December 2019 – Zirconium Metal

How to Ensure the Welding Quality of Zirconium Alloy

In the previous article, we introduced the basic properties of zirconium alloys and the problems that easily occur during the welding process. Next, we will explain how to ensure the welding quality of zirconium alloys and some precautions.

Precautions for zirconium alloy welding

In the welding prefabrication stage of a large number of welds, a special closed clean place needs to be set up, and strict control of environmental dust pollution and air humidity. For example, when entering the construction site, measures such as wearing clean labor insurance shoes must be worn to ensure the cleanness of the welding environment. In the outdoor installation environment, make a temporary operating room to achieve clean conditions.
Strengthening the requirements for the weld joint groove and within 70mm of both sides of the groove and the cleanliness of the surface of the welding wire is an important factor to ensure the welding quality.
In the welding process of zirconium alloy, pores are the most prone to defects, and it is mostly concentrated near the fusion line and the centerline of the weld. The most critical steps to prevent the occurrence of welding porosity defects are to strengthen the control of the cleanliness and humidity of the welding environment, and to enhance the cleaning of the bevel and the surface of the welding material, so as to improve the quality of the internal and external protection of high purity argon in the weld zone.
The zirconium alloy has a low thermal expansion coefficient, a small amount of thermal deformation, and a small volume change during phase change. It has a low content of impurities such as sulfur, phosphorus, and carbon, so there is no obvious tendency to form cracks during welding. However, when the welding seam absorbs a certain amount of oxygen, nitrogen and hydrogen gas impurities, the performance of the welding seam and the heat-affected zone will become brittle. If there is stress in the weld in the peer group, a cold crack will occur. In addition, the hydrogen atoms have the property of diffusing and accumulating to the high-stress parts in the heat-affected zone at a relatively low temperature, which promotes the formation of relatively weak links in these parts, which may lead to the occurrence of delayed welding cracks.
In the welding test, manual tungsten argon arc welding with low welding line energy and convenient gas welding protection should be selected; The larger-diameter welding torch nozzle, the outer surface of the weld seam, and the internal argon filling method of the pipe are used for air isolation to achieve the purpose of the weld seam not being oxidized and absorbing harmful gases.
The filler wire used for zirconium alloy welding should be selected according to the principle of matching the composition of the base metal. The surface of the welding wire must be free from defects such as heavy skin, cracks, oxidation, and metal or non-metallic inclusions. The welding wire should be cleaned and dried before use.
Zirconium alloy tungsten arc welding requires high-purity argon with a purity of not less than 99.999%, and its impurity content meets the requirements of the current GB / T4842 standard. Due to the extremely high requirements for the purity of the welding protective gas, the welding process needs to be continuously inflated and cannot be interrupted halfway, otherwise, the argon filling must be replaced again. The method of using an ordinary single bottle of argon direct gas supply cannot meet the protection requirements. Multiple bottles of argon gas need to be connected in series to increase the gas supply capacity, and multiple welders can be operated simultaneously by dividing the cylinder.
Because zirconium alloys are active at high temperatures, relying solely on the argon gas supplied by the argon arc welding torch nozzle to protect the molten pool and high-temperature bead and heat-affected zone during welding cannot guarantee the welding quality. In order to ensure that the requirements for gas isolation in high-temperature areas and prolonged argon protection time are met, special external gas protection devices for pipes must be added to provide high-purity argon isolation protection for weld pools, high-temperature weld beads and heat-affected zones at high temperatures.

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

Problems Prone to Welding of Zirconium Alloys at High Temperatures

Zirconium is an expensive corrosion-resistant metal material with excellent resistance to corrosion by acids and alkalis. In some media, it even exceeds metals with good corrosion resistance such as niobium and titanium. Zirconium alloys have been gradually used in recent years as structural materials for equipment and pipelines in the chemical industry due to their good corrosion resistance.

The commonly used zirconium alloy grades include Zr702 (UNSR60702), Zr704 (UNSR60704), and Zr705 (UNSR60705). Among them, Zr702 (UNSR60702) is widely used in chemical projects.

Basic characteristics of zirconium alloy

Zirconium alloy has good welding performance, stable chemical properties at room temperature, and outstanding corrosion resistance. However, its high-temperature chemical properties are lively and have a strong affinity for the pollution of oxygen, nitrogen, and hydrogen in the ambient gas, and dust and humidity in the operating environment. As the temperature rises, its chemical activity sharply increases, and it forms ZrH2 with hydrogen at 200 ℃; it can form ZrO3 with oxygen at 300 ℃; it reacts with oxygen in the air above 550 ℃ to form a porous brittle oxide film; at 600 ° C, zirconium absorbs nitrogen to form ZrN; it absorbs oxygen and severely embrittles the material at above 700 ℃. As the temperature increases, its absorption capacity and reaction speed increase. Therefore, the high temperature environment and welding seams generated by welding are the keys to restrict chemical equipment.

The excellent corrosion resistance of zirconium alloys comes from the oxide film formed on its surface and depends on the integrity and robustness of the oxide film. When zirconium alloy absorbs a certain amount of oxygen, nitrogen, hydrogen and other gas impurities, its mechanical properties and corrosion resistance will drop sharply. Therefore, strengthening the protection of environmental dust, humidity and heat-affected zone surfaces and the back of welds is a key element of quality control during welding.

Problems prone to welding of zirconium alloys

High temperature is the natural enemy of zirconium alloys with great changes in corrosion performance. Zirconium generally reacts easily with the atmosphere at high temperatures. It starts to absorb oxygen at 200 ℃, hydrogen at 300 ℃, and nitrogen at 400 ℃. The higher the temperature, the more intense the reaction. Because zirconium is active against oxygen, nitrogen and hydrogen, it must be protected with a high-purity inert gas or welded in a good vacuum chamber.

During zirconium welding, the weld seam and heat-affected zone are easily polluted by oxygen, hydrogen, nitrogen and other elements in the air, forming hard and brittle compounds, and producing a brittle needle-like structure, which increases the hardness and strength of the welded joint , while the plasticity declines, and the corrosion resistance is also greatly reduced. Therefore, zirconium welding should fully protect the molten pool, weld and heat-affected zone to completely isolate the air.

The welding of zirconium alloys is generally performed by the welding method of tungsten inert gas shielded arc. Other welding methods include electron beam welding, plasma arc welding and resistance welding. Its welding performance is close to that of titanium metal welding. Due to the small thermal expansion coefficient and elastic modulus of zirconium, the welding deformation and weld residual stress are relatively small. It is recommended that the stress relief time of the weld at 1100 ° F (594 ℃) be 1 hour/inch thickness.

Another major problem of zirconium welding is that the weld is prone to soften too much and cause the weldment to be distorted. When welding zirconium, the welding piece should be properly fixed and double-sided welding should be used as much as possible. Except for titanium, niobium, silver, and vanadium, zirconium cannot be directly welded to other metals. Therefore, choosing a clean operating environment and strengthening the isolation and protection of welds and heat-affected zones are the keys to ensuring the quality of zirconium alloy welding.

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

Basic Info | Toughening Methods of Zirconia Ceramics

Zirconia (ZrO2) ceramics are special ceramics with unique physical and chemical properties, and their applications in electronic ceramics, functional ceramics and structural ceramics have developed rapidly. However, the fatal shortcomings of zirconia ceramic materials are brittleness, low reliability, and low repeatability, which seriously affect its application range. Only by improving the fracture toughness of zirconia ceramics, strengthening the material and improving its reliability and service life, can zirconia ceramics truly become a widely used new material.

Toughening technology of zirconia ceramics has been a hot spot in ceramics research. At present, ceramic toughening methods mainly include phase change toughening, particle toughening, fiber toughening, self-toughening, diffusion toughening, synergistic toughening, and nano-toughening, etc.

Phase toughening

Phase toughening refers to the metastable tetragonal phase t-ZrO2 undergoing a phase change under the action of the stress field at the crack tip, forming a monoclinic phase, resulting in volume expansion, thereby forming compressive stress on the crack, hindering crack growth, and increasing the role of toughness. In addition, external conditions (such as laser shock, fatigue fracture toughness, low temperature, grain size and content, critical transition energy, etc.) have a great effect on the phase toughening of zirconia ceramics. If the phase transition produces large stress and volume changes, the product is prone to fracture. Therefore, the influence of external factors on the phase toughening of zirconia ceramics should be avoided during production.

Particle toughening

Particle toughening refers to the method of using particles as a toughening agent and adding it to ZrO2 ceramic powder. Although its effect is not as good as whiskers and fibers, if the particle type, particle size, content and matrix material are properly selected, there is still a certain strong effect. The advantage is that it is simple and easy to implement, and it will also improve the high-temperature strength and high-temperature creep performance while toughening. The toughening mechanism of particle toughening mainly includes the refinement of matrix grains and crack-turning bifurcation.

Fiber toughening

The principle of fiber and whisker toughening is that the crystal close to the crack tip adds closing stress to the crack surface due to deformation, offsets the external stress at the crack tip, and passivates the crack propagation, thereby strengthening the toughness. In addition, when cracks are propagated, the frictional force must be overcome when the columnar crystals are pulled out, which also plays the role of toughening.

Self-toughening

Due to the existence of columnar crystals, cracks will be deflected during the fracture process of zirconia ceramics, which will change and increase the path of crack growth, thereby passivating the cracks, increasing the crack growth resistance and achieving toughening.

Diffuse toughening

Diffusion toughening mainly refers to the toughening of the ceramic matrix by the tetragonal ZrO2 particles. In addition to the phase toughening mechanism, there is also a diffusion toughening mechanism of the second phase particles. Before cracks propagate, the internal residual strain energy of the ceramic itself must first be overcome to achieve the purpose of toughening.

Microcrack toughening

Micro-crack toughening refers to adding a tough material at the crack stress tip to cause micro-cracks to achieve the purpose of dispersing stress, reducing the force of crack advance, and thereby increasing the toughness of the material. When a material undergoes a phase transition, it often results in residual strain energy effects and microcracks. Therefore, the effect of phase transition toughening is significant.

Composite toughening

Composite toughening refers to the simultaneous use of several toughening mechanisms during the actual toughening of ZrO2 ceramics, thereby improving the toughening effect of ZrO2 ceramics. In the actual application process, the specific toughening mechanism is selected according to the different properties of the zirconia ceramic material to be prepared.

Nano toughening

At present, there are three main academic viewpoints of nano-toughening, namely: the theory of refinement, trans-crystalline, and “pinning”.

The refinement theory believes that the introduction of nano-phases can suppress the abnormal growth of the matrix grains, refine the matrix structure uniformly, and improve the strength and toughness of the nano-oxide ceramic composites.
The trans-crystalline theory holds that in nanocomposite materials, the matrix particles are densified with the nanoparticles as the core, and the nanoparticles are encapsulated inside the matrix grains to form an “intracrystalline” structure. In this way, the effect of the main grain boundary can be weakened, transgranular fracture is induced, and transgranular fracture instead of intergranular fracture occurs when the material is fractured, thereby improving the strength and toughness of the nano-zirconia ceramic composite material.
The “pinning” theory believes that the nanoparticles existing in the grain boundaries of the matrix produce a “pinning” effect, which limits the occurrence of grain boundary slippage, pores, and creep. The enhancement of grain boundaries leads to the improvement of the toughness of nano-zirconia multiphase ceramic.

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.