There is no documentation for card.io that I can find other than source comments.
The CardIOCreditCardInfo.h file has an enum for CardIOCreditCardType.
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Dave from card.io here.
Does card.io only support automatic card number extraction of Amex, JCB, Visa, Mastercard, and Discover?
Correct.
Does card.io not support card number extraction for merchant cards like Lowe's, Home Depot, or Target?
Correct, with the proviso that some merchant's cards employ numbers that correspond to the format of a standard credit card type, such as Visa or Mastercard. card.io will recognize those cards.
Are there any other requirements on card number extraction, such as the card number having to be embossed?
card.io currently handles only traditional, embossed cards.
Is CardIOCreditCardTypeAmbiguous and Unrecognized only used for manually-entered card numbers?
Correct.