Analysis of application requirements of titanium and titanium alloy materials in civil, aerospace and manufacturing industries

Target application:

The phenomenon that energetic particles (such as argon ions) bombard the solid surface, causing various particles on the surface, such as atoms, molecules or clusters, to escape from the surface of the object is called "sputtering." In magnetron sputtering coating, the positive ions generated by argon ionization are usually used to bombard the solid (target), and the sputtered neutral atoms are deposited on the substrate (workpiece) to form a film. The magnetron sputtering coating has a " Two characteristics: low temperature and fast speed.

Principle of magnetron sputtering:

Add an orthogonal magnetic field and electric field between the sputtered target (cathode) and the anode, and fill the required inert gas (usually Ar gas) in the high vacuum chamber. The permanent magnet forms 250-350 on the surface of the target material The Gaussian magnetic field forms an orthogonal electromagnetic field with the high-voltage electric field.

Under the action of an electric field, Ar gas ionizes into positive ions and electrons, and a certain negative high voltage is applied to the target. The electrons emitted from the target are affected by the magnetic field and the ionization probability of the working gas increases. A high-density plasma is formed near the cathode, and Ar ions are accelerated to the target surface under the action of the Lorentz force, and bombard the target surface at a high speed, so that the atoms sputtered out of the target follow the principle of momentum conversion. The high kinetic energy departs from the target surface and flies toward the substrate to deposit a film.

Magnetron sputtering is generally divided into two types: DC sputtering and radio frequency sputtering. Among them, the principle of DC sputtering equipment is simple, and its rate is also fast when sputtering metal. The application range of radio frequency sputtering is more extensive. In addition to sputtering conductive materials, non-conductive materials can also be sputtered. At the same time, reactive sputtering can be used to prepare compound materials such as oxides, nitrides, and carbides. If the frequency of radio frequency increases, it becomes microwave plasma sputtering. Nowadays, electron cyclotron resonance (ECR) type microwave plasma sputtering is commonly used.
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What effect does drawing have on the performance and organization of medical titanium wire?

With the rapid development of the metallurgical industry, titanium has been popularized and applied as a structural material with high strength and corrosion resistance. In the hydrometallurgical process, because the equipment is exposed to alkali, acid, and various corrosive gases, soot, traditional aluminum alloy, acid-resistant stainless steel, and other materials cannot meet the needs of the production process, which limits the development of hydrometallurgy.

(1) Application of titanium equipment in electrolytic nickel production

In the production of electrolytic nickel, equipment is exposed to solutions with high acid content and active ions, and titanium has excellent corrosion resistance, so it becomes an ideal material for manufacturing electrolytic nickel equipment.

Compared with the stainless steel mother plate, the cathode mother plate in the electrolytic nickel production has a better economic effect and superior performance. For example, the deposited nickel skin is not easy to stick to the plate, easy to peel, the peeling rate is improved, and the starting electrode of the titanium mother plate is flat, Good rigidity, uniform current density during electrolysis, etc. In addition, the heaters, pumps, valves, etc. in electrolytic nickel production equipment also use a lot of titanium materials.

(2) Application of titanium equipment in electrolytic copper production

The cathode rollers of electrolytic copper production equipment were originally steel cathode rollers. Due to the corrosion of the electrolyte, pitting corrosion occurred on the surface of the rollers, which affected the quality of the copper foil, and regular grinding of the rollers also wasted manpower and financial resources. These problems were solved after using titanium rollers. In addition, most of the heaters and cathode motherboards in the production of electrolytic copper are made of titanium.

(3) Hydrometallurgy of other metals

Titanium equipment is also used for cobalt, zinc, aluminum, mercury and other smelting, tungstic acid purification, etc. The main equipment in the metallurgical industry includes electrolyzers, reactors, washing towers, heat exchangers, stirrers, evaporation devices, dust collectors, etc., which Have achieved significant benefits. In foreign countries, when titanium pumps are used to transport chloride, sodium chloride, potassium chloride, and dilute hydrochloric acid, the life of the pump is 5-20 times longer than that of cast iron pumps or stainless steel pumps, and the liquid loss is reduced by three-fifths. Titanium storage in the chlorination workshop The tank can be used for 3-4 years, while the steel storage tank can only be used for 2 months.
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Characteristics and advantages of drawing titanium wire and titanium wire

The superplastic forming method of titanium alloy sheet can be roughly divided into the following three types: (1) vacuum forming; (2) air pressure forming (blow forming); (3) compression forming (coupling die forming). The first two methods are commonly used methods for forming plastic (or glass) products. The superplastic forming of titanium sheet is viscous or semi-viscous flow deformation, so low-pressure forming can be used. Air pressure forming can also be used in combination with vacuum forming.

1. Vacuum forming method

The vacuum forming method can be divided into two types: the convex mold method and the concave mold method.

The punch method is a forming method in which the heated wool is adsorbed on a punch with the inner shape of the part, and it is used to form parts that require high inner dimensional accuracy. The die method is a forming force method in which heated wool is adsorbed on a die with the shape of the part. It is used for the forming of parts that require high dimensional accuracy. Generally speaking, the former is used for the formation of deeper containers, and the latter is used for the formation of shallow containers.

Vacuum forming is also a kind of air pressure forming, but the forming pressure can only be one atmosphere. Therefore, for the titanium plate, only parts with thin thickness, simple shape, and gentle curvature can be formed, and it is not suitable for forming parts with thicker thickness, more complicated shape and severe deformation.

2. Air pressure forming method (blow molding method)

This is a special bulging process.

The traditional bulging process is realized by mechanical, hydraulic bulging or explosive bulging. The pressure and energy used are relatively high, and due to the limitation of material plasticity, the amount of deformation is generally not too large. Blow molding is a kind of forming that can obtain a large amount of deformation with low energy and low pressure. It is a sheet metal forming technology that is different from the traditional process concept. Since the metal is free during the deformation process, almost all the power is consumed in the deformation work, and the friction loss is small (for free blow molding, there is no friction loss), which is essentially different from other stamping forming .

Blow molding can be divided into two types: free blow molding and mold blow molding. Mold blow molding is characterized by half-mold molding. Similar to vacuum molding, it is also divided into two types: convex molding and concave molding; the difference is that the molding pressure can be greater than one atmosphere, and it is also suitable for the air supply system. The pressure can be adjusted so that parts with complex shapes and large curvature changes can be manufactured.

(1) Free blow molding method

This is the simplest form of blow molding. Its characteristic is that it does not use molds, and the typical parts blown are spherical parts.

(2) Punch forming method

This method is to form a closed pressure space on the outside of the titanium plate wool. After the titanium plate is heated to superplastic temperature, under the action of the compressed gas pressure, the wool will produce superplastic deformation and gradually approach the mold surface until it is the same as the mold. Completely fit, make the same parts as the mold surface. The inner surface of the formed part has high dimensional accuracy, accurate shape, large depth and width ratio, and easy mold processing, but it is difficult to demold and raw materials are more expensive. The bottom of the part formed by this method is thicker than the surrounding.

(3) Concave mold forming method

Different from the punch forming method, a closed pressure space is formed inside the titanium sheet wool during the forming process. The outer surface of the formed part has high dimensional accuracy, accurate shape, easy part demolding, less raw materials, but the depth and width are relatively small, and the mold processing is also difficult. The bottom of the part formed by this method is thinner than the surrounding.

3. Compression molding method

Using coupling mold. The difference from ordinary pressing is that the temperature is high and the molding speed is much slower.

Because it is difficult to manufacture metal coupling molds that can withstand the superplastic temperature of titanium plates, and the matching accuracy is difficult to ensure (especially for molds with complex shapes), superplastic forming of titanium plates is rarely used.
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How to enhance the wear resistance of titanium rods and titanium wires?

The unique properties of titanium make it an excellent material for making bicycle frames. Its high strength, low density, and low modulus of elasticity (the modulus of elasticity can be regarded as an index to measure the difficulty of elastic deformation of the material), excellent Fatigue resistance, and corrosion resistance make the manufactured titanium alloy frame not only very strong and durable but also very light.

Titanium materials will not break, will not rust, and will not corrode in any atmospheric environment. Titanium is so resistant to corrosion that it doesn't even need any paint treatment. We just lightly rub the surface to brighten its natural color, and the titanium color can better reflect the low-key and luxurious texture of this metal.

Titanium has inherent flexibility like steel, but this characteristic of titanium is more obvious. Therefore, it has a very slight elasticity, which means that it can absorb vibrations from the road surface. Before it is transmitted to the rider, (the titanium Seatpost can also eliminate some vibrations) will have a very smooth riding feeling.

Unlike aluminum or carbon bicycle frames, titanium bicycle frames will not break suddenly in an accident. This is because, like steel, it has a certain degree of flexibility. (In fact, titanium is more flexible than steel, which is why it is so famous for its riding quality.) It is more like steel because it has incredible strength, but it is much lighter than steel and less Rusty.

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Application of titanium rod, titanium wire and titanium plate in electric power industry

1. Aerospace

The major titanium use countries in the aerospace industry are concentrated in Western countries, especially the United States, where 60% of titanium is used in this field. Asian countries, Japan and China all invest about 10% of titanium in this field. However, with the rapid development of Asian aerospace in recent years, the consumption of titanium in the aerospace field will increase accordingly. From a global perspective, the aviation industry plays a decisive role in the titanium market. Historically, the major cycles of the titanium industry are closely related to the aviation industry.

2. Civil aircraft

(1) Reduce structural weight and improve structural efficiency

(2) Meet the use requirements of high temperature parts

(3) Meet the requirements that match the structure of the composite material

(4) Meet the requirements of high corrosion resistance and long life

3. Military weapons

The development and procurement of military weapons continue to develop in the direction of lightness and flexibility. In order to meet the fighter's combat performance requirements, in addition to the use of advanced design technology, it is necessary to use materials with excellent performance and advanced manufacturing technology. One of the important measures is to choose a large number of titanium alloys and improve the application level of advanced titanium alloys.

4. Car

Reducing fuel consumption and reducing hazardous waste (CO2, NOX, etc.) emissions have become one of the main driving forces and directions for technological progress in the automotive industry. Research shows that lightweight is an effective measure to save fuel and reduce pollution. For every 10% reduction in the quality of a car, fuel consumption can be reduced by 8%-10%, and exhaust emissions can be reduced by 10%.

In terms of driving, the acceleration performance of the vehicle is improved after the weight is reduced, and the vehicle control stability, noise, and vibration are also improved. From the perspective of collision safety, after the car is lightweight, the inertia during a collision is small and the braking distance is reduced.

5. Medical industry

Titanium has a wide range of applications in the medical field. Titanium is close to human bones and has good biocompatibility to human tissues without toxic side effects. Human implants are special functional materials closely related to human life and health. Compared with other metal materials, the main advantages of using titanium and titanium alloys are as follows:

1 Light weight; 2 Low modulus of elasticity; 3 Non-magnetic; 4 Non-toxic; 5 Corrosion resistance; 6 High strength and good toughness.

The amount of titanium alloy used in surgical implants is increasing at an annual rate of 5%-7%. Femoral heads, hip joints, humerus, skull, knee joints, elbow joints, shoulder joints, metacarpophalangeal joints, jaws, and cardiac membranes, kidney membranes, vasodilators, splints, prostheses, made of titanium and titanium alloys Hundreds of metal parts, such as fastening screws, have been transplanted into the human body. Good results have been achieved, and they have been highly praised by the medical community.

6. Chemical industry

Titanium has excellent corrosion resistance, mechanical properties and process properties, and is widely used in many sectors of the national economy. Especially in chemical production, titanium is used instead of stainless steel, nickel-based alloys and other rare metals as corrosion-resistant materials. This is of great significance to increase output, improve product quality, extend equipment life, reduce consumption, reduce energy consumption, reduce costs, prevent pollution, improve working conditions, and increase labor productivity.

7. Ocean Engineering

With the development of science and technology and the depletion of land resources, mankind's development and utilization of the ocean has been on the agenda. Titanium has excellent corrosion resistance to seawater, and is widely used in seawater desalination, ships, ocean thermal energy development, and seabed resource exploitation.

8. Daily life

Titanium is widely used in daily life and can be described as ubiquitous. For example, golf heads, bicycle frames, tennis rackets, wheelchairs, spectacle frames, etc. are all used in titanium.

The application of titanium in sporting goods due to its light weight and high strength has gradually expanded from the earliest tennis rackets and badminton rackets to golf heads, clubs and racing cars.

The light weight of titanium is also applied to spectacle frames, and titanium is not easy to be allergic to the skin, and the surface of titanium can have brilliant colors after anodizing, so it has been used in spectacle frames since the early 1980s.

Titanium is considered a rare metal because it is scattered in nature and difficult to extract. But it is relatively rich, ranking tenth among all elements. Titanium ore mainly includes ilmenite and rutile, which are widely distributed in the crust and lithosphere. Titanium is also present in almost all living things, rocks, water bodies and soil.

The Kroll method or Hunter method is required to extract titanium from the main ore. The most common compound of titanium is titanium dioxide, which can be used to make white pigments. Other compounds include titanium tetrachloride (TiCl4) (used as a catalyst and used to make smoke screens as air cover) and titanium trichloride (TiCl3) (used to catalyze the production of polypropylene).

Titanium alloy characteristics:

High strength, the density of titanium alloy is generally about 4.51g/cm3, which is only 60% of steel. The strength of pure titanium is close to the strength of ordinary steel. Some high-strength titanium alloys exceed the strength of many alloy structural steels. Therefore, the specific strength (strength/density) of titanium alloy is much greater than other metal structural materials, and parts and components with high unit strength, good rigidity and light weight can be produced. At present, titanium alloys are used in aircraft engine components, skeletons, skins, fasteners, and landing gear.
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Application of titanium alloy materials such as titanium rod, titanium wire and titanium plate in construction industry

When there is a corrosive medium in the titanium tube heat exchanger, it is suitable to use composite plates and titanium-lined tube plates. Nowadays, large-scale exchangers are mostly made of integral tube sheets with a thickness of 100mm and integral heads of the same thickness. Since the use of titanium is often associated with strong corrosive media, in order to avoid corrosion, in the structural design of titanium equipment, attention should be paid to:

(1) Avoid gaps and stagnant areas. In order to achieve a complete seal and prevent a gap between the tube and the tube sheet, expansion and sealing welding should be adopted. Regardless of whether it is an all-titanium or composite board, many designers support the use of step welding based on the consideration of weld penetration, but some people think that this will cause greater difficulties in repair welding. The fasteners in the tower should be connected by wedges instead of bolts. The sealing surface of the flange should be covered with asbestos gasket with PTFE film. Under the conditions of high temperature, high pressure and strong corrosion, it is recommended to use titanium reinforced polytetrafluoroethylene winding and T0.2Pd metal pad.

(2) In the conductive medium, avoid contact between titanium and other metals as much as possible. In the structure, a third material with a potential between the two can be used as a transition layer (such as by surfacing) or isolated by insulating materials. When the medium is seawater, a heat exchanger made of titanium tubes filled with different metal tube sheets and rolled up can be used. The premise is that the tube sheet material is compatible with titanium.

(3) The expansion coefficient of titanium is smaller than that of steel. Therefore, thermal stress cracking may occur in the heating equipment of the titanium steel composite structure, and the thermal compensation link should be set in the design.

(4) In some corrosive media with high flow rates and sudden changes in flow rate, titanium equipment and components are prone to erosion, so when the flow rate exceeds 6m/s, an anti-scouring baffle should be installed. In the titanium tube heat exchanger, due to vibration, the contact between the titanium tube and the supporting hole is prone to fracture. Therefore, shock absorption measures should be taken and a PTFE ring can be caulked at the contact between the titanium tube and the supporting hole.

(5) The thermal conductivity of the titanium surface depends to a large extent on the design and process parameters. For the heat exchanger using cold water as the coolant, the available value is 425~550W/(m2·℃); for the heat exchanger using steam or hot water to heat the static liquid, the available value is 800~1450W/(m2·℃) . For the condenser cooled by seawater, when the tube wall thickness is 0.5~1.0mm and the flow velocity is lower than 3.9m/s, the measured data is 54006800W/(m2·℃).
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Nuclear submarine made of titanium rod, titanium wire and titanium plate

Among the titanium materials, the most commonly used industrial pure titanium (TA2 is the most widely used), Ti-6Al-4V (when a certain strength is required), and Ti-0.8Ni-0.3Mo (when there are gaps or in a non-oxidizing medium). When hydrogen absorption and hydrogen embrittlement may occur, especially in the case of weld corrosion and hydrogen absorption, low-iron (<0.05%) titanium materials are required. Titanium heat exchangers, condensers, and related auxiliary equipment have been successfully used for more than 20 years in petrochemical enterprises.

There are many products and complicated processes in the petrochemical industry. Here is an example to introduce the application of titanium:

1. Terephthalic acid is the raw material for synthetic polyester, which is prepared by the p-xylene oxidation method in the industry. No matter high-temperature oxidation or low-temperature oxidation, there is high-temperature corrosion of acetic acid and bromide. In the medium with a temperature higher than 135℃, pitting corrosion of 316L stainless steel will occur after dozens of hours. Therefore, the design specification stipulates that titanium must be used above 135°C. Beijing Petrochemical Plant has introduced a complete set of titanium equipment, including 16 oxidation reactors, solvent dehydration towers, heaters, condensers, and reboilers. Nanjing Yangzi Petrochemical Company has introduced an annual output of 450,000 tons of terephthalic acid equipment, 56 sets of titanium equipment, and a large number of titanium pipeline valves. The oxidation reactor introduced by Shanghai Petrochemical Plant is 32m high, with an upper diameter of 4m, a lower diameter of 5.3m, a volume of 505m, and a weight of 175t. The effect of using titanium material is very good, and the prospect of promotion and application is bright.

2. In the device where ethylene is oxidized to acetaldehyde, acetaldehyde is oxidized to acetic acid, and propylene is oxidized to acetone, the main corrosive medium is a catalyst, except that the raw materials and products are corrosive. Stainless steel corrodes quickly, and only titanium has Good corrosion resistance. As early as 1963, the United States successfully applied titanium in the production of acetaldehyde by oxidation of ethylene. my country's first ethylene oxidation to acetaldehyde plant was put into use in 1976, and the titanium plant has been operating well so far. Foreign titanium-lined reactors are as high as 9.6m, with a diameter of 3m, and there are 11 sets of titanium equipment including heat exchangers, catalyst regeneration towers, and acetaldehyde solution coolers. Since the 1980s in my country, Shanghai and Jilin have introduced foreign complete sets of equipment for the production of acetaldehyde by ethylene oxidation. Many of the equipment and pump valves are made of titanium. Compared with stainless steel, it has obvious advantages and the use effect is very satisfactory.

3. Urea is a high-quality fertilizer and a raw material for petrochemicals. Since the first titanium-lined urea synthesis tower was put into production in 1963, there have been nearly 10,000 equipment in operation all over the world, and practice shows that there is no obvious corrosion in the titanium-lined synthesis tower. The converted corrosion rate of 316L stainless steel is 4.1-4.5 mm/a. Therefore, titanium has better economic benefits than stainless steel. In addition to the titanium-lined urea synthesis tower, CO 2 stripping towers, heat exchangers, mixers and pump valves have been used in China since the 1970s.

4. In the refining of crude oil with high sulfur and high salt content, titanium equipment is ideal. In foreign countries, titanium equipment has been successfully used in many processes such as atmospheric distillation equipment, sewage treatment equipment, desulfurization separation tower condenser, and stripping tower radiator for many years. Our country has also used cast titanium seawater pumps, titanium condensers in catalytic cracking fractionation, cryogenic separation titanium condensers, and porous titanium plates in this system, all of which have been in normal operation for more than ten years.

5. Chlorinated hydrocarbon is one of the largest varieties of the petrochemical industry. Due to the chlorination reaction involved, stainless steel equipment has been difficult to handle. In foreign countries, titanium materials have been used to manufacture methylene chloride rectification towers, trichloroethane heat exchangers, condensation towers and fractionation towers, trichloroethylene condensation towers, perchloroethylene heat exchangers, and polychloride coil heaters. In the production of vinyl chloride in my country, the cooling tower, wastewater stripping tower, and wastewater storage tank tray support frame, connection pipe, flange sealing surface, using Ti-0. 2Pd lining has been used for nearly ten years without corrosion. Titanium pipes, joints, and gas distributors have all been made of titanium for many years.

6. Phenol is an important raw material for the petrochemical industry. It is a new process to obtain phenol and acetone from cumene and cumene peroxide using propylene and benzene in oil and gas refining as raw materials. Foreign countries have adopted titanium equipment more than ten years ago, and this technology is still under development in my country. The old process used benzene sulfonated alkali solution to produce phenol. Our country has adopted a titanium neutralization reactor, titanium coil cooler, ion titanium nitride agitator sleeve, and titanium target, and the effect is very good.

7. Oxidation of acetaldehyde to acetic acid is a common technology in our country. Titanium is now used as a high-boiling material reboiler, first-grade acetic acid tower reboiler and condensing cooler and other equipment. Foreign countries have adopted titanium equipment in rectification towers, fractionation towers, and distillation towers. Especially in the oxidation of lower alkane to produce acetic acid, there are many by-products, with a formic acid content of 8%, which is extremely corrosive. At this time, titanium is used to replace stainless steel, and the effect is very ideal.
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