Background and overview

Globally, Iron Oxide is the second largest inorganic pigment after Titanium Dioxide and the first largest color inorganic pigment. Iron oxide pigments mainly include iron oxide red, yellow, black and brown with iron oxide as the basic material. Iron oxide yellow, also known as hydroxyl iron oxide (FeOOH), will be dehydrated and decomposed into red at about 177 ℃, so the application of ordinary iron yellow pigment in high-temperature occasions such as plastic processing and baking coatings is limited. Iron oxide yellow pigment can improve its temperature resistance through surface coating, so as to expand the application field of iron oxide yellow pigment.

The chemical formula of iron oxide yellow (also known as hydroxyl iron) is α- Fe2O3 · H2O or α- FeOOH, with needle like structure and yellow powder, is a kind of particle size less than 0.1 μ m. Iron series pigment with good dispersibility in transparent medium has strong coloring power, high covering power, insoluble in alkali and slightly soluble in ACID. Synthetic iron oxide yellow has the characteristics of light resistance, good dispersion, non-toxic, tasteless and difficult to be absorbed by human body. It is widely used in coatings, plastics, ink and pharmaceutical industry.

Physical and chemical properties and structure

1. Iron oxide yellow pigment has acid and alkali resistance, resistance to general weak and dilute acids, and is very stable in alkaline solution of any concentration.

2. Iron oxide yellow pigment has certain light resistance, heat resistance and weather resistance. Its coating color is durable and can keep the coating from being damaged in light. Iron oxide yellow pigment is stable in a certain temperature range, but beyond the limit temperature, its color begins to change, and the degree of change is more significant with the increase of temperature. Iron oxide yellow pigment is not affected by cold, heat, dry and wet weather conditions.

3. Iron oxide yellow pigment is very stable in any ambient atmosphere (such as gases containing H 2S, Co, so 2, HCl, no, etc.). And resistant to pollution, water, oil and solvent penetration, insoluble in water, mineral oil or vegetable oil.

4. Iron oxide yellow pigment has strong coloring power and high hiding power. With the decrease of pigment particle size, its coloring power is stronger.

application

Nano iron oxide yellow has the characteristics of acid resistance, alkali resistance, non toxicity and low price. It is widely used in coatings, plastics and rubber. The particle size of nano iron yellow is less than 100 nm, which makes it have some unique characteristics. When light shines on its surface, transmission and diffraction will occur, showing transparent yellow, and can strongly absorb ultraviolet rays, Therefore, it can be used as a functional pigment for the surface paint of high-grade cars, precision instruments, bicycles, motorcycles, cosmetics, food, drugs and other coloring additives.

preparation

In 1970, Japanese scholars studied the phase diagram of iron oxide microcrystalline formation, which laid a theoretical foundation for the preparation method of iron oxide yellow crystal seed. According to the research results, iron yellow crystal seeds can be formed under acidic or alkaline conditions. Because iron yellow is a crystal structure, in order to crystallize into pigment particles, it must first form crystal nucleus and become crystal seed, and then the crystal nucleus grows into iron yellow. Otherwise, only thin and dim color paste can be obtained, which does not have pigment properties. Acid process can be divided into iron sheet process and drop addition process.

1. Sheet iron method

The raw material used in this method is FeSO4. In order to maintain the Fe3 + concentration in the reaction medium in a specific range, reducing agent iron sheet is added in the reaction process. Iron yellow crystal seed was added and air was introduced to synthesize iron yellow under certain pH conditions. The method mainly includes two steps: (1) firstly, FeSO4 · 7H2O is used as raw material, NaOH or NH3 · H2O is used as precipitant or pH regulator, and air is used as oxidant to prepare crystal seed; (2) Iron yellow is produced by two-step oxidation with crystal seed, FeSO4, iron sheet and air.

Here, NaOH or NH3 · H2O is used as a precipitant or pH regulator to react with FeSO4 to form ferrous hydroxide precipitation; Air is used as oxidant; The iron sheet reacts with sulfuric acid produced during the oxidative hydrolysis of FeSO4 to provide ferrous ions required in the reaction system and maintain the pH value of the solution. The alkali consumption of acid method is less and the particles are easy to wash. The relative rates of seed preparation and crystal growth determine the particle size, particle size distribution and particle morphology of iron yellow particles.

In the experiment, the growth of iron yellow particles can be inhibited by adding additives, so as to prepare iron oxide yellow crystals with small particle size and narrow distribution. In the crystal growth stage, the acid generated in the reaction process is neutralized by dropping alkali solution or reacted with the acid generated in the reaction process with iron sheet. The advantage of acid method is that it can avoid precipitation of metal impurities and reduce alkali consumption; The disadvantage is that even after repeated washing, the pigment still contains anions, which will reduce its dispersion, and a certain transparency needs to be sacrificed to obtain high dispersion.

2. Drop addition

In two-step oxidation, if ferrous sulfate solution is added dropwise instead of iron sheet, and the acid produced in ammonia and oxidation process is added dropwise, this method is called dropwise addition.

The reaction involved is: 4feso4 + O2 (air) + 6H2O = 4 α- FeOOH↓+4H2SO4

For dropping addition, ferrous sulfate mother liquor and ammonia shall be added to the three mouth bottle at a certain speed. The pH value of the reaction system shall be measured with a pH meter at regular intervals, and the concentrations of Fe2 + and Fe3 + shall be analyzed with potassium dichromate method to control the pH value and Fe2 + concentration of the reaction system. Iron oxide yellow is an important inorganic pigment second only to titanium dioxide. Appropriate raw materials and processes should be adopted according to local conditions to produce transparent iron oxide yellow with high added value. However, because the reaction involves gas-solid-liquid three-phase, the production process is complex, the reaction and crystallization mechanism is not very clear, and the process is difficult to accurately control. Therefore, it is necessary to focus on the reaction and crystallization mechanism of iron oxide yellow in order to produce iron oxide yellow with high quality and low cost.