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June 16, 2022 - BY Ruchika Dwivedi

Cyanoacrylate Fuming

Background 

Researchers aiming to produce an acrylic polymer for the aerospace industry inadvertently developed the liquid commercial adhesive, super glue, in the 1950s. CA adhesive was also used as a field dressing in Vietnam in the 1960s, however it never got FDA approval for this application. Researchers in Japan and the United Kingdom identified the latent fingerprint development capabilities of liquid glue fumes almost simultaneously in the late 1970s. Latent print examiners from the United States Army Criminal Investigation Laboratory in Japan and the Bureau of Alcohol, Tobacco, and Firearms brought the technology to North America shortly after. Once CA fuming was proven to be a viable technology, ways to make it faster and more efficient were developed.

Since those early discoveries, thousands of crimes have been solved thanks to the routine use of CA ester (typically methyl or ethyl) fuming of evidence, and a significant amount of study has gone into determining the best atmosphere for the procedure.

CA fuming is still a versatile and effective development procedure for practically all nonporous surfaces, such as glass, metal, coated papers, and all types of plastics, today. On rough surfaces, where physical contact with a fingerprint brush tends to develop the material's texture as well as the latent fingerprints, the procedure is particularly effective. CA vapours are highly sensitive to fingerprint residue, may be used in a variety of crime scene and laboratory settings, and are relatively inexpensive to use. 

Studies into the explicit polymerization initiators and the role of water in the development of latent prints are ongoing. These studies should eventually lead to a better understanding of latent print polymerization as it relates to latent print composition, pH, aging, and humidity. 


Theory 

The creation of latent prints using super glue or CA is best described as a three-stage process that produces polymer growth and hence enables latent print viewing.

When vapours of CA ester monomers are applied to latent fingerprints, they promptly link with initiators in the residue in the first step. The fingerprint residue monomer combines with another CA monomer in the vapour phase to generate a dimer on the print in the second stage. This combines with more monomers, eventually generating a polymer, which is a long chain of CA molecules. The polymer chain reaction comes to an end in the final phase. The entire development period is short, especially when the liquid glue volatilization is increased. However, the polymerization process might be restarted at a later time.

CA prints that have been fully developed are a white three-dimensional matrix that can be seen with the naked eye and can be enhanced with a variety of procedures. Because of the plasticization of the print, CA-developed impressions are often more durable than untreated fin-gerprints. As a result, several authorities advise CA treatment prior to evidence packaging in the field to safeguard otherwise vulnerable fingerprints during transportation and storage. When observed using a scanning electron microscope, CA polymerized under ambient laboratory environmental conditions appears as noodlelike, fibrous structures for normal eccrine sweat fingerprints (SEM). When variables such as the age of the latent print, the residue composition, and ambient conditions change, these polymer morphologies change.

 Lewis et al. discovered differences in the effects of ageing on clean and greasy latent print residues. Latent prints that lacked sebum (clean prints) were much more susceptible to the effects of ageing than prints that contained sebum. Clean prints revealed a shift away from the fibrous morphology previously stated and toward polymer structures that appeared rounded under SEM after 1 day of ageing. After only 2 weeks, clean prints proved difficult, if not impossible, to form, but prints contaminated with sebum produced detectable polymer growth for up to 6 months. Lewis et al. also discovered that ageing latent prints in a low-humidity environment had a noticeable and negative impact on CA formation, whereas prints aged in a high-humidity environment survived longer and produced higher-quality polymerization. Surprisingly, latent prints created in a vacuum chamber produce smooth spherical or capsule-like forms that may be seen with a SEM and are more translucent to the naked eye. This could be due to the print being exposed to the vacuum's near-zero-humidity environment, which apparently removed moisture from the fingerprints. At this time, the role of humidity in the development of latent prints in CA remains unknown. In the mid-1990s, Kent discovered that humid settings outperformed vacuum environments in the CA formation of latent prints, although Lewis et al. discovered that humidity had a bigger effect on latent print ageing than on polymerization. Clearly, the effect of humidity in polymerization and ageing has to be investigated further.

The real initiators of latent print polymerization are only now being discovered. CA was thought to predominantly react with the water in fingerprint residue at first. Current study suggests that the key initiators of CA polymerization are water-soluble amines and carboxylic groups in latent print residue. These two groups produce polymer growth with significantly larger molecular weights than water alone. Furthermore, in the absence of water, amines and carboxylic acids will polymerize, leaving the role of water in the ageing and development process uncertain.

Prior to CA treatment, the pH of the humidity to which the latent prints are exposed may also play a role in revitalising latent prints before the polymerization process. The molecular weights of latent prints exposed to acetic acid vapours and then CA fumed were higher than those not exposed. In contrast, CA growth appears to be aided by basic humidity created by ammonia vapours. According to current research, both acidic and basic humidity settings improve latent print polymer formation, with acidic enhancement proving to be more effective. Although the actual mechanism is not fully understood, it is currently thought that exposure to ammonia vapors primarily enhances the functionality of the amine groups, whereas acetic acid vapors favorably influence the more robust carboxylic initiators. 


Application 

It's worth noting that liquid CA and its vapours can cause immediate skin, eye, and mucous membrane damage, and the long-term effects of exposure are unknown. The user must utilise proper ventilation and personal protection equipment, as well as practise safe handling at all times. During usage, all manufacturer's cautions, including those found on material safety data sheets, must be followed.

The optimum result of CA development is light scattering polymerization on the latent print that does not coat the backdrop, allowing the white imprint to be seen against the substrate. This style of "minimum" development yields the most detail, particularly when used in conjunction with fluorescent dye stains. Overfuming will result in prints that appear "frosty" and lack edge sharpness, making them difficult to distinguish from a background that has also been coated with CA polymer. Developed imprints can seem translucent or glassy in nature, depending on latent makeup and environmental circumstances, and can be difficult to notice without special lighting or fluorescent dye staining. In reality, before recording, most impressions will benefit from some type of augmentation.

Fuming with CA can be as easy as vaporising the glue in a fish tank with a tight-fitting lid, or as complex as employing a professionally constructed chamber with dynamic temperature and humidity controls. Both technologies are designed to achieve the same goal: vaporising liquid glue in a polymerization-friendly atmosphere.

Warming a tiny amount of liquid glue (about 0.5 g or less) in an aluminium evaporation dish over a heating block or coffee cup warmer is a common and effective method for the volatilization of CA. The use of an aluminium dish is recommended because it prevents polymerization. The warm vapours rise, but as the chamber cools, they fall to the bottom. As a result, during fuming, a circulation fan is frequently utilised to maintain the fumes equally distributed around the evidence at all levels of the tank. Prints that are found to be underfumed later on can be fumed again, thus restarting the polymerization process.

A commercially available fuming wand is used in a second method of vaporising CA. Butane is used to heat a small brass cartridge with ethyl CA in these wands. The heated cartridge on the end of the wand emits fumes that can be directed at evidence or used to fill a chamber. Air currents readily blow the CA vapours away from the evidence when employing a fuming wand in an open area, making development difficult to manage. Outside of a fume hood, using a fuming wand has various health and safety issues that must be considered.

Vaporization can also be achieved without an external heat source. Instead, chemical acceleration is produced by the exothermic reaction that can be achieved by pouring liquid glue on a pad of high cellulose content pretreated with sodium hydroxide. Pretreatment simply involves a cotton ball prepared with a few drops of NaOH solution. 

CA Increase the total surface area of the liquid glue, which increases the rate of evaporation, to accomplish fuming without acceleration. Sandwiching a bead of liquid glue between two sheets of aluminium foil is one way to accomplish this. The sheets are then pushed together, and the adhesive is thoroughly dispersed across the entire inside of the foil surfaces with an ink roller. These sheets are then opened and placed within a chamber, exposing the adhesive layers to the air, which are relatively volatile. The length of time it takes for CA to develop in this procedure is dependent on the size of the chamber.

The use of a vacuum chamber to fume CA has also been suggested as a way to increase its volatility. At normal temperature, the decreasing air pressure decreases the boiling point of the liquid glue, allowing it to evaporate more quickly. The negative pressure also reduces humidity in the tank, which has an impact on the overall appearance of the impressions. Prints made in a vacuum are generally transparent, making them difficult to spot without liquid dye stains. However, some experts have discovered that this method is less effective in the long run than using regulated humidity conditions.

Although it is preferable to cultivate CA in a laboratory chamber, improvised chambers can be simply constructed in the field. Cardboard boxes, small frames with clear plastic sheeting, big tents, vehicle interiors, and even full rooms are examples of chambers. The automotive interior is arguably the most ubiquitous of these field chambers. A hot plate (about 60 °C) in the centre of the vehicle with roughly 1 gramme of glue in an evaporation dish is one method of fuming. After that, all of the doors and windows are closed to seal off the interior. The heated glue fumes quickly permeate the vehicle inside, leaving impressions all throughout. The time it takes to complete this operation varies between 10 and 30 minutes. To avoid destroying the entire vehicle, pieces of it may be removed and fumed separately in some situations (e.g., steering wheel, mirror). CA fuming of a firearm may interfere with later firearms testing in some cases. Before any CA processing, firearms examiners may need to be consulted.

The length of time it takes to fume depends on the size of the chamber, the amount of glue used, the heat source's temperature, and the substrate's and latent print residue's type. Fumigation should be stopped as soon as the first evidence of fingerprints occur, under any circumstances. Some examiners will place a test strip with fingerprints in the chamber to watch for the development of prints. This not only helps to determine when processing should cease but also acts to ensure that the equipment is functioning prop¬erly. Fuming can be restarted later if impressions appear underdeveloped. 


Enhancement 

After the prints have been formed, they can be enhanced optically with oblique, axial, reflected, and transmitted lighting techniques, chemically with fluorescent dye stains, and physically with fingerprint powder application, in that order. The most dramatic results are usually obtained by staining fluorescent dyes and examining them with a laser or forensic light source; however, not all CA-polymerized prints will receive dye stains.

Preparing a commercially available fluorescent stain in solution and applying it on the polymerized fingerprints is all that is required for dye staining. See the FBI Processing Guide for Developing Latent Prints or the Home Office document for a comprehensive list of fluorescent dye stain preparations. Once a dye solution has been chosen, it is dipped or sprayed onto nonporous surfaces that have been exposed to CA vapours. Dye-staining polymerized prints is supposed to act like a molecular sieve, with dye molecules being stuck in the polymer by filling gaps. As a result, it's critical to thoroughly rinse the surface with the dye stain that contains the fingerprints. When seen with a forensic light source or laser, the print emits bright fluorescence. Proper photography at this step might go beyond simply documenting the image to improve the visibility of the fluorescing print by capturing detail that is invisible to the naked eye.

Powdering polymerized imprints is also a useful approach to view and document them. Impressions are often robust enough that they can be dusted with fingerprint powder and elevated with tape until the lift achieves the desired contrast.


Conclusion 

Since the late 1970s, CA fuming has been used as a validated and effective method of creating latent print impressions incorporating eccrine and sebaceous remnants. CA molecules polymerize with residue to create a visible and long-lasting product that can be amplified and recorded via fluorescence, photography, and lifting. The chemistry and physics of the CA reaction are still being studied. The heat-accelerated procedure in controlled high humidity (60–80 percent relative humidity) is currently the most commonly recommended application method. CA development should also be done as soon as possible following fingerprint deposition for best results. Although CA fuming has been shown to be effective for long periods of time after deposition, it can also be used before evidence packaging. Although CA fuming has proven effective for considerable durations of time after deposition, CA fuming prior to evidence packag¬ing can also be an effective means of stabilizing fragile latent impressions during storage and transportation 


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