Lisa K.Ross – Zirconium Metal

Steps for Producing Zirconium Sulfate from Zircon

Zirconium sulfate is an important compound that has numerous industrial applications, such as in water treatment, cosmetics, and pharmaceuticals. The process of preparing zirconium sulfate from zircon involves several steps, including alkali decomposition, preparation of zirconium sulfate solution, and precipitation of acidic zirconium sulfate. This article will explore these steps in more detail, including the different methods of alkali decomposition, the preparation of zirconium sulfate solution, and the acid zirconium sulfate precipitation process.

Step 1: Alkali decomposition

There are three methods of alkali decomposition: sodium hydroxide fusion, sodium carbonate sintering, and lime sintering. The sodium hydroxide fusion method uses zircon and sodium hydroxide at a low temperature to achieve a high decomposition rate. The sodium carbonate sintering method involves sintering zircon and sodium carbonate at a high temperature and requires sulfuric acid for leaching. The lime sintering method uses zircon, limestone, and calcium chloride at a high temperature to achieve a moderate decomposition rate and requires hydrochloric acid or sulfuric acid for leaching. Each method has its advantages and disadvantages in terms of cost, efficiency, and process requirements.

Step 2 Preparation of zirconium sulfate solution

The alkali decomposition products of zircon obtained by washing with water and filtering are leached with sulfuric acid. During the leaching process, the zirconium in the alkali decomposition product turns into zirconium sulfate and goes into the solution, while the silicon turns into insoluble silicic acid. Sulfuric acid leaching is usually carried out in enameled reaction pots. First, a solution containing 50% H2SO4 is added to the reaction pot, heated to close to the boiling point, and then the required amount of alkali decomposition product is added while stirring. After the reaction, water is added to the specified total volume, then heated to close to the boiling point, and gelatin is added to thicken the silicic acid. The mixture is then filtered to remove silicon and other impurities. The concentration of sulfuric acid in the leaching solution is generally controlled at 2mol/L, and the leaching solution contains ZrO2100g/L, approximately 100g/L. This process is easy to operate, fast to filter, and produces a clear filtrate with a high zirconium leaching rate. It is also possible to use a calculated amount of concentrated sulfuric acid to react with the alkali decomposition product under stirring, followed by leaching with water. This method yields good leaching results, but the operation is more complicated.

Step 3: Acid zirconium sulfate precipitation

The solubility of zirconium in sulfuric acid solution depends on the acidity of the solution. Precipitation of zirconium sulfate crystals from zirconium sulfate solution generally adopts the method of evaporation and concentration. A good crystallization product can only be obtained by controlling the concentration and acidity of the evaporating liquid. Therefore, concentrated sulfuric acid is added in production to increase the acidity of the zirconium solution.

Conclusion

The preparation of zirconium sulfate from zircon is a complex process that involves several steps, including alkali decomposition, preparation of zirconium sulfate solution, and precipitation of acidic zirconium sulfate. Each step requires careful attention to detail and precise control of various process parameters to ensure a high-quality product. Despite its complexity, zirconium sulfate is an important compound with many industrial applications, and the preparation process outlined in this article is an essential part of its production.

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3 Alkaline Decomposition Methods for Preparation of Zirconium Sulfate

Zirconium and sulfuric acid can produce a variety of compounds, the most common ones being acidic zirconium sulfate and basic zirconium sulfate. Acidic zirconium sulfate, also known as zirconyl sulfuric acid, is widely used in industry, and its molecular formula is H2[ZrO(SO4)2]•3H2O or Zr(SO4)2•4H2O. The tetrahydrate of zirconium sulfate appears as hexagonal plate crystals, while the anhydrous form is a white powder. It is a main intermediate product of zirconium and can be used as a white leather tanning agent. The preparation of zirconium sulfate from zircon involves three steps: alkali decomposition, preparation of zirconium sulfate solution, and precipitation of acidic zirconium sulfate. This article focuses on explaining these three methods of alkali decomposition. Currently, there are three methods of alkali decomposition, namely the sodium hydroxide melting method, the sodium carbonate sintering method, and the lime sintering method.

Sodium Hydroxide Fusion Method

The sodium hydroxide fusion method, also known as the alkali fusion method, involves adding zircon and sodium hydroxide to the reaction tank in a 1:1.3 ratio and reacting them at a temperature of 923-973K to form Na2ZrO3. The main reaction formula is ZrSO4+4NaOH=Na2ZrO3+Na2SiO3+2H2O, and the decomposition rate of zircon can reach about 99%. The alkali fusing material is then washed with water to remove soluble impurities such as excess alkali and sodium silicate. The resulting filter cake is sent for leaching to obtain a zirconium sulfate solution. The washing materials include sodium zirconate, sodium zirconium silicate, hydrated zirconia, and sodium titanate. The main features of this method are the low reaction temperature and the high decomposition rate of zirconium.

Sodium Carbonate Sintering Method.

Sodium carbonate sintering method, also known as the direct sintering method, involves putting zircon and sodium carbonate in a pan-type ball forming machine in a molar ratio of 1:3 to create pellets. The mixture is then sintered in a rotary kiln at 1373K, and the main reaction that takes place is:

ZrSiO4+3Na2CO3=Na2ZrO3+Na4SiO4+3CO2↑

After the firing process, the material is crushed and washed with water to eliminate soluble impurities such as sodium silicate. The resulting mixture is then filtered to obtain a filter cake, mainly comprising of sodium zirconate, which is later leached to produce a zirconium sulfate solution. Alternatively, zircon and sodium carbonate can be used in a molar ratio of 1:1.3. In this case, the primary sintering reaction is:

ZrSiO4+Na2CO3=Na2ZrSiO5+CO2↑

As observed from the reaction formula, the sintered product primarily consists of sodium silicon zirconate. The sintered product is then decomposed using sulfuric acid. During this process, zirconium produces zirconium sulfate and enters the solution, while silicon forms silicic acid, which can be effectively polymerized and removed during filtration. Although this method saves a significant amount of sodium carbonate, it consumes a considerable amount of acid and requires high reaction temperatures. The decomposition rate of zircon is approximately 95%.

Lime Sintering Method

The lime sintering method involves adding zircon and limestone (or chalk) in a molar ratio of 1:3, with an excess of 10% to 20% limestone. Then, calcium chloride with a mineral content of 5% is added, mixed evenly, and sent into a rotary kiln at a temperature of 1373-1473K for 4-5 hours. The decomposition rate of zircon is about 97%-98%. After sintering, the material is first washed with a cold solution containing 5% to 10% HCl to remove excess CaO, CaCl2, and most of Ca2SiO4. The generated colloidal silicic acid is also removed together with the solution. The resulting calcium zirconate is then leached with a solution containing 25% to 30% HCI at a temperature of 358-363K. Alternatively, sulfuric acid can be used for leaching. The biggest advantage of this method is that the decomposition agent is cheap and easy to obtain, but it has the disadvantage of high decomposition temperature and low decomposition rate.

Conclusion

In summary, zirconium sulfate is an important industrial material produced through alkali decomposition of zircon. The three primary methods of alkali decomposition are the sodium hydroxide fusion method, sodium carbonate sintering method, and lime sintering method. Each method has its advantages and disadvantages in terms of decomposition rate, reaction temperature, and cost of decomposition agents. Ultimately, the choice of method depends on the specific requirements of the production process.

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Does Zirconium Have Any Effect on Human Health?

Zirconia ceramics and jewelry made of zirconium are widely used in daily life, and it is generally believed that zirconium is not harmful to human health. However, some people suspect that zirconium in tiles can cause cancer.

It is possible for radioactive elements to cause malignant tumors, usually by inducing cell lesions, leading to leukemia, lymphoma, skin cancer and other blood cancers. As for the malignant tumor caused by excessive radioactivity of ceramic tiles, there are no such cases and related records in clinical experience and domestic and foreign case literature.

Adding zirconium silicate to ceramics is mainly used to increase the whiteness of ceramics. If you are still concerned about its safety, don’t blindly pursue whiteness when buying tiles.

How to Distinguish Zircon from Diamond?

Colorless and transparent zircon is a good substitute for diamonds after careful consideration. The refractive index of zircon is close to 2, and the dispersion is similar to that of the diamond. Therefore, from the appearance, zircon will also shine with colorful light, which is very similar to diamond. Before the advent of man-made diamonds, zircon was the best diamond substitute.

Zircon is very similar to diamond in appearance, but zircon is far from diamond in price. Because the two are not easy to distinguish, some unscrupulous merchants use zircon as a diamond to deceive consumers and make huge profits. So as consumers, how do we differentiate them?

The main identification features of zircon are high refractive index, strong luster, high birefringence, high density, high dispersion, and typical spectral characteristics, etc., resulting in a very special optical phenomenon: When the polished zircon is observed with a magnifying glass, it can be seen from the top surface that there are obvious double shadows on the bottom surface and the ridge line. Because diamonds are “homogeneous”, there will never be a double shadow phenomenon, so zircons can be distinguished from real diamonds.

Diamond is a homogeneous body, completely black and hard under-crossed polarizers; while zircon appears as four bright and four dark under-crossed polarizers. Diamonds are lipophilic, and a ballpoint pen can easily leave uninterrupted marks on the surface of the diamond. Of course, this mark can be easily wiped off. Zircon is not lipophilic, and a ballpoint pen cannot leave uninterrupted marks on its surface. Sharpness marks.

Hydrogenation Method: A Method for Preparing Zirconium Powder

Introduction

Hydrogenation is one of the main methods for producing zirconium powder in the industry. This method refers to the process of preparing metal zirconium powder by hydrogenating and dehydrogenating bulk metal zirconium. The product metal zirconium powder prepared by the method has a purity of more than 98%, and can be mainly used in powder metallurgy additives and pyrotechnic industries.

Reaction Process

Zirconium has good plasticity and is difficult to be crushed by mechanical means, but it can be transformed into a brittle intermediate product zirconium hydride for further processing.

When hydrogen is sufficient, zirconium reacts with hydrogen to form zirconium hydride, releasing a lot of heat. The reaction formula is:

Zr+H2→ZrH2

When dehydrogenated by heating under a vacuum, zirconium hydride decomposes into metallic zirconium. The reaction formula is:

ZrH2→Zr+H2

Zirconium hydride is a non-stoichiometric substance in the interstitial phase, and the hydrogen content (x) can vary from zero to 2 with different process conditions. When x>1.65, it is brittle zirconium hydride, and the brittleness increases with the increase of x value. Zirconium powder can be obtained by grinding the brittle zirconium hydride finely and then dehydrogenating it in a high-temperature vacuum.

According to the requirements for product purity, the bulk zirconium raw materials used for hydrogenation include sponge zirconium, zirconium ingots, or zirconium scraps in zirconium processing; in order to ensure product quality, high-purity hydrogen must be used; the hydrogenation process should be in a well-airtight environment in a stainless steel reaction tank.

Specific steps are as follows:

After the reaction tank is filled, vacuum until the pressure is lower than 0.1Pa, heat to a temperature of 873-973K, and stop vacuuming.
Introduce high-purity hydrogen for hydrogenation. Sponge zirconium and zirconium shavings have a large specific surface area, which can be met by hydrogenation once. The dense zirconium with a large size needs to undergo multiple hydrogenation and dehydrogenation treatments at high temperatures to make it fully burst to ensure that the product is easy to grind. As long as the temperature and pressure of the hydrogenation process are well controlled, zirconium hydride with the desired hydrogen content can be obtained.
After the hydrogenation reaction is completed, continue to pass hydrogen to cool to room temperature, then extract the residual hydrogen, slowly fill in argon or air, and start unloading.
Put block zirconium hydride into a grinding tank, add the appropriate amount of water or ethanol to grind, then sieve and dry to get zirconium hydride powder. This zirconium hydride powder can be used as a heat-burning agent or powder metallurgy additive.
Spread the dried zirconium hydride powder into a thin layer in a tray, then put it into a dehydrogenation tank, and heat it slowly under a vacuum. Zirconium hydride releases a large amount of hydrogen at a temperature of about 673K.
When the temperature rises to 873-973K and the vacuum pressure reaches below 0.1Pa again, cool the dehydrogenation tank to room temperature, slowly pour water or ethanol into it, and then unload.
After grinding, sieving, and drying, the product zirconium powder is obtained.

Advantages

The zirconium powder produced by this method can maintain the content of metal impurities at the level of the raw material while ensuring that it is not contaminated by the container, and the content of some volatile impurities will be reduced, but the content of gas impurities, especially oxygen, will be reduced. Increase. The average particle size of zirconium powder can reach 5-10μm, and finer particle sizes can be separated through liquid countercurrent classification. The finer the particle size of the zirconium powder, the higher the oxygen content.

Attention

Zirconium powder, zirconium hydride powder, and hydrogen are flammable and explosive substances, and fine zirconium powder can oxidize, spontaneously ignite or explode even at room temperature. Explosion-proof measures should be taken during the production, storage, transportation, and use of zirconium powder to ensure safety.

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4 Methods for Making Metal Zirconium

Zirconium and its alloys not only have good machinability, moderate mechanical strength, and high corrosion resistance, but also have a low neutron cross-section. In the nuclear energy industry, they are widely used as structural materials for water reactors. Zirconium widely exists in zircon, so most methods of preparing metal Zr use zircon as a raw material for extracting zircon. This article will mainly introduce four methods for purifying zirconium.

Metal Thermal Reduction Method

The reducing agents used in the thermal reduction method are mainly calcium and magnesium.

(1) Calcithermic reduction

Using ZrO2 as raw material and calcium as a reducing agent, the reduction reaction is carried out at 1273-1373K under vacuum. The reduction product is a powdery mixture of Zr, CaCl2, CaO, and Ca, which can be pickled, washed with water, filtered, dried, and sieved to obtain metal zirconium.

(2) Magnesium reduction method

The magnesium reduction method mainly includes steps such as the preparation of zirconium tetrachloride, purification, magnesium reduction, and vacuum distillation. Chloride zirconium dioxide or zircon sand to obtain zirconium tetrachloride, purify, remove impurities such as SiCl4, TiCl4, AlCl3, FeCl3, and then use molten magnesium to reduce ZrCl4 to obtain a mixture of metal zirconium, magnesium, and magnesium chloride, and finally, Zirconium metal is obtained by distillation and purification.

Hydrodehydrogenation

This method uses the reversible absorption characteristics of zirconium to hydrogen to prepare zirconium powder. At a certain temperature, zirconium and zirconium alloys absorb hydrogen to form hydrides or solid solutions. When reaching a certain level, the material will produce microcracks, become brittle, and contain a lot of hydrogen. Such powder is called zirconium hydride powder. Zirconium hydride powder is dehydrogenated under high temperature and vacuum conditions to obtain zirconium powder. After years of improvement and promotion, this method has become the main method for producing zirconium powder.

Molten Salt Electrolysis

Metals or alloys that are difficult to electrodeposit in an aqueous solution usually use molten salt electrodeposition. Insoluble anodes are usually used, stainless steel or other refractory metals are used as cathodes, and molten salts of electrodeposited metals and alkali metal chlorides or fluorides are used as electrolytes. During the electrolytic reduction process, they are decomposed by the electrolytic metal molten salts. and deposited at the cathode.

Direct Electro-Deoxidation Method

The direct electro-deoxidation method uses a single or mixed metal oxide as the raw material, presses it into a block as the cathode, removes the oxygen in the cathode by electrolytic deoxidation, and obtains a metal element or alloy with low impurity content in a high-temperature molten salt, also known as FFC Law. The metals successfully prepared by the FFC method include Zr, Hf, Be, Mg, Ca, Ba, V, Nb, W, Fe, and Cu.

Among the four methods, the magnesium reduction method and hydrogenation-dehydrogenation method are the main production methods in the industry.

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The Importance of Surface Coatings for Zirconium Alloy Cladding

Safety Issues in The Application of Zirconium Alloys

In the past few decades, zirconium alloy cladding has been successfully applied to light water reactors (LWR), and has shown good radiation resistance and corrosion resistance. However, a major problem in the application of zirconium alloys in stacks is that they react violently with water vapor at high temperatures, and when the temperature is greater than 1200 °C, a large amount of hydrogen and heat will be released. After the Fukushima nuclear power accident in Japan, the safety of nuclear power has once again been placed in front of all nuclear workers. How to further improve the safety and reliability of light water reactor nuclear fuel elements under accident conditions has become an urgent problem to be solved. Research and development directions include accident-resistant fuel cores and accident-resistant cladding materials.

Cladding Material for Zirconium

The accident-resistant cladding material has good thermodynamic properties, which can improve the reaction kinetics of zirconium and water vapor and reduce the hydrogen release rate. The development of this material is mainly reflected in two aspects: one is to improve the high-temperature oxidation resistance and strength of the zirconium alloy cladding; the other is to develop non-zirconium alloys with high strength and oxidation resistance. This paper discusses the research on the surface coating of zirconium alloy cladding for the former.

The main advantage of the application of coated zirconium cladding is economical. The technical challenge it faces is to meet various performance requirements of the fuel cladding and components without changing the size of the fuel cladding. During long-term operation, the coating should have certain stability under corrosion, creep, and abrasion conditions.

Research Status of Zirconium Alloy Cladding Surface Coating

The anti-oxidation coating technology on the surface of zirconium alloy is the main method to improve the anti-oxidation ability of the surface of zirconium cladding. The outer surface of the zirconium alloy is coated with a layer of material to enhance the wear resistance and high-temperature oxidation resistance of the cladding, thereby improving the accident resistance of the zirconium cladding under normal working conditions and accident conditions. At present, some preliminary screening results have been obtained in international research on the surface coating of zirconium alloy cladding, and the coating materials mainly involve MAX phase and metal Cr.

MAX-phase coating

A series of studies have shown that:

The essence of the MAX phase coating is the dressing effect, and the key to the problem is to solve the diffusion of oxygen atoms to the zirconium substrate.
No matter whether in a fast neutron reactor or thermal neutron reactor, under the three activation time conditions, the activity of MAX phase material is similar to that of SiC, but three orders of magnitude lower than that of 617 alloys.
The thickness of the MAX phase coating should be controlled at 10~30 μm to limit the loss of neutrons.
Ti3SiC2 shows better prospects than Ti2AlC as a candidate material for MAX-phase coatings for high-temperature nuclear energy applications.
At room temperature, the radiation resistance of Ti3AlC2 is better than that of Ti3SiC2, and the radiation stability of the two MAX phase materials at 600 ℃ is better than that at room temperature.

Metal Cr Coating

A series of studies have shown that:

The high-temperature oxidation resistance of the coated zirconium alloy is obviously better than that of the Zr-4 substrate.
The high-temperature oxidation resistance of the coated zirconium alloy is significantly stronger than that of the zirconium alloy substrate, and the Cr-coated zirconium cladding has better ductility.
The metal Cr coating has good high-temperature oxidation resistance and can be used as a candidate coating material for accident-resistant zirconium alloy cladding.

For more information about zirconium materials, please visit https://www.samaterials.com/70-zirconium.html.

If you are interested in coating materials, you can find more information at https://www.sputtertargets.net/.

3 Manufacturing Methods of Zirconium-containing Refractories

What is Zirconium-containing Refractory Material?

Zirconium-containing refractory materials are made of zirconia (ZrO2) and zircon (ZrSiO4) as raw materials. “Zirconium-containing” usually refers to materials containing the following zirconium products: zirconia, zircon, zirconium mullite and zirconium corundum. Zirconium-containing products have good corrosion resistance to various molten metals, acidic reagents and liquid glass.

Zirconium-containing refractory materials can be divided into the sintered, fused cast, and non-fired products based on different manufacturing methods.

What are the Different Manufacturing Methods?

Sintered Zr-Containing Refractory Product

The basic steps to manufacture zirconium-containing sintered bricks are to prepare raw materials, press green bodies, and sinter at high temperatures.

Another method is to obtain blanks by granulation, kneading, machine pressing or extrusion molding, and the clinker fired at high temperature is used as aggregate, and the clinker fine powder is used for batching, kneading, molding, drying, and sintering to finally obtain the finished product.

Cast Zr-Containing Refractory Product

1) Use zircon concentrate or industrial zirconia and industrial alumina powder as raw materials.

2) Add sodium oxide, calcium oxide, boron oxide and rare earth metal oxides as additives.

3) The powder is melted at a temperature above 2500°C by means of electric arc melting, cast in a mold, cooled, annealed, and machined.

Non-fired Zr-Containing Refractory Product

The manufacturing process of zirconium-containing refractory products without firing is simple, and the product qualification rate is high.

1) Use stabilized zirconia clinker or zircon as raw material.

2) Use water glass, phosphoric acid, phosphate, or sulfate as the cementing agent.

3) Mix the raw materials and cementing agents, and undergo high-pressure molding and low-temperature heat treatment to make zirconium-containing non-fired materials.

The heat treatment temperature varies with different binders. When aluminum dihydrogen phosphate is used as the cement, the heat treatment temperature is about 300°C; when phosphoric acid is used as the cement, the heat treatment is carried out at a temperature of about 600°C.

What Are These Products Used for?

Zirconium-containing refractory products can be widely used in metallurgy, building materials, the chemical industry, machinery and other professional fields due to their high refractoriness, mechanical strength and chemical stability.

Zirconia bricks can be used in thermal equipment in the building materials industry and metallurgical industry, such as billet continuous casting sizing nozzles, submerged nozzles and slag lines in long nozzles.
Zircon bricks are resistant to low-alkali glass corrosion. They can be used for the kiln wall of the glass melting furnace, as well as the arch feet of the upper structure of the glass melting furnace or the intermediate transition layer between silica bricks and corundum bricks.
Zirconia-mullite fused cast bricks can be used in heating furnaces, soaking furnaces in the metallurgical industry, glass melting furnaces in the building materials industry, etc.
Zirconium corundum bricks have good resistance to melt erosion. As a high-grade abrasive, it has a good grinding effect on steel, cast iron, heat-resistant steel, and various alloy materials.

If you want to know more about zirconium material, we would like to advise you to visit Stanford Advanced Materials (SAM) for more information.

10 Common Zirconium Products and Their Applications

1. Zirconium Silicate

Zirconium silicate is an important variety in traditional zirconium products. The product is made of zircon sand, which can be obtained after grinding, calcining and powdering. It is a high-quality and cheap opacifying agent for ceramic glazes.

Zirconium silicate is mainly used for color glazes of architectural ceramics, daily-use ceramics and electric porcelain. It is also widely used in high-grade refractory materials, precision casting, emulsified glass and other industries.

2. Zirconium Carbonate

Zirconium carbonate is a source of zirconium that is insoluble in water but is easily transformed into other zirconium compounds. It is mainly used as an additive for cosmetics, waterproofing agent, flame retardant, opacifying agent, and surface aid for fibers and paper, and can also be used to prepare zirconium-cerium composite catalytic materials. It is an important raw material in the textile, papermaking, paint, and cosmetic industries, and its consumption has been increasing in recent years.

3. Zirconium Oxychloride

Zirconium oxychloride is the main raw material for the production of other zirconium products such as zirconium dioxide, zirconium carbonate, zirconium sulfate, composite zirconium oxide, and the separation of zirconium and hafnium to prepare metal zirconium and hafnium. In addition, it can be used in textiles, leather, rubber additives, metal surface treatment agents, paint drying agents, refractory materials, ceramics, catalysts, fire retardants, and other products. The primary source material for zirconium oxychloride is zircon sand.

4. Fused Zirconia

Fused zirconia is mainly used in the production of glazes and refractory materials. Due to the high content of impurities in fused zirconium, its use is sometimes limited.

5. Zirconium Sulfate

Zirconium sulfate is an intermediate raw material for the production of zirconium chemicals and metal zirconium and hafnium. It is also an important raw material for the production of leather tanning agents, wool treatment agents and paint surface oxidants. Additionally, it can be used as a catalyst carrier, amino acid and protein, precipitant and deodorant.

Consumption Structure of Zirconium Products

6. Zirconium Dioxide

Zirconium dioxide, or zirconia, is a non-toxic, odorless white solid. It has sufficient stability in alkaline solutions and many acidic solutions. ZrO2 ceramic is suitable for precision ceramics, electronic ceramics, optical lenses, glass additives, electrolytic zirconia bricks, ceramic pigments, enamel, artificial gemstones, refractory materials, grinding and polishing and other industries and products.

7. Composite Zirconia

Composite zirconia, referring to stabilized zirconia, is a non-toxic, odorless white powder. It has stable chemical properties and controllable specific surface area. It is the basic raw material for the manufacture of various special ceramics, advanced refractory materials, optical communication devices, and new energy materials.

8. Nuclear Grade Zirconium

Nuclear-grade zirconium is mainly used as the structural material of nuclear-powered aircraft carriers, nuclear submarines, and civil power reactors, and the cladding of uranium fuel elements. It is an important strategic metal.

9. Industrial Grade Zirconium

Industrial-grade zirconium is mainly used in the production of chemical acid and alkali-resistant equipment, the military industry, the electronics industry, pipeline valve materials, special high-strength, and high-temperature alloy materials, and getters for electric vacuum and lighting bulb industries.

10. Metallurgical Grade Zirconium

Metallurgical grade zirconium is used as a firearms sponge zirconium combustion agent and is also suitable for alloy additives and metallurgical deoxidizers, the chemical industry, civilian flash fireworks, etc.

Comparison of zirconia ceramic teeth and metal ceramic teeth

Broken or missing teeth usually require fillings. The two conventional options are zirconia ceramic teeth and metal-ceramic teeth. This article will analyze the difference between the two and help those in need to choose the one that suits them.

Metal ceramic teeth

Metal-ceramic crowns are accepted by most patients because of their good strength, but they have many disadvantages. The metal substrate is easily oxidized to form gray oxides, which are scattered and deposited on the edge of the gums, causing the gums to turn gray and affecting the appearance; at the same time, metal porcelain teeth may have a strong stimulating effect on the gums, and even cause gum swelling, bleeding, allergies and other symptoms; the color of the metal-ceramic crown should be covered with opaque porcelain, so that the ceramic crown can block the light to a certain extent, thus affecting the aesthetics of the teeth.

Zirconia all-ceramic teeth

At present, there are many types of all-ceramic dental materials, such as leucite, lithium-based porcelain, alumina, zirconia, etc. There are also a variety of fabrication methods, such as infiltrated ceramics, hot pressure casting ceramics, porcelain deposition, computer-aided design, and computer-aided fabrication. In comparison, among all all-ceramic restoration materials, zirconia material has higher flexural strength, so it is accepted by more and more patients and doctors.

Zirconium dioxide all-ceramic crown has its own unique advantages. Since there is no metal bottom crown, its restoration has permeability and aesthetics, which provides a guarantee for aesthetic restoration. At the same time, zirconium dioxide has strong biocompatibility and is non-irritating to the gums. Most patients will not experience symptoms such as gum swelling, bleeding, and allergies, which meet the clinical requirements.

Advantages of zirconium dioxide

(1) Good mechanical properties: it has a flexural strength greater than 900MPa, so it can also be used for the repair of posterior teeth and porcelain bridges with more than 6 units.

(2) Good biocompatibility: The zirconia all-ceramic crown itself does not contain metal, which can exclude metal allergic reactions; zirconia also has good biocompatibility.

(3) No obstruction to X-rays: There is no need to remove the dentures when performing cranial X-rays, CT, and MRI examinations, because zirconia ceramic teeth have no obstruction to X-rays.

(4) Good strength and density: Zirconium dioxide is widely used, especially in high-precision instruments, such as aviation equipment. Because of its good crack resistance and tough curing after cracking, it can be made into a porcelain bridge with more than 6 units, and it can also solve the problem that the all-ceramic system cannot be used as a long bridge.

(5) The color is comparable to real teeth: the color of the base crown of the ceramic is white, so the neck of the porcelain tooth will not become black and darkened for a period of time after the porcelain tooth is inserted, thus avoiding the problem of discoloration of the metal porcelain crown.

(6) Healthy biological material: Zirconium dioxide is an excellent high-tech biological material with good biocompatibility, which is healthy and safe to use.

(7) High-tech quality: Zirconium dioxide ceramic teeth are made by good computer-aided design, laser scanning, and then controlled by computer-aided program grinding.

Hopefully, the above analysis will help you a lot in making your choice between metal ceramic teeth and ceramic teeth.

Purification of Zirconium by Vacuum Distillation

Vacuum distillation refers to the process of removing metal magnesium and MgCl2 in sponge zirconium by distillation under the condition of lower pressure than normal pressure. The zirconium sponge produced by distillation is then vacuum cast into metal or alloy, which is used in industrial sectors such as atomic energy, metallurgy, and chemistry.

Principle of Vacuum Distillation

The raw material of vacuum distillation is generally the product of the reduction of zirconium tetrachloride and magnesium, containing 55% to 60% of zirconium, 25% to 30% of magnesium, 10% to 15% of MgCl2 and a small amount of Zrcl3 and ZrCl2.

The vapor pressures of these components are different at a certain temperature and pressure. For example, in the standard state, the boiling point of magnesium is 1380K, MgCl2 is 1691K, and zirconium is 4673K; at normal pressure and 1173K temperature, the equilibrium vapor pressure of magnesium is 13332.2Pa, MgCl2 is 999.9Pa, and zirconium is less than 130μPa. Therefore, by controlling the appropriate distillation temperature and pressure, zirconium and other components can be separated.

In addition, under a 10Pa vacuum, the boiling points of magnesium and magnesium chloride dropped to 789K and 950K, respectively, and the volatilization rate was many times greater than that of atmospheric distillation. Therefore, the use of vacuum distillation can shorten the distillation time, reduce the distillation temperature, improve the separation effect, and avoid the formation of Zr–Fe alloys that contaminate the zirconium sponge and iron.

System for vacuum distillation

The vacuum distillation system is mainly composed of a distillation furnace, a distillation tank, a condensation sleeve, a condenser, a heat shield, and a vacuum system.

According to the installation position of the condenser, it can be divided into two types: upper cooling type and lower cooling type, and the structure of the two is basically the same. In industrial production, the distillation furnace and the reduction reactor are the same. Therefore, the structural design and material selection of the reduction reactor should take into account the requirements of the reduction and distillation processes.

The condenser is a hoistable bell-shaped cylindrical tank with a cooling water jacket. The condensing sleeve is cylindrical, and the condensing area is set according to the amount of condensate discharged by distillation. A heat shield is arranged between the distillation tank and the condenser, the function of which is to reduce the radiant heat from the heating area to the condenser, without hindering the passage of the airflow escaping from the distillation tank. In order to improve the thermal insulation effect, most of the heat shields are multi-layer structures.

The structure of the distillation furnace is the same as that of the reduction reactor, but the furnace shell of the former should be sealed and connected to a vacuum device. During operation, the furnace is in a low vacuum state to reduce the external pressure on the distillation tank and prevent the latter from deforming.

Process of vacuum distillation

The reducing crucible together with the reaction product is placed upside down in the distillation pot of the distillation furnace.
The distillation tank was evacuated to 13.3-1mPa, and then the distillation furnace was heated to a temperature of 573-673K and kept at a constant temperature for 1-4 hours to remove the crystal water adsorbed by MgCl2 during the assembly process of the distillation equipment.
Then the furnace temperature was raised to 1023-1073K. At this time, since the metal magnesium and MgCl2 begin to volatilize in large quantities, the vacuum degree drops sharply, and the heating rate needs to be controlled well.
After the distillation enters the constant temperature stage, the temperature should be controlled at 1223-1273K.
After 20-25 hours of constant temperature, when the vacuum in the distillation tank rises to less than 1Pa and tends to be stable for a certain period of time, the residual amount of volatiles is very small, and the distillation operation is over.

In the whole distillation process, process parameters such as distillation temperature, vacuum degree and distillation time should be well controlled. It takes about 50 to 60 hours to distill 700 to 800 kg of zirconium. The zirconium sponge produced by distillation is self-igniting. When the distillation tank is cooled to 323K temperature, a mixed gas consisting of 60% dry air and 40% indoor air should be slowly introduced to reduce the surface activity of the sponge zirconium and make it passivated before it is released.

Product handling after vacuum distillation

Zirconium sponge is a hard and tough metal. Usually, the zirconium lump is cut into pieces by a vertical hydraulic press equipped with a cutter, and then it is medium and finely crushed to make the particle size reach 5-25mm, and then sieved, classified, mixed in batches, and packed with argon. The typical impurity content (mass fraction ω/%) of sponge zirconium is Fe 0.08, Al 0.006, Mg 0.002-0.02, Cl 0.001-0.04, O 0.08-0.1, N 0.002-0.004.

Sponge zirconium taken out from the reduction crucible can be divided into four types: A, B, C, and D.

A type of zirconium sponge accounts for about 35% of the total and is a bulk dense metal that contains almost no metal magnesium and MgCl2.
B-type zirconium sponge accounts for about 20% of the total. It is the product formed in the initial stage of the reaction, which is plate-shaped and about 10mm thick. In addition to metal magnesium, it contains a lot of iron and nitrogen impurities.
C-type sponge zirconium accounts for about 35% of the total, is a light and porous sponge with the least impurities but contains a considerable amount of metal magnesium and chloride in the pores.
D-type zirconium sponge is a product that is close to the crucible wall and contains a lot of impurities. Generally, it is returned to the chlorination treatment to recover the zirconium in it.

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