Rewritable paper: Prints with light, not ink

A new type of paper can be used and reused up to 20 times. What’s more, it doesn’t require any ink. Its designers think that this new technology could cut down on tons of waste — and save people tons of money.

A special dye embedded in the paper makes it printable and rewritable. The dye goes from dark to clear and back when chemical reactions move electrons around. (Electrons are the subatomic particles that orbit in the outer regions of an atom.) The paper’s color-change chemical undergoes what are known as redox reactions. Redox is short for reduction and oxidation.

Oxidation steals one or more electrons from a molecule. Rust is an example of oxidation. “When iron rusts in air, its electrons move to nearby oxygen atoms,” explains Yadong Yin. He’s a chemist at the University of California, Riverside.

Reduction is the opposite of oxidation. It adds one or more electrons. As rust oxidizes iron, the process reduces those nearby oxygen atoms. That means that they gain electrons, which have a negative charge.

When dye in the new paper is oxidized, it appears blue, red or green. (What color depends on which dye is in the paper.) When the dye on some parts is reduced, color on those areas disappears. Controlling these two reactions makes it possible to print on, erase and reuse the new paper.

The starting base of the “paper” used in the study was a clear plastic. That allowed it to show how the paper works. But the technology also could be used with glass or conventional paper — the type made from wood pulp — as long as each contains the redox dyes and the other chemically active components.

How it works

The paper starts out with all of the dye oxidized, and therefore colored. Nano-scale crystals of titanium dioxide — each around a billionth-of-a-meter in size — cover the paper’s surface.

To print something, scientists cover this solid-color paper with words or an image printed on a see-through base. You might think of it as a stencil, or mask. Next the scientists expose the masked surface with ultraviolet (UV) light. The light triggers a reduction reaction on sections of the paper not shaded by the printing. So it removes color from those sections.

Only the oxidized parts that had been covered by the stencil stay dark, explains Yin. Those areas become the “printing.” So the writing is done chemically, using light. The process chemically reduces dye in all of the areas that should be blank space.

The tiny size of the surface nanocrystals lets electrons move easily out of them and into the dye. In effect, Yin explains, when the crystals are exposed to the UV light, “electrons are kicked out.”

Afterward, other organic materials in the paper give up electrons. Those electrons fill “holes” made when electrons left the molecules of titanium dioxide. Now the nanocrystals can work again.

To start over, the paper needs to turn back into a solid-colored sheet. Oxygen in the air makes this happen. That oxygen pulls electrons from the “unprinted” areas. But you don’t want this happening seconds after you write on the paper. People need time to read the printing first!

Special cellulose in the paper slows that erasure. Among other things, this cellulose makes it hard for oxygen to react with the dye. Printing can remain visible for two days or so, Yin’s research team has shown.

On the flip side, some people may want to reuse the paper right away. Heating speeds the erasure time. At the right temperature, oxidation can return the entire paper to its solid color in five minutes or less. Yin’s team at UC-Riverside describes its new, rewritable paper in the Dec. 2, 2014, issue of Nature Communications.

Still a work in progress

Yin’s group smartly chose ingredients for the new technology so that it will operate well, says Howon Lee. This makes the new paper “significant,” he says. In other words, the paper can be printed on. It doesn’t turn dark again immediately. And the paper can be reused.

Lee is an engineer at Seoul National University in Korea and did not work on the new paper. But he knows Yin’s work. In fact, Lee worked with Yin and other scientists in 2009 on another project. That study explored how light interacts with nanostructures. This happens naturally on butterfly wings and peacock feathers. That team wanted to learn more about the science of this natural process. The group published its findings in Nature Photonics.

Yin’s current project is “more like a delicate engineering work,” Lee now says. It does explore some basic science. But beyond that, he explains, it puts science principles to work. “The rewritable paper project aims to help people in real life,” Lee says.

The paper can work with blue, green or red dye. But full color printing is not yet practical. To do that, scientists need a way to use a combination of dyes. They also will need to vary how much light different parts of the paper get during printing.

Another issue is that someone couldn’t read an article and then decide to save it on the new paper. The whole paper still would darken in two days or so.

Nonetheless, the cost savings and environmental benefits of rewritable paper could be “enormous,” Yin says. Lower paper use could help preserve forests. Yin also argues that using less paper not only could reduce the amount of trash from printed materials, but also the amount of chemical pollutants.

Still, don’t yet throw out your notebooks and computer printers. Rewritable paper has a long way to go before it’s ready for use in homes, schools and offices.

Power Words

atom   The basic unit of a chemical element. Atoms are made up of a dense nucleus that contains positively charged protons and neutrally charged neutrons. The nucleus is orbited by a cloud of negatively charged electrons.

cellulose   A type of fiber found in plant cell walls. It is formed by chains of glucose molecules.

dye   (noun) A substance that adds or changes the color of something. (verb) To apply a colorant to something.

electron   A negatively charged particle usually found orbiting the outer regions of an atom; also, the carrier of electricity within solids.

engineering   The field of research that uses math and science to solve practical problems.

landfill  A site where trash is dumped and then covered with dirt to reduce smells. If they are not lined with impermeable materials, rains washing through these waste sites can leach out toxic materials and carry them downstream or into groundwater. Because trash in these facilities is covered by dirt, the wastes do not get ready access to sunlight and microbes to aid in their breakdown. As a result, even newspaper sent to landfill may resist breakdown for many decades.

liquid crystal display (LCD)   A screen with one or more layers of material that flow like liquid but have a structure similar to crystals. In general, the material’s structure affects how much light it lets through. LCDs are used in many electronic devices.

molecule   An electrically neutral group of atoms that represents the smallest possible amount of a chemical compound. Molecules can be made of single types of atoms or of different types. For example, the oxygen in the air is made of two oxygen atoms (O₂), but water is made of two hydrogen atoms and one oxygen atom (H₂O).

nano   A prefix indicating a billionth. In the metric system of measurements, it’s often used as an abbreviation to refer to objects that are a billionth of a meter long or in diameter.

nanocrystal   A small crystal with dimensions measured in billionths of a meter.

Nanotechnology   Science, technology and engineering that deals with things and phenomena at the scale of 100 billionths of a meter or less.

organic  (in chemistry) An adjective that indicates something is carbon-containing; a term that also relates to the chemicals (including carbon) that make up living organisms.

oxidation   A process that involves one molecule’s theft of an electron from another. The victim of that reaction is said to have been “oxidized,” and the oxidizing agent (the thief) is “reduced.” The oxidized molecule makes itself whole again by robbing an electron from another molecule. Oxidation reactions with molecules in living cells are so violent that they can cause cell death. Oxidation often involves oxygen atoms — but not always.

oxygen   A gas that makes up about 21 percent of the atmosphere. All animals and many microorganisms need oxygen to fuel their metabolism.

reactive   (in chemistry)  The tendency of a substance to take part in a chemical process, known as a reaction, that leads to new chemicals or changes in existing chemicals.

redox   A short-hand term in chemistry for reactions that involve reduction and/or oxidation, changes that occur with the gain and/or loss of an electron.

reduction   In chemistry, a process in which an atom gains an electron by stealing it from another atom or molecule. Reduction is the opposite of oxidation.

titanium dioxide   A white, unreactive, solid material that occurs naturally as a mineral and is used extensively as a white pigment.

ultraviolet   A portion of the light spectrum that is close to violet but invisible to the human eye.