Photographic film
Photographic film is a strip or sheet of transparent film base coated on one side with a gelatin emulsion containing microscopically small light-sensitive silver halide crystals, for the purpose of taking photographs. The sizes and other characteristics of the crystals determine the sensitivity, contrast, and resolution of the film. Film is typically segmented in frames, which give rise to separate photographs.
The emulsion will gradually darken if left exposed to light, but the process is too slow and incomplete to be of practical use. Instead, a very short exposure to the image made possible by a camera lens is used to produce only a very slight chemical change, proportional to the amount of light absorbed by each crystal. This creates an invisible latent image in the emulsion, which can be chemically developed into a visible photograph.
In addition to visible light, most films are sensitive to ultraviolet light, X-rays, gamma rays, and high-energy particles. Unmodified silver halide crystals are sensitive only to the blue part of the visible spectrum, producing unnatural-looking renditions of some colored subjects. This problem was resolved with the discovery that certain dyes, called sensitizing dyes, when adsorbed onto the silver halide crystals, made them respond to other colors as well. First orthochromatic and finally panchromatic films were developed. Panchromatic film renders all colors in shades of gray approximately matching their subjective brightness. By similar techniques, special-purpose films can be made sensitive to the infrared region of the spectrum.
In black-and-white photographic film, there is usually one layer of silver halide crystals. When the exposed silver halide grains are developed, the crystals are converted to metallic silver, which blocks light and appears as the black part of the film negative. Color film has at least three sensitive layers, incorporating different combinations of sensitizing dyes. Typically, the blue-sensitive layer is on top, followed by a yellow filter layer to stop any remaining blue light from affecting the layers below. Next comes a green-and-blue sensitive layer, and a red-and-blue sensitive layer, which record the green and red images respectively. During development, the exposed silver halide crystals are converted to metallic silver, just as with black-and-white film. But in a color film, the by-products of the development reaction simultaneously combine with chemicals known as color couplers that are included either in the film itself or in the developer solution to form colored dyes. Because the by-products are created in direct proportion to the amount of exposure and development, the dye clouds formed are also in proportion to the exposure and development. Following development, the silver is converted back to silver halide crystals in the bleach step. It is removed from the film during the process of fixing the image on the film with a solution of ammonium thiosulfate or sodium thiosulfate. Fixing leaves behind only the formed color dyes, which combine to make up the colored visible image. Later color films, like Kodacolor II, have as many as 12 emulsion layers, with upwards of 20 different chemicals in each layer.
Photographic film and film stock tend to be similar in composition and speed, but often not in other parameters such as frame size and length. Silver halide photographic paper is also similar to photographic film.
Before the emergence of digital photography, photographs on film had to be developed to produce negatives or projectable slides, and negatives had to be printed as positive images, usually in enlarged form. This was usually done by photographic laboratories, but many amateurs did their own processing.
Characteristics of film
Film basics
There are several types of photographic film, including:- Print film, when developed, yields transparent negatives with the light and dark areas and colors inverted to their respective complementary colors. This type of film is designed to be printed onto photographic paper, usually by means of an enlarger but in some cases by contact printing. The paper is then itself developed. The second inversion that results restores light, shade and color to their normal appearance. Color negatives incorporate an orange color correction mask that compensates for unwanted dye absorptions and improves color accuracy in the prints. Although color processing is more complex and temperature-sensitive than black-and-white processing, the wide availability of commercial color processing and scarcity of service for black-and-white prompted the design of some black-and-white films which are processed in exactly the same way as standard color film.
- Color reversal film produces positive transparencies, also known as diapositives. Transparencies can be reviewed with the aid of a magnifying loupe and a lightbox. If mounted in small metal, plastic or cardboard frames for use in a slide projector or slide viewer they are commonly called slides. Reversal film is often marketed as "slide film". Large-format color reversal sheet film is used by some professional photographers, typically to originate very-high-resolution imagery for digital scanning into color separations for mass photomechanical reproduction. Photographic prints can be produced from reversal film transparencies, but positive-to-positive print materials for doing this directly have all been discontinued, so it now requires the use of an internegative to convert the positive transparency image into a negative transparency, which is then printed as a positive print.
- Black-and-white reversal film exists but is very uncommon. Conventional black-and-white negative film can be reversal-processed to produce black-and-white slides, as by dr5 Chrome. Although kits of chemicals for black-and-white reversal processing may no longer be available to amateur darkroom enthusiasts, an acid bleaching solution, the only unusual component which is essential, is easily prepared from scratch. Black-and-white transparencies may also be produced by printing negatives onto special positive print film, still available from some specialty photographic supply dealers.
The concentration of dyes or silver halide crystals remaining on the film after development is referred to as optical density, or simply density; the optical density is proportional to the logarithm of the optical transmission coefficient of the developed film. A dark image on the negative is of higher density than a more transparent image.
Most films are affected by the physics of silver grain activation and by the statistics of random grain activation by photons. The film requires a minimum amount of light before it begins to expose, and then responds by progressive darkening over a wide dynamic range of exposure until all of the grains are exposed, and the film achieves its maximum optical density.
Over the active dynamic range of most films, the density of the developed film is proportional to the logarithm of the total amount of light to which the film was exposed, so the transmission coefficient of the developed film is proportional to a power of the reciprocal of the brightness of the original exposure. The plot of the density of the film image against the log of the exposure is known as an H&D curve. This effect is due to the statistics of grain activation: as the film becomes progressively more exposed, each incident photon is less likely to impact a still-unexposed grain, yielding the logarithmic behavior. A simple, idealized statistical model yields the equation, where light is proportional to the number of photons hitting a unit area of film, k is the probability of a single photon striking a grain, and density is the proportion of grains that have been hit by at least one photon. The relationship between density and log exposure is linear for photographic films except at the extreme ranges of maximum exposure and minimum exposure on an H&D curve, so the curve is characteristically S-shaped. The sensitivity of a film can be affected by changing the length or temperature of development, which would move the H&D curve to the left or right.
If parts of the image are exposed heavily enough to approach the maximum density possible for a print film, then they will begin losing the ability to show tonal variations in the final print. Usually those areas will be considered overexposed and will appear as featureless white on the print. Some subject matter is tolerant of very heavy exposure. For example, sources of brilliant light, such as a light bulb or the sun, generally appear best as a featureless white on the print.
Likewise, if part of an image receives less than the beginning threshold level of exposure, which depends upon the film's sensitivity to lightor speedthe film there will have no appreciable image density, and will appear on the print as a featureless black. Some photographers use their knowledge of these limits to determine the optimum exposure for a photograph; for one example, see the Zone System. Most automatic cameras instead try to achieve a particular average density.
Color films can have many layers. The film base can have an antihalation layer applied to it or be dyed. This layer prevents light from reflecting from within the film, increasing image quality. This also can make films exposable on only one side, as it prevents exposure from behind the film. This layer is bleached after development to make it clear, thus making the film transparent. The antihalation layer, besides having a black colloidal silver sol pigment for absorbing light, can also have two UV absorbents to improve lightfastness of the developed image, an oxidized developer scavenger, dyes for compensating for optical density during printing, solvents, gelatin and disodium salt of 3,5-
disulfocatechol. If applied to the back of the film, it also serves to prevent scratching, as an antistatic measure due to its conductive carbon content, and as a lubricant to help transport the film through mechanisms. The antistatic property is necessary to prevent the film from getting fogged under low humidity, and mechanisms to avoid static are present in most if not all films. If applied on the back it is removed during film processing. If applied it may be on the back of the film base in triacetate film bases or in the front in PET film bases, below the emulsion stack. An anticurl layer and a separate antistatic layer may be present in thin high resolution films that have the antihalation layer below the emulsion. PET film bases are often dyed, specially because PET can serve as a light pipe; black and white film bases tend to have a higher level of dying applied to them. The film base needs to be transparent but with some density, perfectly flat, insensitive to light, chemically stable, resistant to tearing and strong enough to be handled manually and by camera mechanisms and film processing equipment, while being chemically resistant to moisture and the chemicals used during processing without losing strength, flexibility or changing in size.
The subbing layer is essentially an adhesive that allows the subsequent layers to stick to the film base. The film base was initially made of highly flammable cellulose nitrate, which was replaced by cellulose acetate films, often cellulose triacetate film, which in turn was replaced in many films by a polyethylene terephthalate plastic film base. Films with a triacetate base can suffer from vinegar syndrome, a decomposition process accelerated by warm and humid conditions, that releases acetic acid which is the characteristic component of vinegar, imparting the film a strong vinegar smell, accelerating damage within the film and possibly even damaging surrounding metal and films. Films are usually spliced using a special adhesive tape; those with PET layers can be ultrasonically spliced or their ends melted and then spliced.
The emulsion layers of films are made by dissolving pure silver in nitric acid to form silver nitrate crystals, which are mixed with other chemicals to form silver halide grains, which are then suspended in gelatin and applied to the film base. The size and hence the light sensitivity of these grains determines the speed of the film; since films contain real silver, faster films with larger crystals are more expensive and potentially subject to variations in the price of silver metal. Also, faster films have more grain, since the grains are larger. Each crystal is often 0.2 to 2 microns in size; in color films, the dye clouds that form around the silver halide crystals are often 25 microns across. The crystals can be shaped as cubes, flat rectangles, tetradecadedra, or be flat and resemble a triangle with or without clipped edges; this type of crystal is known as a T-grain crystal or a tabular grain. Films using T-grains are more sensitive to light without using more silver halide since they increase the surface area exposed to light by making the crystals flatter and larger in footprint instead of simply increasing their volume.
T-grains can also have a hexagonal shape. These grains also have reduced sensitivity to blue light which is an advantage since silver halide is most sensitive to blue light than other colors of light. This was traditionally solved by the addition of a blue-blocking filter layer in the film emulsion, but T-grains have allowed this layer to be removed. Also the grains may have a "core" and "shell" where the core, made of silver iodobromide, has higher iodine content than the shell, which improves light sensitivity, these grains are known as Σ-Grains.
The exact silver halide used is either silver bromide or silver bromochloroiodide, or a combination of silver bromide, chloride and iodide. Silver iodobromide may be used as a silver halide.
Silver halide crystals can be made in several shapes for use in photographic films. For example, AgBrCl hexagonal tabular grains can be used for color negative films, AgBr octahedral grains can be used for instant color photography films, AgBrl cubo-octahedral grains can be used for color reversal films, AgBr hexagonal tabular grains can be used for medical X-ray films, and AgBrCl cubic grains can be used for graphic arts films.
In color films, each emulsion layer has silver halide crystals that are sensitized to one particular color via sentizing dyes, to that they will be made sensitive to only one color of light, and not to others, since silver halide particles are intrinsically sensitive only to wavelengths below 450 nm. The sensitizing dyes are absorbed at dislocations in the silver halide particles in the emulsion on the film. The sensitizing dyes may be supersensitized with a supersensitizing dye, that assists the function of the sensitizing dye and improves the efficiency of photon capture by silver halide. Each layer has a different type of color dye forming coupler: in the blue sensitive layer, the coupler forms a yellow dye; in the green sensitive layer the coupler forms a magenta dye, and in the red sensitive layer the coupler forms a cyan dye. Color films often have an UV blocking layer. Each emulsion layer in a color film may itself have three layers: a slow, medium and fast layer, to allow the film to capture higher contrast images. The color dye couplers are inside oil droplets dispersed in the emulsion around silver halide crystals, forming a silver halide grain. Here the oil droplets act as a surfactant, also protecting the couplers from chemical reactions with the silver halide and from the surrounding gelatin. During development, oxidized developer diffuses into the oil droplets and combines with the dye couplers to form dye clouds; the dye clouds only form around exposed silver halide crystals. The fixer then removes the silver halide crystals leaving only the dye clouds: this means that developed color films may not contain silver while undeveloped films do contain silver; this also means that the fixer can start to contain silver which can then be removed through electrolysis. Color films also contain light filters to filter out certain colors as the light passes through the film: often there is a blue light filter between the blue and green sensitive layers and a yellow filter before the red sensitive layer; in this way each layer is made sensitive to only a certain color of light.
The couplers need to be made resistant to diffusion so that they will not move between the layers of the film and thus cause incorrect color rendition as the couplers are specific to either cyan, magenta or yellow colors. This is done by making couplers with a ballast group such as a lipophilic group and applying them in oil droplets to the film, or a hydrophilic group, or in a polymer layer such as a loadable latex layer with oil-protected couplers, in which case they are considered to be polymer-protected.
The color couplers may be colorless and be chromogenic or be colored. Colored couplers are used to improve the color reproduction of film. The first coupler which is used in the blue layer remains colorless to allow all light to pass through, but the coupler used in the green layer is colored yellow, and the coupler used in the red layer is light pink. Yellow was chosen to block any remaining blue light from exposing the underlying green and red layers. Each layer should only be sensitive to a single color of light and allow all others to pass through. Because of these colored couplers, the developed film appears orange. Colored couplers mean that corrections through color filters need to be applied to the image before printing. Printing can be carried out by using an optical enlarger, or by scanning the image, correcting it using software and printing it using a digital printer.
Kodachrome films have no couplers; the dyes are instead formed by a long sequence of steps, limiting adoption among smaller film processing companies.
Black and white films are very simple by comparison, only consisting of silver halide crystals suspended in a gelatin emulsion which sits on a film base with an antihalation back.
Many films contain a top supercoat layer to protect the emulsion layers from damage. Some manufacturers manufacture their films with daylight, tungsten or fluorescent lighting in mind, recommending the use of lens filters, light meters and test shots in some situations to maintain color balance, or by recommending the division of the ISO value of the film by the distance of the subject from the camera to get an appropriate f-number value to be set in the lens.
Examples of Color films are Kodachrome, often processed using the K-14 process, Kodacolor, Ektachrome, which is often processed using the E-6 process and Fujifilm Superia, which is processed using the C-41 process. The chemicals and the color dye couplers on the film may vary depending on the process used to develop the film.