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Ambrotypes are similar to daguerrotypes in that they were often preserved in similar cases, but the difference comes down to the process used and how it looks.
While "dags" were produced on sheets of copper/silver, ambrotypes were produced on an actual mirror that was coated in a silver iodized sulfate solution.
ambrotypes or daguerrotypes that were always cased.
If you want to verify that you have a tintype, however, there is a sure-fire method: place a magnet near the back of the photo. Now let's move on to the next one: Carte de Visites!
This means that the image will be much crisper and appear the same from all angles.
Many of the photographers also treated the images with some hand-tinting like the one above.
I have a collection of CDVs of women that I have been studying to see if I can learn anything about the jewelry that the women are wearing.
One way to try to learn about the fashions of a specific time period is to study the images that are available for that era.
For the four years of the American Civil War, several types of early photographic processes were available at photographic studios.
It is also helpful to note the name of the photographer, as that may help you further narrow down the date and location, if no other information is available. I wasn't able to find anything else about this couple with a quick search. University archive finding aids frequently help pinpoint this type of information, as mentioned in this blog post.
Be creative in your Google searches to find what you are looking for. I'll give some more clues to help you pinpoint dates in a future blog post.