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.

nuclear-reactor

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 alloy

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.

How is Zirconia Ceramic Cell Phone Panel Produced?

With the advent of the era of 5G signals, intelligent wearable devices are bound to shift from metal to glass and ceramics. Especially, in the mobile phone panel industry, more and more mobile phone manufacturers began to use zirconia ceramic material. So what is the manufacturing process of zirconia ceramic cell phone panel?

Ceramic powder

Microcrystalline zirconium is generally used as the raw material for the shell of 3C products. Zirconia powder is the most widely used ceramic material for the shell of 3C products due to its good appearance treatment effect and the advantages of phase change toughening.

Zirconium Oxide Powder

Ceramic Machining

Ceramic shell molding processes such as mobile phones and smart wear mainly include injection molding, dry pressing molding, and tape casting. Injection molding is similar to plastic injection molding, which is mainly used to produce small and sophisticated ceramic parts with complex shapes. In general, the larger the size, the less advantageous the injection molding; dry pressing mainly produces flat products with high production efficiency; tape casting is an important forming method for thin ceramic materials. The above three molding methods can be used to produce mobile phone panels.

1. Injection molding

Ceramic Injection Molding (CIM) is a new process for ceramic parts manufacturing combining polymer Injection Molding with ceramic manufacturing.

2. Dry Pressing

Dry compression molding is a method to make the powder into a certain shape of the blank body by applying external pressure through the plunger of the press. Due to the moisture content of powder under 7%, the subsequent sintering time is reduced, so the forming efficiency is high and the cost is low, but the density is not uniform.

3. Tape casting

Tape casting is an important forming method for thin ceramic materials with high productivity and automation, but the shrinkage rate of firing is as high as 20-21%. It can be used to prepare high-quality ceramic films with a thickness of 10-1000 microns. Tape casting is used in the ceramic panel of MI 5 mobile phones and the ceramic fingerprint cover of various mobile phones.

4. Debinding and sintering

Debinding is the removal of organic matter from the body of an injection-molded billet by heating or other physicochemical means.

Under the action of high temperature, with the extension of time, the green body finally becomes a hard polycrystalline sintered body with a certain microstructure, which is called sintering. Sintering is a process to reduce the pores in the forming body, enhance the combination of particles and improve mechanical strength.

5. Postprocessing

The panel of 3C products, such as mobile phones and smart wearers, has very high requirements on the surface effect of engineering ceramics, such as smooth and clean surface, precise geometric size, fingerprint protection, and so on. This requires a complex post-processing process, including CNC machining, grinding, polishing, laser /PVD, AF processing, etc.

The above is all about the production process of the zirconia ceramic cell phone panel, I hope it can provide a reference for you. Stanford Advanced Materials supplies high-quality zirconia products to meet our customers’ R&D and production needs. Please visit http://www.samaterials.com for more information.

What Do You Know About Zirconium And Zirconium Alloys?

Compared with traditional iron, copper, nickel, and other metal elements, zirconium has a lower density and smaller thermal expansion coefficient. In addition, zirconium has a low thermal neutron absorption cross-section (only 0.18×10-28 m2) and good corrosion resistance, which makes zirconium and zirconium alloys have a wide range of applications in the nuclear industry, aerospace and other special fields.

Zirconium and its alloys have been widely used as cladding materials in nuclear reactors. Zirconium and its alloys reflect neutrons back into the reactor more efficiently than stainless steel, greatly saving uranium fuel; Zirconium alloy has good corrosion resistance at high temperature and high-pressure steam of 300 ~ 400 ℃, which also makes the reactor have a long service life. Therefore, zirconium is regarded as the first metal in the atomic age.

zirconium alloy

Development status of zirconium and its alloys

Zirconium, which is found in the earth’s crust at about 220 g /t, ranks 20th, ahead of other common metals such as copper, nickel, lead, and cobalt. Initially, zirconium alloys were mainly used as cladding materials in the nuclear industry. In recent decades, zirconium alloys have been widely used in the chemical industry, medical industry, and some special fields.

Zirconium alloy for nuclear use

Zirconium alloys have been widely used in the nuclear industry because of their very low thermal neutron absorption cross-section and good resistance to high temperature and pressure corrosion. France, the United States, Germany, and Russia have developed a series of zirconium alloys for nuclear use. At present, Zr-2, Zr-4, Zr2.5nb and ZIRLO, E635, M5, and NDA zirconium alloys have been successfully applied in the nuclear industry. These newly developed zirconium alloys have lower radiation creep properties and better resistance to iodine stress corrosion. In addition, they are able to meet the requirements of high burnup of the fuel assemblies, increasing the service life of the assemblies to 30 years.

nuclear reactor 2

Corrosion-resistant zirconium alloy

Zirconium has excellent corrosion resistance against most organic acids, inorganic acids, strong alkalis, and some molten salts. Therefore, zirconium can be used to improve the service life of some key components in corrosive environments. Another way to improve the corrosion resistance of alloy parts is surface pretreatment. In industry, zirconium is placed in high-temperature air to obtain a dense oxide film, so as to improve the corrosion resistance and erosion resistance of zirconium and its alloys. The results show that the corrosion rate of zirconium treated by surface oxidation in sulfuric acid medium is only 5% of that of pure zirconium, but the erosion resistance is increased by twice.

At present, zirconium is widely used as corrosion-resistant material in the chemical industry, and it has been widely used in the heat exchanger, dike washing tower, reactor, pump, valve, and corrosion medium pipeline. For example, zirconium alloys have been used to produce concentrated and hydrolyzed tubes in hydrogen peroxide production lines, while zirconium pressure reducing valves, agitators and flow meters are used in fertilizer production, sewage treatment, and dye industries.

Biomedical materials are a new high-tech material in recent years, and biomedical alloys must have good compatibility and corrosion resistance with the environment of biological fluids. Zirconium is valued by researchers for its good biocompatibility, elastic modulus similar to bone and corrosion resistance. Ti6Al4V, a titanium alloy implanted earlier in hard tissues of the human body, has an elastic modulus of nearly 110 GPa, which is much higher than the elastic modulus of 15 ~ 30 GPa of natural bones of the human body.

High-strength zirconium alloy

In the fields of space exploration, deep-sea exploration, and high-speed railway, there are often some special operating environments, such as the alternating temperature environment of -200 ~ 200 ℃, continuous space irradiation, and relative motion of structural parts, etc. Under these special circumstances, long-serving structural components are often faced with fatigue damage, dimensional instability, atomic oxygen erosion, and friction wear. At present, the structural parts used in these special fields are mainly made of 20Cr, GCr15, and other alloy steel materials, which often have problems such as poor radiation resistance, easy damage of moving parts, high density, and high cost.

Compared with traditional alloy steels, zirconium and its alloys have several important potentials:

  • The thermal expansion coefficient of zirconium is small and the size structure is stable, so it has the potential to produce precise structural components;
  • It has the potential of resisting space radiation damage;
  • It has the potential to resist atomic oxygen erosion;

Therefore, zirconium and its alloys are expected to adapt to unconventional environmental conditions in special fields and have the potential to be used as structural components in special environments.

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Zirconia Ceramics: A Hotspot in the Field of Micro-machinery

Zirconia ceramic materials are gradually being widely used in the field of micromachinery, because of its maintain excellent properties such as high-temperature resistance, oxidation resistance, acid and alkali corrosion resistance, hardness, etc.

The development of science and technology has made the miniaturization technology of zirconia ceramic materials become an important issue concerned by all countries, while the equipment tends to be miniaturized, and zirconia ceramics have a broad application prospect in the fields of automobile, medical treatment, aviation, aerospace, military, and environmental detection.

All countries in the world began to invest a lot of money, scientific research forces and too micromechanical system research. Organizations such as the National Natural Science Foundation of the United States and the Department of Defense attach great importance to MEMS(Micro-electromechanical Systems)technology and invest a lot of money in related research; The European Union has set up a multi-functional Microsystems research cooperation agency to strengthen interaction among countries; Japan has formulated the nano-manufacturing plan, the AI(artificial intelligence)technology plan, the microrobot plan, and established the micro machinery center and the micro machinery society; At present, there are more than 60 units engaged in MEMS research in China, and some scientific achievements have been made in the field of sensors and micro-actuators.

micromachinery

Zirconia ceramics are used in micro pressure sensors to detect engine inlet pipe pressure, micro accelerometers for vehicle safety airbag systems, and micro angular velocimeters for wheel sideslip and roll control. Microdevices such as micro pumps, microvalves, micro tweezers, and micro flowmeters applied in zirconia ceramics, and the micro-inertial measurement device, micro-whole analysis system, RF sensor, etc. are used in the military field. Moreover, zirconia ceramic materials can be used as a micro burner, a microreactor, and a pressure sensor at high temperatures and they can also be used as a composite, bone tissue scaffold, and in other biomedical fields because of their good biological solubility.

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Alumina VS Zirconia

Alumina (Al2O3) is a very common technical ceramic material. Zirconia (ZrO2), including yttrium stabilized zirconia (YSZ), is also widely used in machinery industries. Since both of them are oxide materials and could be sintered without vacuum, they share a lot in manufacturing equipment and have a similar appearance. However, there are still quite a lot of differences between these two materials.

Price: alumina VS zirconia

The most significant difference between these two materials is the price. Cost for zirconia is more than doubled for even the best alumina material. One of the reasons is the cost of the raw material. Compared with Zirconium, Aluminum is far more abundant in the crust and it’s much cheaper. On the other hand, Yttrium oxide, widely used as a stabilizer for Zirconia, is a rare earth element with limited sources.

Alumina Grinding Ball

However, it is the cost of shaping zirconia that contributes the major part. The density of zirconia is much higher than alumina and the wear resistance of zirconia is far better than alumina. To ground down the same thicknesses for zirconia takes almost 10x more time than alumina and consumes more diamond tools. Also, since the thermal shock resistance for zirconia is poor and requires a higher sintering temperature, the sintering process also costs more than alumina.

Applications: alumina VS zirconia

As the wear resistance for zirconia is much better, it is frequently used as mortar and pestles, grinding jars and grinding media, bearing balls and ceramic parts in valves and pumps. Zirconia parts will last longer in machines and have less contamination than grinding jars. Zirconia is generally better in mechanical applications but alumina is a better bulletproof material due to the lower density.

Although zirconia could withstand higher temperatures, application in industrial furnaces is rare. The advantage in working temperature is not quite significant, while the cost for zirconia is much higher.

High-density ZrO2 also provides better corrosion resistance. Zirconia could survive longer in a highly corrosive environment and is considered better material in chemistry laboratories.

Generally, zirconia performs better if the density and heat shock resistance is not considered. Stanford Advanced Materials (SAM) is a trusted supplier of customized zirconia products, such as zirconia rods, zirconia crucibles, zirconia tubes, etc. Please visit http://www.samaterials.com for more information.

Application of Zirconia in Fingerprint Identification

The Fingerprint recognition module is widely used in intelligent portable devices because of its fast, safe, convenient, and other advantages. However, due to the small area of the fingerprint module and complex application environment, it requires high identification sensitivity and speed, which also puts forward very high requirements for fingerprint identification chips and surface protection materials.

At present, there are two commonly used fingerprint identification schemes: pressing on the front of the sapphire cover and coating on the back.

iPhone-6S-Touch-ID

Cost and Performance

In terms of cost and performance, sapphire has high hardness and corrosion resistance, but it has some weaknesses such as high cost and weak anti-falling ability, while the coated back fingerprint recognition scheme has the disadvantages of easy wear and sweat corrosion due to the low hardness of the coating.

Operation

In terms of operation, the two schemes have their own merits. The back fingerprint identification is convenient only for holding the index finger of the hand, while other fingers are inconvenient, and it can’t be used on a plane, it has to be picked up, too, which is not convenient in some special applications scenarios (such as driving). Meanwhile, the positive fingerprint is much smoother for the current hot fingerprint payment.

fingerprint-scanner

Appearance

In terms of appearance, the texture of backside fingerprint recognition is slightly poor, and it is easy to destroy the overall aesthetics of the backside putting fingerprints on the front not only makes the back of the phone more beautiful but also more in line with users’ habits and aesthetics.

Overall, a positive fingerprint is more popular with users, but it costs more. Many years of research have proved that zirconia ceramic cover products can be used for positive pressure fingerprint identification schemes.

The ceramic cover is zirconia ceramic (ZrO2), also known as the zirconium gem. It has superior hardness, toughness, insulation, heat conduction, and other advantages, showing abrasion resistance, fall resistance, corrosion resistance, high-temperature resistance, and other excellent characteristics, which is very suitable for pressing fingerprint identification module cover.

Zirconia ceramic is a cost-effective alternative to sapphire, and the zirconia product has been used in many well-known brands of mobile phones, which has the following advantages.

High hardness

The hardness of zirconia ceramics is 8.5 and that of single crystal alumina (sapphire) is 9, so they are quite similar in wear and scratch resistance.

High permittivity

The permittivity of zirconia is 32-35, which is three times that of sapphire, while all other materials are within 10. This characteristic is beneficial to improve the capacitance difference between the high and low levels of fingerprint identification module, so that fingerprint identification is more sensitive, the success rate is higher, and the speed is faster.

Thin in thickness

At present, the thinnest mass production thickness is as low as 0.1mm under the protection of falling strength of the zirconia protective layer, which is easier to identify than the thinnest sapphire cover with a thickness of 0.3mm. If the thickness is the same as that of sapphire, the strength and fall resistance of zirconia protective coating will be significantly better than that of sapphire.

Good processability

Zirconia ceramics are directly prepared by casting, polishing, and other ceramic processes. Its process is simple and its shape is easy to process, so it costs less than sapphire.

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10 Applications of Zirconium You Should Know

Zirconium, chemical symbol Zr, atomic number 40, melting point 1852°C, is one of the high melting point metals. Zirconium with special excellent properties, such as the resistance to high temperature, oxidation, corrosion, and abrasion, all of which made it a wide range of applications as the structured and functional ceramic material in many industrial sectors, especially in the high-tech industry.

Zirconium products and their applications

  1. Zirconium silicate

Zirconium silicate is an important kind of traditional zirconium product. Products can be prepared with zircon sand as raw material, after grinding, calcination, and powder, is a kind of high-quality and inexpensive ceramic glaze opacifying agent, mainly used in ceramics and porcelain, building ceramics color glaze production, has been widely used in high-grade refractory materials, precision casting, emulsified glass and other industries.

Zirconium Silicate Powder

  1. Zirconium carbonate

Zirconium carbonate is mainly used as cosmetic additives and waterproof agents, flame retardants, sunscreen, fiber and paper surface additives, and can be used for preparing zirconium cerium catalytic composite material, is an important raw material for textile, papermaking, paint, cosmetics industry, the amount of growth in recent years.

  1. Zirconium oxychloride

It can be used for other zirconium products such as two – zirconium oxide, zirconium carbonate, zirconium sulfate, zirconium and hafnium compound preparation and separation of zirconium and hafnium metal material, can also be used for textile, leather, rubber additives, metal surface treatment agent, coating driers, refractories, ceramics, catalyst, fire retardant, and other products.

  1. Fused zirconia

Fused zirconia is mainly used in the production of glazes and refractories. Due to the high content of impurities in the fused zirconia, the use is limited.

  1. Zirconium sulfate

It is the important raw material in the production of leather tanning agent, wool processing agent and paint surface oxidation agent, can be used as a catalyst carrier, amino acid, and protein, precipitant, and deodorant, intermediate raw materials are for zirconium chemicals and metal zirconium and hafnium.

  1. Zirconium oxide

The white solid, non-toxic, tasteless, has enough stability of alkali solution and many acidic solutions, suitable for precision ceramics, electronic ceramics, optical lenses, glass additives, dissolving zirconia brick, ceramic pigment, glaze, artificial stone, refractory materials, grinding and polishing industry and products.

It is also known as semi-stable, stable zirconia is a white powder with non-toxic, tasteless, and stable chemical properties, the specific surface area is controllable, manufacturing all kinds of special ceramics, advanced refractories, new energy materials, optical communication devices, based on raw materials.

  1. Zirconia structural ceramics

Using the composite zirconium oxide as the raw material, including two kinds of products such as zirconia grinding and zirconia structure, the structure of zirconia mainly includes the zirconia special ceramic valves, fiber optic connectors, ceramic knives, watches accessories, ceramic scissors, textile porcelain, etc.

Since Zirconium has very good chemical corrosion resistance, zirconium shapes, such as zirconium tubes and zirconium rods are used to make equipment for the chemical industry.

Zirconium Rod

  1. Nuclear grade zirconium

It is an important strategic metal used primarily for nuclear-powered aircraft carriers, nuclear submarines, and civilian power reactors, as well as the cladding of uranium fuel elements.

  1. Industrial grade zirconium

It is mainly used for the production of industrial-grade zirconium – chemical corrosion resistance equipment, military industry, electronic industry, pipeline valve materials, special high strength and high-temperature alloy materials, electric vacuum, and lighting industry getter.

  1. Firearm zirconium

It is also used in the combustion of the flame zirconium sponge, and also can be used in alloy additives and metallurgical deoxidizers, chemical industry, civil flash fireworks and so on.

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Application of Chemical Zirconia Ceramics in Aeroengines

To maintain their leading position in the field of aviation power in the 21st century, aero-engine companies around the world are seeking new ways to improve the performance of military and civil engines and maintain their competitiveness. Half of that will depend on material improvements, including low-temperature polymer composites and high-temperature ceramics; the other half relies on improving design guidelines, methods, and procedures.

As the key to the improvement of military engine materials is to rely on high-temperature ceramic materials, the military engine will be the primary verifier of ceramic technology. Why is it necessary to use chemical zirconia ceramics? The operating temperature of the existing engine is already very high, and the only way to increase the temperature again is through the fine design of the cooling air circuit or the increase of cooling air volume.

However, the effects of these methods follow the law of diminishing, and only by improving the working temperature of the material can the maximum effect be achieved. Because raising the operating temperature can improve working efficiency, reduce fuel consumption and obtain the maximum thrust, using the saved high-pressure air for cooling for circulation can also improve the thrust and efficiency. Another option is to reduce weight by choosing materials with greater specific strength and greater stiffness. At present, only ceramic materials have the potential in this respect.

The application of ceramics to aero-engines will be developed with new materials and manufacturing methods. Considering the brittleness of ceramic materials and the lack of design and use experience, the process will be very long, no less than 15-20 years of metal materials. The applications of chemical zirconia ceramics in aviation are as follows.

Chemical zirconia ceramics have high-temperature resistance, low density, good oxidation resistance, corrosion resistance and wear resistance. In the case of the cooling, the working temperature of chemical zirconia ceramics can reach 1600 ℃, the density is only 40% of that in the high-temperature alloy, and the same volume of parts can reduce the weight by about 60%, which can greatly reduce the centrifugal load of the high-speed rotor. The use of ceramics also simplifies the chemical zirconia by reducing or eliminating the cooling system, making the engine compact.

The increasing turbine inlet temperature is the key to improving the thrust-to-weight ratio of the aero-engine and reducing fuel consumption. Sages for example, when the ratio is 10 level, the temperature of the engine turbine can reach above 1500 ℃, while the use temperature of high-temperature alloys and intermetallic compounds highest is less than 1200 ℃. Therefore, the research of high-temperature chemical zirconia ceramics and their ceramic matrix composites becomes one of the key technologies for high thrust-weight ratio aero-engines.

Radar remains one of the most reliable means of detecting military targets in future wars. The essence of stealth technology is to reduce the target’s RCS(Radar Cross-Section), that is, to select materials with good radar wave absorption to reduce its RCS.

Absorbing materials can be divided into coating type and structure type according to process and bearing capacity. The former has a poor bearing capacity and low strength, while the latter is a new functional composite chemical zirconia material, which has the characteristics of absorbing waves and can be directly used as the chemical zirconia material for aircraft.

We use the excellent mechanical and physical properties of chemical zirconia ceramics to carry out the research on absorbing materials, which can not only enhance the national defense force but also is an important aspect of expanding the application of chemical zirconia ceramics. Some new nano absorbents and their composites are being applied in this field, such as nano Silicon Carbide (SiC), nano nitride, carbon nanotube (CNT), and other nanocomposites.

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What Are the Uses of Advanced Composite Ceramic Substrates in Missiles?

In the mid-1980s, the United States developed an aerospace aircraft program that required both high-temperature tolerance and light mass. For this purpose, a variety of new high-temperature materials were developed, including advanced resin matrix composites, metal matrix composites, ceramic matrix composites, and carbon/carbon composites. Ceramic material is the preferred material for missile radome because of its excellent mechanical, thermal and electrical properties. The radome is the most widely used ceramic matrix composite material in missile structure.

Missile radome

The missile radome is located at the front end of the missile. Its function is to protect the navigation antenna from damage so that the missile can effectively hit the target. It is not only an important part of the aerodynamic shape of the missile but also the protection device of the antenna. During the flight of the missile, the radome should not only withstand aerodynamic heating and mechanical overload, resist the erosion of rain, sand, and other adverse working conditions, but also meet the stringent requirements of electrical performance proposed by the missile control loop. Therefore, the missile radome material should have the following properties:

  • Excellent dielectric properties

In the guidance system, the transmission efficiency and aiming error of the radome are very sensitive to the dielectric properties of the material and its relationship with temperature and frequency. It is required that the material has low dielectric constant (10) and dielectric loss, and the dielectric properties do not change obviously with temperature and frequency.

  • Good heat resistance and thermal shock resistance

The high Mach number of the missile can make the radome of instantaneous heating rate is as high as above 120 ℃ / s, so the material is required to have good thermal shock resistance, and the molecular structure of the material is required to be stable when the temperature is raised, and the material properties (such as dielectric properties and mechanical properties) change little to ensure that the radome can work normally when the temperature is raised.

  • High-strength structural properties

The strength of the radome material should be high and rigid enough to satisfy the mechanical stress and bending moment caused by the longitudinal or transverse acceleration of the aerodynamic forces in the spacetime of the missile flying at high speed.

  • Resistance to rain erosion

It plays a decisive role in the design allowable range of impact Angle and the sensitivity of aircraft in rain erosion.

  • Low-temperature sensitivity

The dielectric properties and strength properties of general materials change obviously when they work at high temperatures. Therefore, the properties of the radome material, especially the dielectric properties and strength, are affected by the temperature change as little as possible.

Ceramic-based missile radome

Ceramic-based missile radome materials mainly include silicon nitride-based, silicon oxide-based and phosphate-based materials. Silicon nitride ceramics have not only excellent mechanical properties and high thermal stability but also low dielectric constant. Its decomposition temperature is 1900 ℃, its erosion resistance is better than fused silica, and it can withstand 6 ~ 7 Ma rating of flight conditions. Silicon nitride ceramic composite radome is one of the main research targets in various countries, which has been identified as the most promising radome material by the test of the Georgia Institute of Technology. Yttria Stabilized Zirconia (YTZ), also known as yttria-zirconia, is the strongest ceramic material. This material offers the highest flexural strength of all zirconia-based materials, and the research on zirconia-based materials as missile radome is in progress.

Ceramic-based-missile-radome

  • Silica-based material

Because of the high flying Mach number of the missile and the relatively long heating time, if the radome of the medium-range missile is made of a single quartz ceramic material, it cannot meet the bearing requirement of thermal stress. In order to meet the requirements of medium and long-range ground-to-ground tactical and strategic missile radome, quartz glass, high-silica puncture fabric and orthogonal tri-directional quartz fabric reinforced silica matrix composites have been developed and successfully applied.

  • Phosphate-based materials

Phosphate matrix composite material is a kind of Russian characteristic permeable material, which is made by impregnating cloth or fabric with a phosphate solution and then curing under pressure. Aluminum phosphate has stable performance in 1500 ~ 1800 ℃. At present, such materials have been used in cruise missiles, anti-missile missiles, tactical missiles and space shuttles. The most obvious disadvantage of phosphate is that it is highly hygroscopic, so the surface of the composite material needs to be coated with an organic coating for moisture-proof treatment.

  • Silicon carbide ceramic matrix composites

Silicon carbide ceramic matrix composites have a series of excellent properties, such as low density, high-temperature resistance, ablation resistance, erosion resistance, and oxidation resistance, and it has a wide application prospect in the field of aerospace. Since the late 1980s, the United States has successfully developed a series of C/SiC, SiC/SiC ceramic matrix composites, which can be applied to the re-entry nose cone of missiles, the front end of wings and other heat-resistant structures.

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What Are the Nano Zirconia Composite Ceramic Powders?

Zirconia is a new structural ceramic material developed in the 1970s. It is widely used in metallurgy, electronics, chemical industry, machinery and other fields due to its abrasion resistance, corrosion resistance, high strength, and high melting point.

Zirconia ceramic material, the most important material in advanced ceramics, is an important basic material for the development of the modern high-tech industry. In particular, nano-oxide ceramics with their special structure and performance has become the focus of the industry. The following is a brief introduction to the powder materials needed to prepare nano zirconia ceramics.

Ni-P coated nano zirconia composite powders

The preparation process of Ni-P coated nano zirconia (ZrO2) composite powders is firstly to prepare nano-ZrO2 powders by the chemical precipitation method, and then to prepare Ni-P nano-ZrO2 powders by an electroless plating method. Since ZrO2 has no autocatalytic activity in the electroless nickel plating solution, it is necessary to pretreat ZrO2 nanoparticles. Generally, Pd2+ is directly adsorbed on the surface of ZrO2 powder by the one-step palladium catalysis method, and then Pd2+ is reduced to palladium in a reducing solution so that the surface of nanopowder has the catalytic activity of electroless nickel plating. The two-step sensitization-activation method is usually used in the pretreatment of non – conductive powders. However, it is difficult to remove the residual nickel ions in the powder after two-step treatment, which often brings adverse effects on the activity of the powder. At present, one-step palladium catalysis and in-situ palladium pretreatment are used.

At present, Ni-P coated nano zirconia composite powders have been widely used and studied in semiconductor nanomaterials.

Zirconia toughened alumina ceramic composite powder

Zirconia toughened alumina ceramic is one of the most widely studied structural ceramic materials. The toughening mechanism of zirconia toughening alumina ceramics is the refinement of matrix grain, the toughening of phase change, the toughening of microcrack, and the turning and bifurcation of crack. The properties of zirconia toughened alumina ceramics are mainly determined by the microstructure formed during sintering, and the microstructure is mainly determined by the powder state of raw materials. Therefore, the preparation of high-quality Al2O3/ZrO2 nanocomposite ceramic powders is the prerequisite for the preparation of zirconia toughened alumina ceramics with excellent properties. The preparation methods of Al2O3/ZrO2 nanocomposite ceramic powders mainly include the mechanical mixing method, multi-phase suspension mixing method, the sol-gel method, chemical precipitation method, etc.

Alumina is a kind of high-strength matrix in the composite ceramic system of zirconia toughening alumina, and the zirconia in the intercalation provides a phase change toughening mechanism. The use of ZrO2 phase change properties to toughen ceramic materials is still one of the main research topics of ceramic toughening in the future.

Zirconia toughened alumina composite ceramics have excellent corrosion resistance, thermal shock resistance, high strength, and toughness, as well as wide application prospects. Zirconia toughened alumina composite ceramics can be used to make ceramic cutters for the processing of cast iron and alloy, and the interface structure of engineering ceramics can be made to extend the service life of engineering materials. Alumina toughened with zirconia can be used to make wear-resistant ceramic balls. Due to its good biocompatibility, alumina can also be used as a biomedical material for the reconstruction and repair of hard tissues (teeth).

Boron nitride-zirconia composite powder

Boron nitride-zirconia composite powders were prepared by mechanical mixing method. Boron nitride, zirconia, and additives were used as the main raw materials. After mixing, the powders were ball-ground and mixed in an alcohol medium, and then the zirconia composite ceramics were sintered in a hot press sintering furnace. Due to the poor sintering capacity of pure boron nitride and its difficulty in sintering densification, CaO, B2O3, Al2O3, and ZnO are generally added as sintering AIDS.

Boron nitride-zirconia composite ceramics are characterized by high strength, high toughness, high thermal conductivity, low expansion, and excellent physical and chemical properties, such as chemical inertness and chemical corrosion, which are present in molten metals. In addition, it also has excellent thermal shock resistance, erosion resistance, wear-resistance and easy processing and other properties, which make the material suitable for thin strip continuous casting side seal plate, jet forming liquid guide pipe, the nozzle for metal spinneret, continuous casting functional refractories and other fields.

Boron nitride-zirconia composite powder

Nano cerium-zirconium composite oxide powder

The preparation methods of nano cerium-zirconium composite oxide powders include high-temperature roasting, the sol-gel method, coprecipitation method, hydrothermal method, and solid-phase reaction method. High-temperature roasting was carried out in a water-ethanol solvent, and the suspension consisted of dry Al (NO3) 3•9H2 O•Ce (NO3) 3•6H2O and monocline phase zirconia nano-powder was pyrolyzed by high-temperature, Al2O3 doped CeO2 coated monoclinal zirconia powders with a particle size less than 100 m were prepared.

Nano cerium-zirconium composite oxide materials are used as auxiliary catalysts, mainly used in automobile exhaust treatment, with good high-temperature stability, high REDOX ability, high oxygen storage, and release capacity.

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