 20% ZnO, 20% talc, 25% glycerol and 35% water) which was intended for external treatment had been mistaken for the propofol syringe. During autopsy, an anatomic cause of death could not be found. In order to exclude an intoxication and to determine the significance of the perfusion fluid in this context, toxicological and histological investigations were performed. Propofol and other drugs applied to the patient were found in therapeutic or sub-therapeutic range. However, in comparison to a control case, the zinc concentrations determined by AAS were about 200 times higher in lung tissue, 10 times higher in heart blood and 3–4 times higher in kidney and liver tissue. No increase was seen in venous blood. Histology showed a strong embolism of the lung tissue with birefingent sharp-edged crystals, which were identified as the talcum, and an amorphous component (ZnO). The same embolism was seen to a medium extent also in the brain sections and to a low extent in heart, liver, pancreas and kidney. Pulmonary embolism by talcum and zinc oxide was established as the cause of death which occurred by syringe swap due to insufficient security precautions in the drug administration. The results are discussed in context of pulmonary microembolism cases frequently described for drug addicts after injection of crashed talcum containing tablets.     

The Effect of Light Exposure on the Degradation of Latent Fingerprints on Brass Surfaces: The Use of Silver Electroless Deposition as a Visualization Technique

We have studied the degradation of sebaceous fingerprints on brass surfaces using silver electroless deposition (SED) as a visualization technique. We have stored fingerprints on brass squares either (i) in a locked dark cupboard or (ii) in glass‐filtered natural daylight for periods of 3 h, 24 h, 1 week, 3 weeks, and 6 weeks. We find that fingerprints on brass surfaces degrade much more rapidly when kept in the light than they do under dark conditions with a much higher proportion of high‐quality prints found after 3 or 6 weeks of aging when stored in the dark. This process is more marked than for similar fingerprints on black PVC surfaces. Identifiable prints can be achieved on brass surfaces using both SED and cyanoacrylate fuming (CFM). SED is quick and straightforward to perform. CFM is more time‐consuming but is versatile and can be applied to a wider range of metal surfaces than SED, for example brass surfaces which have been coated by a lacquer.     

Fluorescent technique for macroscopic detection of electrical metallization

A fluorescence method for the detection of trace metals was investigated to visualize in situ latent current marks or electrical metallic traces on cloth. The main electrodes metallization (iron, copper, zinc, aluminum, nickel, chromium, and brass) can be identified by spraying a 0.2% solution of 8-hydroxyquinoline in ethanol followed by observation under shortwave UV light. Advantages and disadvantages of this technique are compared with previously described methods.     

High Resolution Imaging of Latent Fingerprints by Localized Corrosion on Brass Surfaces

Abstract:  The Atomic Force Microscope (AFM) is capable of imaging fingerprint ridges on polished brass substrates at an unprecedented level of detail. While exposure to elevated humidity at ambient or slightly raised temperatures does not change the image appreciably, subsequent brief heating in a flame results in complete loss of the sweat deposit and the appearance of pits and trenches. Localized elemental analysis (using EDAX, coupled with SEM imaging) shows the presence of the constituents of salt in the initial deposits. Together with water and atmospheric oxygen—and with thermal enhancement—these are capable of driving a surface corrosion process. This process is sufficiently localized that it has the potential to generate a durable negative topographical image of the fingerprint. AFM examination of surface regions between ridges revealed small deposits (probably microscopic "spatter" of sweat components or transferred particulates) that may ultimately limit the level of ridge detail analysis.     

The effect of electrostatic fingerprint visualization on integrated ballistic identification systems

Visualization of fingerprint corrosion on spent brass cartridge cases by the application of a high electrical potential and conducting carbon powder is becoming an accepted method of fingerprint enhancement. However, to date, no examination has been made of any effect this technique has on ballistic identification. To resolve this, images of the breech face and firing pin marks were captured on six plated nickel and six brass primer cup spent cartridge cases. Three nickel and three brass cases were then subjected to the application of a potential of +2500 V for a period of 1 min. The remaining cases were additionally subjected to the application of carbon powder. These latter cases were then washed to remove all traces of powder. Each case was recaptured with the same ballistic identification apparatus and imaging procedure. None of the twelve cases showed any visual difference after the application of the potential or conducting powder.     

微束X射线荧光光谱法检测电流损伤皮肤金属化

目的建立微束X射线荧光光谱（μ-probe X-ray fluorescence,μ-XRF）检测电流损伤皮肤金属化的方法。方法新西兰大白兔32只,随机分为黄铜电击组、紫铜电击组、铁电击组、铝合金电击组,每组8只。电极一极固定于左后腿中部,另一极固定于左前腿,建立电击模型。提取左后腿触电部位皮肤,以及对侧右后腿相应部位皮肤作为对照,应用μ-XRF光谱仪对电流损伤皮肤内金属元素进行测定。结果正常对照组皮肤中检测出磷、氯、钾、钙元素成分;在电击组皮肤中,除正常皮肤检出的元素外,黄铜电击组检测出铜、锌元素,紫铜电击组检出铜元素,铁电击组检出铁元素,铝合金电击组检出铝元素。渗透到电流损伤皮肤内的金属元素呈不均匀分布。结论μ-XRF光谱法检测皮肤金属化可作为诊断电流损伤的特征性指标,并可为触电材料的推断提供依据。     

1,2,4‐Triazine‐Based Chromogenic Reagents for the Detection of Microtraces of Various Metals Left on Human Skin*

Abstract: This article extends the application of 1,2,4‐triazine‐based chromogenic reagents to the detection of nonferrous metal traces left on contact with canvas and human skin. The possibility of detection of iron traces resulting from contact with objects made of stainless steel was investigated as well. Additionally, the ability of triazines to form chromatic complexes with Zn²⁺, Ni²⁺, Co²⁺, Cu²⁺, Cr³⁺, and Al³⁺ ions was studied spectrophotometrically. Molar absorption coefficients, ranging from 8.8 to 29.9 × 10³/M/cm, provide high sensitivity of 1,2,4‐triazines toward nonferrous ions, thus, enabling the detection at concentrations as low as a few μM. The method was sensitive enough to detect traces resulting from a 1‐min contact with a stainless steel made object, which is commonly considered as a corrosion‐resistant material. The amounts of metal ions transferred to the skin after a 2‐min contact with objects made of brass, zinc, and copper were sufficient to develop chromatic imprints.