Zirconium Metal – Page 9 – Provide you with various industry information about zirconium

How is the Zirconia Industry Laid Out?

Globally, zirconia producers are mainly concentrated in a few countries, mainly including China, Japan, France, the United Kingdom, the United States, and Australia. Companies with a comprehensive zirconia industrial layout include Saint-Gobain, Japan’s Tosoh, Japan’s First Element, Showa Denko, France’s Suvi, and Japan’s Sumitomo Osaka Cement. Among them, the main business of First Element is zirconium-based, and most of the other companies are large-scale integrated enterprises.

With zirconia as the main component, after adding rare earth elements (mainly cerium oxide) and other oxides, composite zirconia powders with different performance characteristics can be formed. The nature of the composite zirconia depends on the type of material or crystal structure with which it is combined. Depending on the specific needs of the application, different formulations of composite zirconia materials with different properties can be prepared using different formulations.

In general, zirconia ceramics are divided into three categories: PSZ partially stabilized zirconia, also known as ceramic steel (with superior impact resistance); TZP tetragonal polycrystalline zirconia (better mechanical strength and fracture toughness); FSZ fully stabilized zirconia, crystalline phase cubic phase, with high-temperature conductivity, but high thermal expansion coefficient and poor thermal shock resistance.

Catalyst

Since zirconia is the only metal oxide that has both acidic and basic and oxidizing and reducing properties and is also a p-type semiconductor, it is easy to generate oxygen vacancies. As a catalyst carrier, it can interact with the active component, so its supported catalyst has more excellent properties than other materials-supported catalysts.

Precise ceramic parts

Zirconia ceramics can have excellent mechanical properties and fracture toughness, chemical resistance, and biocompatibility, so you can see the back of zirconia ceramic materials in industry and life.

Battery material

Solid oxide fuel cells (SOFC) are a new type of green energy that developed rapidly in the 1980s. Due to its high energy conversion efficiency (up to 65%) and the use of various fuels such as hydrogen, carbon monoxide, methane, etc., the system design is simple, and the pollution-free emission is low, which will be applied to the power generation system. The solid electrolyte is the core component of SOFC.

Zirconium oxide ceramics have become the most researched and widely used solid electrolyte materials because of their high ionic conductivity, good chemical stability, and structural stability.

Refractory

Zirconium oxide is an excellent special oxide refractory material and used at a high temperature (2300 ℃ – 2400 ℃). It has good chemical stability and is not easy to decompose, and is highly corrosive and resistant to acid and alkali slag. The industry uses zirconia-based refractories to produce refractory materials with excellent thermal shock resistance, corrosion resistance and wears resistance, which can make refractories have better performance and longer service life. It has been applied to the manufacturing process of industrial continuous casting steel and alloy materials and has important significance for improving the quality and cost of metal materials such as steel.

Optical material

Zirconium dioxide ZrO2 is a high refractive index, low absorptive material that can be used in coatings in the near-ultraviolet (<300 nm) to infrared (~8 μm) spectral regions. Nano-zirconia is added to the special coating material to increase the refractive index of the coating without changing the light transmittance. In the field of optical materials, in addition to being used as a coating, nano zirconia can also be used as a polishing material for optical lenses.

Electronic materials

For engines that use three-way catalytic converters to reduce pollution emissions, oxygen sensors are essential in the automotive industry. It uses the ceramic sensitive component to measure the oxygen potential in the exhaust pipe of the automobile, and calculates the corresponding oxygen concentration by the principle of chemical balance, and achieves the measuring component that monitors and controls the combustion air-fuel ratio to ensure the product quality and the exhaust gas emission standard. There are two types of oxygen sensors currently in use: titanium oxide and zirconium oxide. The core component is a porous zirconia ceramic tube, which is a solid electrolyte with sintered porous platinum (Pt) electrodes on both sides.

Plumbum zirconate titanate (PbZrxTi1-xO3, PZT) ceramics are a commercially important class of piezoelectric materials. Compared with other piezoelectric ceramics, PZT ceramics not only have high Curie temperature and piezoelectric coefficient, but also are easy to be doped and modified, and have good stability, so they have an important position in the electronic machinery manufacturing industry. They are the basic material for the preparation of most electromechanical devices such as sonar, hydrophone, ultrasonic generator, volt generator, and position trimmer.

Brake material

Ceramic materials have high heat resistance, thermal stability, and hardness. As an important member of advanced ceramics, zirconia ceramics certainly have similar characteristics. In view of the excellent quality of advanced ceramics, researchers have introduced it into friction materials to obtain longer-lasting and more durable friction materials under the most extreme working conditions. Today, more and more composite formulations for brake pads and clutch linings contain ceramic materials.

Many ceramic materials can be added to the brake material, including the zirconia ceramics we introduce today, in addition to silicon carbide, alumina, silica, and magnesia

Thermal spray material

Using thermal spraying technology, the ceramic coating is deposited on the metal collective, and the characteristics of high-temperature resistance, heat insulation, wear resistance, corrosion resistance and insulation of the ceramic are combined with the toughness, workability, the electrical and thermal conductivity of the metal material. The ideal composite coating product has become an important development direction in the field of composite materials and product development.

Aviation surface protection technology is a hotspot of thermal spraying for many years. The key components of aero-engines are high-temperature alloy turbine blades and turbine disks. The current engine turbine inlet temperature is close to or exceeds the melting point of the alloy, and such high temperatures will affect the function of the engine and dye. Therefore, an important development trend of superalloys is to coat the surface of the alloy with a high-melting ceramic coating (Thermal Barrier Coatings – TBCS) with good thermal insulation properties. At present, the most widely used TBCS is yttria-stabilized zirconia materials.

Stanford Advanced Materials supplies high-quality zirconium products to meet our customers’ R&D and production needs. Please visit http://www.samaterials.com for more information.

Zirconia Ceramic Phone Backplane Stands Out in 5G Era

By the end of 2018, 154 mobile operators around the world are carrying out 5G technology tests or trials, and the number of countries participating in 5G has been expanded to 66. With the advent of 5G era, the mobile phone industry will usher in a new round of reform, and the mobile phone backboard market is facing a reshuffle.

Zirconia ceramic phone backplane stands out

5G era requires faster signal transmission, 1 to 100 times faster than 4G. 5G communications will use a spectrum of more than 3Ghz, with shorter millimeter-wave wavelengths. Compared with the metal backplane, ceramic backplane has no interference to signal and has incomparable superior performance of other materials, which is favored by mobile phone manufacturers.

The contrast of the backplane of several kinds of mobile phones

Among all-ceramic materials, zirconia ceramic has the advantages of high strength, high hardness, acid and alkali resistance, corrosion resistance and high chemical stability, as well as the characteristics of scratch and wear resistance, no signal shielding, excellent heat dissipation performance, and good appearance. Therefore, it becomes a new mobile phone body material after plastic, metal, and glass. The application of zirconia ceramic in the mobile phone is mainly two parts: backplane and fingerprint identification cover.

Preparation and difficulty analysis of zirconia cell phone ceramics

The preparation of zirconia ceramic backplane mainly includes the preparation, molding, sintering, grinding and polishing process of zirconia ceramic powder, in which the preparation of zirconia ceramic powder is the most important and most difficult part of the whole process.

Technological difficulties

The phone backplane powder of zirconia ceramic is nanocomposite zirconia. In the preparation of ceramics, the quality requirements include that the particle size distribution is normal, the particle shape is close to circular, the dispersion is good, and the purity is high. The preparation methods of nano-composite zirconia powders include the hydrothermal method, precipitation method, alcohol-brine hydrolysis method, and low-temperature gas-phase hydrolysis method.

The quality of powder directly affects the intrinsic quality and performance of finished products. High purity, ultra-fine particle size, narrow particle size distribution, and good dispersibility are important bases for evaluating the quality of ceramic powders. The powder agglomeration and surface modification of nano-composite zirconia have become two major problems. With the development of technology, researchers have found corresponding solutions.

Firstly, the agglomeration of zirconia powder is a big problem. Gan Xuexian et al. investigated the final depolymerization effect by designing and using different grinding equipment and process parameters. With d50＝1.355μm zirconia powder as the research object, when using vertical ball mill, vertical ball mill and horizontal sand mill as the grinding equipment, serving with φ2mm zirconia ball as the grinding medium, with m medium: m material = 5:1 medium material ratio grinding for 15h, detection zirconia slurry size after grinding, the results show that: the horizontal sanding machine has the best grinding effect, and the d50 of zirconia slurry is 0.303μm. When the horizontal sand mill is adopted as the grinding equipment, the grinding effect is best under the conditions that the ratio of medium material (m medium: m material) is 4:1, the solid content of slurry (w) is 45%, the linear speed is 10m•s-1, and the grinding time is 25h.

Secondly, in terms of surface modification of zirconia powder, Yue Liang et al. drew the following conclusions through experiments: the sintering activity of zirconia powder was significantly improved after horizontal stirring grinding and manual granulation, and the sintering density was close to 99.5% at 1400℃; after grinding zirconia powder, the bending strength of sintered samples was lower than that of the original powder mainly because of the large size defect. Therefore, it is necessary to have appropriate granulation technology to improve the powder forming performance; it is suggested that improving the stability of phase transition is beneficial to obtaining high-performance zirconia powders.

Stanford Advanced Materials supplies high-quality zirconia products to meet our customers’ R&D and production needs. Please visit https://www.samaterials.com/ for more information.

Application of Zirconia Electrolyte in Oxygen Sensor

With the gradual improvement of people’s awareness of environmental protection and energy conservation, many large and medium-sized enterprises, such as iron and steel metallurgy, petrochemical industry, thermal power plants, etc., have taken improving combustion efficiency, reduced energy consumption, reduced pollutant emissions, protecting the environment as an important way to improve product quality and enhance enterprise competitiveness.

Generally speaking, the direct way to improve the combustion efficiency is to continuously monitor the composition of flue gas in the flue gas analysis instrument (such as a flue gas analyzer, combustion efficiency tester, zirconia oxygen content detector), then analyze O2 content and CO content in flue gas, adjust the flow rate of combustion air and fuel, and determine better air consumption coefficient. Therefore, as an industrial tool to improve combustion efficiency, the oxygen sensors’ response time and measurement accuracy become key performance indicators. Due to its simple structure, short response time, wide measurement range (from PPM to percentage), high operating temperature (600℃-1200℃) and small maintenance, zirconia oxygen sensor has been widely used in metallurgy, chemical industry, electric power, automobile, and other fields.

Principle of zirconia sensor

The figure below is the schematic diagram of oxygen measurement with an oxygen probe. Porous platinum (Pt) electrodes were sintered on the two sides of the zirconia electrolyte (usually a zirconia tube). At a certain temperature, when the oxygen concentration on both sides of the electrolyte is different, the oxygen molecules on the high concentration side (air) are adsorbed on the platinum electrode and combine with electrons to form oxygen ions, making the electrode positively charged. The oxygen ions then migrate through the oxygen ion vacancy in the electrolyte to the Pt electrode on the low oxygen concentration side, releasing electrons and transforming them into oxygen molecules, making the electrode negatively charged.

This creates a certain electromotive force between the two electrodes. The zirconia electrolyte, the platinum electrode, and the gas with different oxygen concentrations on both sides constitute the oxygen probe, which is called the zirconia concentration difference cell. Then, by measuring the gas temperature and the output electromotive force, the oxygen partial pressure (concentration) can be calculated by the nengest equation, which is the basic detection principle of the zirconia oxygen sensor.

Common types of zirconia oxygen sensors

At present, the commonly used zirconia oxygen sensor includes a detection probe and direct insertion oxygen probe.

Detector probe

The sampling method is to introduce the measured gas into zirconia through a guide tube and then heat the zirconia to the working temperature (above 750℃) through a heating element. Zirconia is typically tubular and the electrode is porous platinum. Its advantage is that it is not affected by the temperature of the gas detected, and the oxygen content of the gas can be detected by using different flow guides at different temperatures.

This flexibility is used in much industrial on-line detection. Its disadvantages are slow response; the structure is complex and easy to affect the detection accuracy; when there are many impurities in the measured gas, the sampling tube is easy to be blocked; the porous platinum electrode is easy to be corroded by sulfur and arsenic or blocked by fine dust, etc. When the temperature of the detected gas is low (0-650℃), or when the measured gas is clean, it is suitable to use this detection method, such as oxygen measurement by nitrogen production machine and laboratory.

Direct probe

The direct insertion method is to directly insert zirconia into the gas measured at high temperature and directly detect the oxygen content in the gas. It uses the high temperature of the measured gas to bring zirconia to its operating temperature without the need for additional heaters.

The key technology of the direct insertion oxygen probe is the high-temperature sealing of ceramic material and the electrode. Due to the need to insert zirconia directly into the detection gas, the length of the oxygen probe is required to be relatively high. The effective length is about 500mm ~ 1000mm, and the special environment length is up to 1500mm, as well as high requirements for detection accuracy, working stability and service life. Therefore, it is difficult to adopt the whole zirconia tubular structure of the traditional zirconia oxygen probe with a direct insert oxygen probe, and the zirconia and alumina tube connection structure with high technical requirements is mostly adopted. The sealing performance is one of the most important technologies for the zirconia oxygen probe. Currently, the most advanced connection mode in the world is the permanent welding of zirconia and alumina tubes together.

Compared with the method of sampling pattern detection, the direct insertion method has obvious advantages: zirconia directly contacts with gas; high detection accuracy; fast reaction speed and small maintenance.

Brief summary

The regulation of oxygen content is a powerful means to monitor combustion conditions and improve combustion efficiency, and the accuracy and time of the measurement of the sensor have put forward certain requirements. Zirconia, as a solid electrolyte, is used to transport conductive ions in oxygen sensors. At present, there are two kinds of zirconia oxygen sensors: detection type and direct insertion type. The direct insertion type probes are widely used because of their direct contact with the measured gas, high measurement accuracy and fast reaction time.

Stanford Advanced Materials supplies high-quality zirconia products to meet our customers’ R&D and production needs. Please visit https://www.samaterials.com/ for more information.

Why Does Zirconium Explode? How to Solve It?

Zirconium (Zr) is estimated to make up about 0.017% of the lithosphere. Because zirconium is chemically active at temperatures only slightly above normal atmospheric temperatures, it exists only in a bound state. The most common ores are zircon (ZrO2) and barium lead (ZrSiO4).

The hafnium (Hf) coexists with zirconium in all its terrestrial ores. The content of hafnium fluctuates greatly, accounting for 2% (the total amount of hafnium and zirconium). The two elements are chemically closer than any other in the periodic table, and the similarities are so great that no difference in mass has been found to separate them.

Zircon

Zircon has been considered a gem since ancient times because it is usually found in large single crystals. However, most commercial deposits of zirconium ore are in beach sand, where the relatively heavy and chemically inert zirconium minerals are retained, while the lighter parts are broken down and washed away by water. India, Malaya, Australia and the United States are known to have large deposits of this sand. Harmful substances have been found in commercially useful deposits, first in Brazil and later in other places, including Sweden, India, and Italy, while some zirconium ores are also commercially mined in Madagascar, Nigeria, Senegal, and South Africa.

Zircon is used as a component of foundry sand, abrasive, and laboratory crucible zircon and zirconia refractories. It is found in ceramic compositions and acts as an emulsifier in glazes and enamels. Zirconium and zirconia bricks are used as glass linings, zirconia templates are also used for extrusion iron and non-ferrous metal molds and injection metal nozzle linings, especially for continuous casting.

Zirconium metal

More than 90% of zirconium is now used in nuclear power generation because zirconium has a low neutron absorption cross-section and is highly resistant to corrosion in atomic reactors, provided it contains no hafnium. In addition, zirconium is used in the manufacture of cast iron, steel, and surgical instruments, as well as in arc lamps, fireworks, special solder, plastic pigments, etc.

The powdered zirconium metal is used as a “getter” in thermionic tubes that absorb traces of residual gas after it has been drained and expelled. The metal, in the form of filaments or wool, is also used as a filter for camera flashes. Block metals can be used in the lining of reaction vessels, either pure or alloyed. It is also used as lining for pumps and piping systems in chemical processes. Excellent zirconium and niobium superconducting alloys are used in the magnetic field of 6.7T.

Zirconium compounds

Zirconium carbide and zirconium diboride are hard, refractory, metallic compounds that have been used in metal cutting tools. Diboride is also used as the shell of open-hearth thermocouples with long life. Zirconium tetrachloride is used in organic synthesis and water repellent in textiles, and it is also useful as a tanning agent.

The metal hafnium has been used as a coating for the tantalum components of rocket engines, which must work at very high temperatures and under corrosive conditions. Because of its high thermal cross-section, it is also used as a control rod material in nuclear reactors. In addition, hafnium is used in the manufacture of electrodes and filament bulbs.

The harm of zirconium

It is not accurate to say that zirconium compounds are physiologically inert, but most organisms seem to tolerate zirconium quite well compared to most heavy metals. Zirconium salts have been used to treat plutonium poisoning to replace the deposition of plutonium (and yttrium) in the skeleton and to prevent precipitation when early processing begins.

Some studies have shown that more than 20% of zirconia can be absorbed in rats for a long time without harmful effects. LD50 of rats injected with sodium zirconium citrate is about 171mg/kg. Other investigators found an intraperitoneal injection of LD50 rats with zirconium lactate 670mg/kg, barium zirconium 420mg/kg, and mice with sodium zirconium lactate 51mg/kg.

Zirconium compounds have been recommended for topical treatment of suede dermatitis and body deodorants, among which are zirconia carbide hydrate, zirconia hydrate, and sodium zirconium lactate. There have been some reports of persistent granulomas on the skin as a result of these applications.

More immediate interest in occupational exposure is the effect of inhaled zirconium compounds, which have not been studied as extensively as other approaches to drug administration. However, there are several experiments and at least one report on human exposure. In this case, a chemical engineer who had been at a zirconium and hafnium processing plant for seven years was found to have granulomatous lung disease. As no similar damage was found on all other employees, it was concluded that the situation was most likely due to relatively high levels of beryllium prior to zirconium contact.

Animal exposure to zirconium compounds has shown that severe persistent chronic interstitial pneumonia occurs in both zirconium lactate and barium zirconium at atmospheric concentrations of about 5mg/m3. Short exposure to sodium zirconium lactate at a higher air concentration of 4900mg/m3 resulted in peribronchoabscess, peribronchogranuloma, and lobular pneumonia. Despite the lack of literature on human zirconia pneumoconiosis, the authors of one study suggest that zirconium should be considered as a possible cause of pneumoconiosis and recommend appropriate precautions in the workplace.

A small number of studies on the toxicity of hafnium compounds indicate that their acute toxicity is slightly higher than that of zirconium salts. Like soluble zirconium salts, hafnium chloride-induced cardiovascular failure and respiratory arrest in cats at 10mg/kg.

Safety and health measures

Zirconium is burned as a fine powder in air, nitrogen or carbon dioxide. The spontaneous air explosion of these powders at concentrations of 45,000 to 300,000 mg/m3 may be caused by static electricity generated by the separation of the disturbed particles.
Metal powders should be transported and treated in a wet state; water is usually used for wetting. When the powder is dried before use, the amount used should be as small as possible and should be operated in a separate compartment to prevent the spread of the explosion.
All ignition sources including electrostatic charges should be eliminated. All surfaces in the area should be impermeable and seamless so that they can be washed down with water and completely free from dust. Any spilled powder should be washed with water immediately so that it has no chance to dry. Old paper and cloth contaminated with powder should be kept moist in a covered container until they are removed and burned, at least daily.
Dry powders should be treated with as little interference as possible, and then only sparkless tools should be used. Rubber or plastic aprons, if worn on overalls, should be treated with antistatic compounds. Work clothes shall be made of non-synthetic fibers unless effectively treated with antistatic materials.
All processes using zirconium and hafnium should be designed and ventilated to keep air pollution below exposure limits.

Stanford Advanced Materials supplies high-quality zirconium products to meet our customers’ R&D and production needs. Please visit https://www.samaterials.com/ for more information.

What Are the Main Industrial Uses of Zircon?

Zircons are highly resistant to high temperatures and acid corrosion, and their melting can reach 2,750℃. 80% of the world’s zircons are used directly in the foundry, ceramics, glass, and refractory industries, while a small amount is used in ferroalloys, pharmaceuticals, paint, leather, abrasive, chemical, and nuclear industries. The main industrial uses of zircon are as follows.

Zircon sand

Zircon sand containing ZrO2 65~66% is directly used as casting material for the iron metal in foundry due to its melting resistance (melting point above 2500℃). Zircon sand has a lower thermal expansion, higher thermal conductivity, and stronger chemical stability than other common refractory materials, and high-quality zircon and other adhesives have a good bond and are used in the foundry industry. Zircon sand is also used as bricks in glass kilns. Zircon sand and powder are mixed with other refractory materials for other purposes.

Zirconium oxide

Zirconium and dolomite react together at high temperatures to produce zirconia or zirconium oxide (ZrO2). Zirconium oxide is also a good melting material, although its crystal shape varies with temperature. Stable zirconium oxide also contains small amounts of oxides of magnesium, calcium, scandium, or yttrium. The stable melting point of zirconium oxide is close to 2700℃, and it is more resistant to thermal shock than zirconium in some metallurgical applications. Stable zirconium oxide has low thermal conductivity, and the use of hafnium dioxide as fusible in industrial zirconium oxide is harmless.

Zirconium metal

Zirconium metal is mainly used in the chemical and nuclear reactor industries, as well as in other industries requiring corrosion resistance, high-temperature resistance, special fusion properties or special neutron absorption. In the United States, about 8% of the total consumption of zirconium metal is used in these industries, while the only meaningful application of the hafnium metal is in the nuclear reactors of warships.

Zirconium metal is obtained by multistage extraction. Initially, zircon reacts with coke in an electric furnace to produce zirconium hydrocarbons and then chlorinates to produce zirconium tetrachloride. The magnesium reduction of the zirconium tetrachloride process involves the reduction of tetrachloride by placing magnesium metal in an inert gas to obtain spongy zirconium.

High purity zirconium metal can be refined by iodide thermal dissociation. In this process, metal and iodine vapors react at 200℃ and send volatile iodine to the connector, separating zirconium in the form of volatile iodine from most impurities. At about 1300℃, iodide is separated on a heated filament attached to highly purified zirconium. The released iodine is transferred from the filament, and the product is called a zirconium crystal rod.

Zirconium sponge

More than 90% of zirconium sponge is used as a zirconium-based alloy for structural and cladding materials in nuclear reactors. Zirconium is used in the chemical industry, pesticide industry, printing, and dyeing industry to manufacture corrosion-resistant reaction towers, pumps, heat exchangers, valves, stirrers, nozzles, pipes, and container lining. It can also be used as a deoxidizing and denitrifying agent in the process of steelmaking and grain finisher of aluminum alloy. Zirconium wire can be used as grid support, cathode support and grid material, as well as air plasma cutting machine electrode head. Zirconium powder is mainly used as a deflagrant in the arms industry, a degassing agent in electronic devices, and it can also be used to make igniters, fireworks and flash powder.

Stanford Advanced Materials supplies high-quality zirconium products to meet our customers’ R&D and production needs. Please visit https://www.samaterials.com for more information.

The Strength of Structural Ceramics: Zirconia

In order to enable the equipment to work in a variety of harsh environments, structural ceramics, as a new material with excellent mechanical, thermal and chemical properties, have gradually replaced similar metal products and occupied an important position in modern industry. Among them, zirconia ceramics, which has excellent mechanical and thermal properties, has become a famous strength in the field of structural ceramics.

Zirconia cylinder liner and plunger

Zirconia ceramic cylinder liner and plunger have the characteristics of wear resistance, corrosion resistance, high-temperature resistance, high strength, high hardness, long service life and high impact resistance, which are widely used in oil and gas operation equipment such as mud pump, oil pump, injection pump, and fracturing pump. Compared with metal products, its product performance has been improved by 8-10 times, which greatly improves the efficiency of oil and gas exploitation, reduces the cost of exploitation, and has good economic and social benefits.

Sander accessories

With the wide use of new energy and nano-new materials, horizontal sand mill, vertical sand mill, mixing mills and other kinds of ultra-fine grinding equipment demand is rising. Because of its excellent performance, small wear and other advantages, zirconia ceramic accessories (including zirconia grinding media, turbine and left wheel, zirconia rods, grinding block, sieve, etc.) effectively improve the grinding efficiency of grinding equipment and reduce wear, so it is widely used in electrode materials, nanomaterials, ink, medicine, chemical industry, ceramics, and other industries.

Wear-resistant ceramic

Zirconia wear-resistant ceramics have the advantages of large hardness, high strength, good wear-resistant performance, long service life, heat shock and so on, and can withstand all kinds of tests in a harsh working environment, so it is often used for grinding and polishing materials, wear-resistant coating, pipe or equipment lining, equipment structure parts, and other fields. Common zirconia wear-resisting ceramic products are a wear-resisting cylinder, wear-resisting block, lining board, lining brick and liner, and so on, different product types and specifications can be selected according to different equipment and usage.

Yellow zirconia

The yellow zirconia is mainly used in various zirconia wire drawing wheel, wire drawing wheel, tower wheel. It has the characteristics of high strength, corrosion resistance, high wear resistance, good self-lubrication, good thermal stability, fatigue resistance, and high-cost performance.

Zirconia grinding media and ball

Zirconia grinding balls are prepared by isostatic pressure process with micron and sub-nano zirconia and yttrium oxide as raw materials. Due to the characteristics of extremely low grinding loss, high density, strong toughness, high hardness, high temperature resistance, acid and alkali resistance, corrosion resistance, magnetic resistance, etc., it is often used in the ultra-fine grinding and dispersion of materials requiring “zero pollution” and high viscosity and high hardness, which is common in electronic ceramics, magnetic materials, zirconia, medicine and food, pigments, dyes, inks, special chemical industries.

Stanford Advanced Materials supplies high-quality zirconia products to meet our customers’ R&D and production needs. Please visit https://www.samaterials.com/ for more information.

Applications of Zirconia in Structural And Functional Ceramics

Zirconia is a kind of inorganic nonmetallic material with high-temperature resistance, corrosion resistance, abrasion resistance, and excellent electrical conductivity. Since the mid-1970s, developed countries have invested heavily in the research and development of zirconia products, extending the application field of zirconia to structural and functional materials. Zirconia is also one of the new high-performance materials in the national industrial policy, which is widely used in various industries.

Applications of zirconia in structural ceramics

In 1975, R.G.Garvie, Australia, prepared partially stabilized zirconia with calcium oxide as a stabilizer, and improved the toughness and strength of zirconia for the first time, which greatly expanded its application in the field of structural ceramics.

1. Zirconia ceramic bearings

Zirconia ceramic bearing has the characteristics of wear resistance, corrosion resistance, high-temperature resistance, high cold resistance, oil-free self-lubrication, resistance to magnetoelectric insulation, etc. It can be used in an extremely harsh environment and under special working conditions.

Zirconia ceramic bearings have been used in micro cooling fans, and the product life and noise stability are better than traditional ball and sliding bearing systems. Foxconn is the first company to use zirconia ceramic bearings in computer cooling fans.

2. Zirconia ceramic valve

At present, valves commonly used in various industries are made of metal materials. Due to the limitation of metal material itself, the corrosion damage of metal has a considerable impact on the working life, reliability and service life of valve wear resistance.

The working climate of the valve pipeline is very complicated. Hydrogen sulfide, carbon dioxide, and some organic acids in oil, gas, and reservoir water increase the destructive power of their surfaces, rapidly disabling them. Zirconia ceramic valve has excellent wear resistance, corrosion resistance, high-temperature resistance, and thermal shock resistance, so it is suitable for this field.

3. Zirconia abrasive material

Zirconia ball has the advantages of high hardness, low wear rate and long service life, which can greatly reduce the pollution of grinding materials and ensure the quality of products. Besides that, zirconia material has high density and strong impact energy when used as a grinding medium, which can greatly improve the grinding dispersion efficiency. Good chemical stability determines its corrosion resistance and can be used in acidic and alkaline media.

Applications of zirconia in functional ceramics

1. Zirconia ceramic knives

Zirconia ceramic knife has the characteristics of high strength, wear resistance, no rust, no oxidation, acid and alkali resistance, anti-static, and no reaction with the food. Its body is as shiny as jade, which also makes it an ideal high-tech green knife. At present, the main products on the market are zirconia ceramic knife, scissors, razor, scalpel and so on, which has become popular in Europe, America, and Japan in recent years.

2. Zirconia high-temperature heating element

Zirconia is an insulating material at room temperature, its resistivity is as high as 1015 Ω cm, and it can conduct electricity when the temperature to 600 ℃. When the temperature reaches 1000℃ above, it is a good conductor and can be used as 1800℃ high-temperature heating element, with the highest operating temperature of 2400℃. At present, zirconia has been successfully used in heating elements and equipment with an oxidation atmosphere above 2000℃.

3. Zirconia bioceramics

The quality of ceramic tooth material directly affects its quality and patients’ health. The inner crown of porcelain teeth is made of different metal materials, which is easy to oxidize with saliva. Since there is no metal inner canopy, zirconia ceramic teeth have good transparency, excellent gloss, and effectively avoid tooth allergies and gum black lines.

4. Zirconia coating material

Zirconia thermal barrier ceramic coating material with a high-performance stabilizer such as yttrium oxide (Y2O3) is mainly used in high-performance turbine aero-engine. The thermal barrier coating uses ceramic insulation and corrosion resistance to protect the metal material, which can not only improve the fuel combustion efficiency but also greatly extend the life of the engine. Thermal barrier coating has important application value in aviation, aerospace, surface ships, large thermal power generation, and automobile power, etc. It is one of the most important technologies in modern national defense.

5. Zirconia oxygen sensor

Oxygen sensors are essential in the automotive industry for engines that use three-way catalytic converters to reduce pollution emissions. Currently, there are two kinds of oxygen sensors in use: titanium oxide and zirconia. Japanese scientists made a porous oxygen sensor out of zirconia, which is installed in an engine to automatically detect the ratio of oxygen to combustion gas in the engine, and automatically control the ratio of input gas and output gas, thus greatly reducing the harmful gas emissions from cars.

Stanford Advanced Materials supplies high-quality zirconia ceramic products to meet our customers’ R&D and production needs. Please visit https://www.samaterials.com for more information.

Why Are Zirconia Ceramic Teeth So Expensive?

The all-ceramic dental prosthesis has excellent mechanical properties, no gingival inflammation, and excellent biocompatibility, and it has no obstruction to X-ray rays. In addition, it has excellent wear resistance, corrosion resistance, and aesthetic properties of no gingival black edge and emulating natural teeth, all of these make it the first choice of dental repair materials.

Zirconia ceramic teeth

At present, there are three kinds of materials used in all-ceramic dental restorations, namely, zirconia all-ceramic dental restorations, cast ceramic dental restorations and alumina all-ceramic dental restorations.

Among the three kinds of all-ceramic teeth, zirconia all-ceramic teeth are the strongest dental restorations. Its fracture toughness ratio is two or three times that of alumina all-ceramic, and it is not easy to break the teeth with it; secondly, it can be used for cosmetic dentistry and restoration of missing teeth. It can be used to repair multiple teeth, which can be used to repair even crowns, which can perfectly solve the problem that the strength of ceramic casting material is too poor to make continuous crown; moreover, its color is perfectly adjustable, so it can be used to make very realistic dentures.

Zirconia denture, as such an excellent product, should have been favored by the public. But zirconia restorations are expensive, costing thousands or even thousands of dollars for a single crown, which makes it unaffordable for ordinary people.

Why are zirconia ceramic teeth so expensive?

The main reason for the high price of zirconia ceramic teeth is that the overall production cost of zirconia teeth is really high.

The zirconia prosthesis underwent a series of complex processes before it was put into the patient’s mouth to achieve its chewing, vocal and aesthetic functions, including raw material production of raw material manufacturers, production of zirconia block manufacturers, dental surgeons’ spare tooth mold, processing design, selection of the right zirconium block, cutting, dyeing, sintering, dyeing, polishing, dental doctor’s grinding, etc. As long as one of the above processes goes wrong, it will affect the currently visible quality of the restoration or the currently invisible but potential quality problems in the future.

Zirconium blocks used for all-ceramic teeth can cost anywhere from hundreds to thousands of dollars just from the cost of materials alone. From the above analysis, we can see that the proportion of the raw material cost is not large, but the difficulty of processing leads to an increase in the overall preparation cost.

At present, the forming of zirconia ceramic crowns is dominated by CNC processing technology, which has advantages in product precision and processing efficiency. However, due to the material removal by cutting tools on zirconium plates (blocks) during processing, the cost of ceramic crowns remains high due to the waste of materials and the wear of cutting needles, and microcracks are easily introduced in the cutting process, leading to the failure of the restoration. The current zirconia denture is semi-machined, and the zirconia teeth processed by a professional milling machine need to be used to repair the maxillofacial fossae and furrows with a crack drill or a ball drill to achieve a realistic effect. If human ingenuity is lacking, it can also be said that it has a little personality in shape and edge treatment.

To sum up, the waste of raw materials and the high labor cost of advanced technical workers inevitably increase the preparation cost of zirconia teeth due to the inevitable mistakes in manual processing. Therefore, seeking a new dental ceramic prosthesis forming technology is the characteristic of dental ceramic research and the key point of the clinical prosthesis.

Zirconia Ceramic Conversion Film Used in Automobile Coating Field

Phosphating is the most common pretreatment technology in the field of automobile coating. A phosphate conversion film is produced after phosphating the body steel plate, which can not only protect the base metal but also improve the adhesion between the metal and the coating. All cars are phosphated before they are painted.

A-typical-phosphating-and-E-coating-process. Source: researchgate.net

However, the traditional phosphating process has the defects of high energy consumption and high pollution. In addition, nitrite in the phosphating bath has high carcinogenicity, and its storage and use requirements are high, which increases the burden on enterprises. Therefore, under the dual drive of environmental requirements and energy cost, the phosphorus-free film-forming technology represented by the new zirconia conversion film technology has become the development consensus of green coating for automobiles.

Principle of film formation of zirconia ceramics

Zirconia ceramic film-forming technology is one-step film-forming, which means a surface treatment agent is used to treat the metal surface. The following diagram shows the film formation principle of a zirconia ceramic on the steel surface. The main materials are fluoro zirconic acid and zirconium salt. Zirconic acid and zirconium salt react directly with the metal substrate, and the zirconia ceramic film formed is attached to the surface of the metal substrate to play a role in corrosion protection.

At present, the sol-gel is the main method to produce zirconia conversion film. The so-called sol-gel refers to the formation of the three-dimensional network configuration of colloidal particles crosslinked with each other, which can mechanically wrap a large number of solvents inside the aggregate, making it no longer flow and become a semi-solid state and gel. When the density of sol particles in colloidal solution is higher than that in solution, the sol particles tend to sink under the action of gravity. If some parameters in the solution are changed to make the deposition rate of colloidal particles greater than the diffusion rate, the colloidal particles will rapidly precipitate out of the solution.

Characteristics of zirconia ceramic film

In terms of film properties, the ceramic coating formed by zirconia conversion film can completely replace the traditional phosphating film. In addition, zirconia conversion film also has the characteristic of being lightweight, while its film thickness is about 50nm. The film thickness means the low film weight, and the weight of the traditional phosphating film is usually 2-3g/m2, while that of zirconia conversion film is only 20-200mg/m2. The weight of zirconia conversion film varies according to the raw materials provided by the supplier, but in general, the weight of zirconia conversion film is about 200 times lower than that of traditional phosphating film.

In terms of technological process, the new zirconia conversion film technology is simple and fast, and generally only takes about 30s to form a complete film, which can significantly reduce the cost of water consumption, wastewater treatment, energy, and manpower.

Moreover, the new process is suitable for a variety of metals (Fe, Zn, Al, Mg), so various plates can be mixed line processing. In the process of treatment, zinc-plated plate and aluminum plate without waste slag formation, only a small amount of slag was produced in the treatment of cold-rolled plate. The resulting slag can be easily removed using a conventional phosphating system, without clogging the nozzle or adversely affecting coating properties or the appearance of the electrophoretic coating.

In daily process management, the bath of the new zirconia film-forming technology is very stable and easy to control. At ordinary times, the temperature and PH value are only needed to be controlled in production, which does not need to be like zinc phosphating that requires regular daily testing of total acid, free acid and zinc, nickel, manganese content, and many other parameters, so a lot of process management costs are saved.

Zirconia film-forming technology has been applied earlier in foreign countries. Henkel group of Germany has the absolute right to speak in this field. As early as 2002, Henkel was the first company to introduce zirconium pre-treatment materials suitable for a variety of plates; in 2008, GM used Henkel’s zirconium pretreated materials at its SanJose Dos Campos plant in Brazil; Henkel’s pretreatment materials were also used at Ford’s TwinCity plant during the same period.

Stanford Advanced Materials supplies high-quality zirconium and zirconia products to meet our customers’ R&D and production needs. Please visit http://www.samaterials.com for more information.

How Did Nuclear Zirconium Alloys Develop?

Zirconium alloys have a small thermal neutron capture cross-section (0.185b) and are surprisingly resistant to corrosion, so they are widely used in fission reactors, such as core-clad tubes, grids, and guide tubes in boiling water reactors, as well as pressure pipes and exhaust reactor vessels in pressurized water reactors.

Nuclear zirconium alloy

With the application of zirconium alloys in the nuclear energy industry, the zirconium industry has developed rapidly.

In the nuclear giant change reactor, nuclear fuel is fission reaction all the time. In the reaction, the neutron bombards the nucleus of U235, which splits into Ba140 and Kr93, and releases two or three neutrons at the same time; other U235 nuclei are bombarded by these neutrons and re-fission. This is the chain reaction of fission.

A material with a large neutron capture cross-section will absorb many neutrons when they hit the wall, reducing the efficiency of the chain reaction. Meanwhile, the chain reaction produces a lot of heat, which is removed by circulating cooling water (or other coolants) to avoid overheating and damage to the reactor. When metals come into contact with high-temperature water, they can be corroded (oxidized). Materials with poor corrosion resistance need to be replaced frequently, which increases the cost and easily leads to safety accidents. Therefore, as core-cladding and structural materials, zirconium alloys are required to have low neutron capture cross-section and excellent corrosion resistance, so the development of zirconium alloys should be attributed to the nuclear industry.

Origin of zirconium alloys

Initially, zirconium was not considered a suitable material for use in the nuclear industry, because studies have shown that zirconium’s effect on thermal neutron absorption can affect the efficiency of nuclear reactors. Later, researchers at the Oak Ridge Institute found that 2.5% of the hafnium in zirconium was responsible for its large thermal neutron capture cross-section.

Zirconium and hafnium are associated with ore and are generally difficult to separate. Until the 1850s, Admiral in the Naval Nuclear Propulsion project decided to use zirconium in the water-cooled reactor of the Nautilus Nuclear Submarine. Although zirconium had already been used for the project by that time, there were no strict standards for the use of zirconium, and the researchers only knew that improving the purity of zirconium would be good for the properties of the alloy. Some processes are used to purify strip zirconium, but it still contains small amounts of nitrogen, making it less resistant to corrosion at high temperatures. Finally, the researchers realized that purity was not the key to zirconium’s corrosion resistance, because they found that some zirconium materials containing impurities (such as tin, iron, chromium, and nickel) were more resistant to corrosion than higher-purity zirconium materials. Therefore, the development of zirconium alloys is put on the agenda.

Development of zirconium alloys

The first alloy, Zircaloy-1, contains 2.5% tin. It was found that the corrosion rate of Zircaloy-1 alloy was increasing and not consistent with the expected decrease. This was similar to a normal sponge zirconium material, so Zircaloy-1 was quickly abandoned.

At the same time, the researchers found that adding iron and nickel to the Zircaloy-2 could improve corrosion resistance. The tin content was reduced to 1.5% and 0.15% iron, 0.05% nickel and 0.10% chromium were added. It was found that Zircaloy-2 had the same mechanical properties as Zircaloy-1, but the high-temperature corrosion resistance of Zircaloy-2 was much better than that of Zircaloy-1. However, during the service of the pressurized water reactor, the alloy produces a lot of hydrides, resulting in hydrogen embrittlement.

By studying the binding technique, the researchers found that nickel greatly enhanced the hydrogen absorption capacity of zirconium alloys. The researchers removed the nickel from the Zircaloy-2, creating a Zircaloy-3. But Zircaloy 3 was quickly abandoned because its strength was too low. In addition, Zircaloy-3 produced many striated Fe-Cr binary intermetallic compounds when it was processed in the two-phase zone, so it could not provide sufficient corrosion resistance. The strength of Zircaloy-3 was still too low, although changes in the heat treatment process prevented the production of the striated compound.

The researchers compensated for the nickel by increasing the iron content by 0.22 percent and found that the corrosion resistance of the new alloy was similar to that of zircaloy-2, which had only half the hydrogen absorption rate. The new alloy quickly became a major part of the pressurized water reactor, the first Zircaloy-4.

Zirconium alloys for the nuclear industry have been developed into the third generation of products, which are used in various reactors.

The first generation is the standard zircaloy-4 and Zircaloy-2, whose composition and process requirements are specified in the ASTM standard. This generation of zirconium alloy is still in use.

The second generation is low tin Zircaloy-4 and optimized Zircaloy-4. The tin content of low tin Zircaloy 4 decreased from 1.2% ~ 1.70% to 1.20% ~ 1.50%, and the carbon and silicon were controlled at 0.008% ~ 0.020% and 0.005% ~ 0.012%, and the cumulative annealing process parameters in the alpha phase after quenching in the beta phase were strictly controlled; the optimized zircaloy-4 is based on the low tin zircaloy-4, and the content of alloy elements and process parameters are more strictly controlled, so as to improve the uniformity of materials.

The third generation of zirconium alloy has excellent properties and is widely used as a fuel rod cladding tube and fuel assembly guide tube. NDA and MDA from Japan, HANA from South Korea, and composite casings from Siemens are also examples of this generation of products.

Prospect of zirconium alloys

Zirconium alloys above 620℃ (depending on composition) convert to body-centered cubic β-zirconium. After the transformation, the mechanical properties and corrosion resistance of the alloy will be greatly reduced, and it cannot continue to maintain the safe operation of the nuclear reactor. The famous event is the accident at the Fukushima nuclear power plant in Japan. Affected by the big earthquake in eastern Japan, the reaction water of the Fukushima nuclear power plant leaked, and the cladding temperature increased significantly. The zirconium alloy cladding softened quickly, and brittle material formed with the leakage of air, leading to the leakage of nuclear fuel. Large amounts of nuclear-contaminated water flowing into the sea have caused great damage to the ecology of the world.

As a nuclear reactor cladding material, it needs to have a small thermal neutron capture cross-section, which leads to the zirconium alloy cannot be highly alloyed, so it is bound to be difficult to break through the zirconium alloy’s high-temperature performance. At present, countries attach great importance to this problem. On the one hand, they are trying their best to make a breakthrough in the high-temperature performance of zirconium alloy; on the other hand, they are looking for alternative products of existing fuel cladding, such as silicon carbide (SiC) composite material, molybdenum alloy, cobalt alloy and so on. Molybdenum alloys and cobalt alloys were originally intended as structural materials for fusion reactors. Although they do not have the same low thermal neutron absorption cross-section as zirconium alloys, they have excellent high-temperature stability.

Stanford Advanced Materials supplies high-quality zirconium alloys to meet our customers’ R&D and production needs. Please visit http://www.samaterials.com for more information.