Tungsten-Rhenium Thermocouples Introduction and Failure Analysis

Tungsten- rhenium thermocouples is 60 years developed a high-temperature thermocouples, tungsten / ( tungsten- rhenium -26 ) , ( -3 tungsten rhenium ) / ( -25 tungsten rhenium ) , ( tungsten- rhenium -5 ) / ( W - 26 rhenium ) and ( tungsten rhenium -5 ) / ( -20 tungsten rhenium ), etc. Long-term use temperature of 2000 ~ 2400 ℃, short-term use up to 3000 ℃. In the low-temperature thermocouples , ( copper -2.1 cobalt ) / Cu thermocouple, the 10K or more thermoelectric power greater than 10μV / K; gold contains trace amounts ( about 0.07 atomic percent ) alloy of iron and nickel-chromium alloy thermocouples at liquid helium temperature (4K) thermoelectric power greater than 10μV / K, all the better . ( Pt -0.1 Mo ) / ( Pt -5 Mo ) , ( Pt -1 Mo ) / ( Pt -5 Mo ) and tungsten , and 0.5 to 1 ( atomic% ) alloy of osmium and rhenium tungsten alloy thermocouples etc. can be used in the nuclear radiation conditions . In addition to metallic materials, graphite and other non-metallic materials, refractory compounds can also be used as high temperature thermocouples. The advantage of such materials are high melting point , high temperature stability, high thermal potential and thermoelectric power , etc. ; drawback is brittle materials , graphite is easy to absorb moisture and changes in thermal resistance , poor reproducibility , but also in research and development into . Such thermocouples with carbon / graphite , graphite / carbide , carbide / carbide .tungsten-rhenium thermocouples

Tungsten- rhenium thermocouples ! Generally in a vacuum or reducing atmosphere used , if the transmission distance is long , it requires specialized wire compensation .

Tungsten- rhenium thermocouple as an excellent high-temperature measurement sensor , the maximum temperature can reach 2800 ℃, is currently measured temperature above 1800 ℃ better contact industrial thermocouples, are widely used in aero-engine plume exploration , petrochemical heavy oil cracking furnace, coal gasification , metallurgical atmosphere furnace , nuclear reactor core temperature measurement. tungsten rhenium thermocouple wire in an inert gas and dry hydrogen thermoelectric properties stable, but vulnerable in an oxidizing atmosphere oxidation at different oxygen partial oxidization of the linear , when a very complete oxidation of the material properties which cause a qualitative change , it will lead to fundamental changes in thermoelectric properties .

1 In order to make the tungsten rhenium thermocouple wire used in an oxidizing atmosphere , and foreign scholars have done a lot of research, using a variety of oxidation technology so that it can be applied to an oxidizing atmosphere , for example , the coating protection law, taking the sealing Protection Act , taking the inflatable seal protection law, fill seal protection law.

2 , but on the tungsten rhenium thermocouple wire in nitrogen , high temperature stability of carbon in the environment has not been reported in this study through the tungsten rhenium thermocouples field failure analysis , discussion in nitrogen, high-temperature carbon environment, tungsten failure of rhenium thermocouples , has obvious theoretical significance and practical value !

Are many types of thermocouples , thermocouple domestic industry is widely used for the current product quality and classification of the different manufacturers , product quality and performance has a different problem , as technology continues to improve , the product and quality of life has made ​​great progress !


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High-Performance Tungsten Rhenium Alloy Project To Promote the Application Range of Conditions and prospects and Problems and Improvements

Tungsten -3 rhenium tungsten rhenium alloy wire is mainly used for the electron gun , TCD filament , packaging and testing probe card, the alloying element rhenium uniformity and processing difficulty, products are mostly dependent on imports , the project by improving the level of technology and equipment level , successfully prepared tungsten rhenium alloy wire , and to achieve mass production, downstream manufacturers to meet domestic requirements , to replace imported tungsten rhenium wire, mainly used in electronics technology, high-temperature alloy technology and aerospace technology and other aspects :tungsten rhenium alloy wire

Tube material often subject to temperature changes and strong vibration , tube filament tungsten rhenium alloy wire used , a wide composition range . Requires high -performance anti- sagging filament , generally doped tungsten -3 rhenium tungsten rhenium alloy wire , requiring good low temperature ductility filament , usually tungsten -20 -25 rhenium tungsten rhenium and tungsten rhenium alloy wire. Satellite tubes require long life, high reliability , anti- vibration , launch satellites , tubes typically are exposed to 5-8G acceleration of gravity , -3 rhenium tungsten filament material requires tungsten rhenium alloy wire as the filament in order to meet the requirements.

Medical treatment machines and industrial inspection machines accelerated electron gun filament heated tungsten rhenium alloy wire must be used , while ensuring the performance requirements , to meet the long life requirements.

Folding pressure rectifier filament choose tungsten rhenium alloy wire production, not brittle , splitting fracture , rectifier electrical parameters of good consistency.
Tungsten- rhenium alloy is also used in the X-ray tube anode target target surface , the radiation effect, electron impact resistance performance is good , focal path loss, the focus is small, reducing the anode angle , the rotation is an excellent anode material. Tungsten- rhenium alloy target having a tungsten target both high penetration ability, and a molybdenum target and good color characteristics, in practice , the use of low voltage, for different thickness of the soft tissue , light metals and nonmetal soft X radiographs , with good results ; using a high voltage , it has the same effect as the tungsten target , as a target multipurpose .

Many commonly used electrical switch contact material into a car horn contacts and ignition contacts, voltage regulator contacts , telephone contacts and so on. In operation, the friction between each pair of contacts and spark erosion and high frequency characteristics of the contact , the contact material shall satisfy the following requirements, such as materials, contact resistance, arc volt-ampere characteristics and erosion rates of small and small , tungsten- rhenium alloy contact material is used for the development of new products in recent years , its performance can be used with platinum, rhodium and other noble metal contact material comparable.

In short , tungsten rhenium alloys are widely used in resistor technology , thermal control , modern nuclear technology, astronautics technology, high temperature technology , instrumentation , power vacuum , electrical contact and wear-resistant materials.

High-performance tungsten rhenium alloy completion of the project to achieve a tungsten -3 rhenium tungsten rhenium alloy wire production, but only this one type of tungsten- rhenium wire unable to enter the high-temperature thermocouple industry , in the next phase , rhenium tungsten -3 tungsten- rhenium alloy wire preparation techniques , based on improved equipment and processes through exploration, accumulated successful experience and data , other types of tungsten alloy for late development and lay a solid technology, tungsten, rhenium and tungsten -26 -20 rhenium tungsten rhenium alloy wire production.


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High-Performance Tungsten Rhenium Alloy Project To Promote the Role of Meaning and Application Prospects

High-performance tungsten rhenium alloy project role significance ( direct economic and social benefits )tungsten rhenium alloy

1 ) Direct Economic Benefits : in 2008 , the production of tungsten rhenium wire 10 million meters or more, thick wire is higher than 75% of total finished goods ; sales income of 200 million yuan, profit of 500,000 yuan ; 2009 , to achieve industrialization.

2 ) Social Significance : Tungsten -3 rhenium tungsten rhenium alloy wire is mainly used for the electron gun , TCD filament , packaging and testing probe cards , etc., as rhenium alloy element distribution uniformity and processing difficulty is high, products are mostly dependent on imports , the project By improving the level of technology and equipment level , successfully prepared tungsten rhenium alloy wire , and to achieve mass production, downstream manufacturers to meet domestic requirements , to replace imported tungsten rhenium wire , to fill the domestic blank, rich variety of high-end products, tungsten , and promote China development of deep processing power to tungsten .

High-performance tungsten rhenium alloy project promotion prospects

The project has achieved mass production , and achieve good economic returns , the products are mainly used in the electron gun , TCD filament , packaging and testing probe cards. In recent years , China's rapid development of chip production , China's manufacturing base has become the chip packaging and testing requirements of the test probe cards is growing, packaging and testing for the project with a tungsten rhenium wire probe card provides a broad development prospects .

Tungsten- rhenium alloy excellent thermoelectric properties and a high melting point , making it the highest maximum temperature contact method of the material , measurable 2800 ℃ high temperature . As fast thermocouple, use in the metallurgical industry steel and tungsten rhenium thermocouples measure the temperature of molten iron in the chemical industry in the tungsten- rhenium thermocouples used instead of expensive platinum-rhodium thermocouple . This helps greatly reduce costs, but also for the tungsten rhenium alloy explore a wider range of ways to apply . By a combination of a tungsten rhenium alloy wire thermocouple to measure the temperature of the upper electrode is close to the melting point of the rich rhenium . Compare with other thermocouples , tungsten rhenium thermocouple output thermoelectric power maximum , the highest sensitivity , thermoelectric power increases with the rhenium content increased.

Thus, the completion of the project to achieve a tungsten -3 rhenium tungsten rhenium alloy wire production, in the next phase , the tungsten rhenium tungsten rhenium alloy wire -3 preparation techniques , based on improved equipment and processes through exploration, accumulated successful experience and data for other types of post- tungsten alloy development and lay a solid technology, tungsten, rhenium and tungsten -26 -20 rhenium tungsten rhenium alloy wire production, tungsten- rhenium alloy systematically expand the company's product range and product quality, reserves to rely on technology to improve the company's competitiveness and profitability , instead of high-end imported tungsten rhenium wire.


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High-Performance Tungsten Rhenium Alloy Innovation Projects

High-performance tungsten rhenium alloy production must first address the element rhenium alloy homogeneous distribution, which is the production of tungsten rhenium alloy wire preparation of the core technology ; swaged , annealing and drawing process parameters and process selection is tungsten- rhenium alloy wire thermal deformation processing of key technologies.tungsten rhenium alloy

The Innovation of This Project Is To :

A ) the introduction of the food industry used in the medical use of horizontal mixing pot doping , the use of two solid-liquid doping process , to ensure the amount of rhenium and homogeneous distribution of elements are added at the same time , ensure that potassium alloy , aluminum, sulfur content in a certain range .

2 ) tungsten- rhenium alloys with rhenium solid solution strengthening effect now , alloy hardening speed, using a small compression ratio , the corresponding annealing point selection , the successful introduction of
3.7mm tungsten rod to protect high hydrogen annealing process and protection of the filament is energized hydrogen annealing solution annealing process of oxidation caused by burning and tungsten- rhenium combustion phenomenon.

Doping the second liquid , a liquid doping - pickling process , to ensure potassium alloys , aluminum and sulfur contents of the required range of the alloy ; medical food into the pot as a dopant doped with horizontal , 30kg pickling tungsten powder and the amount of ammonium perrhenate solution was stirred until dry, combination through this process to ensure that the ammonium perrhenate crystals wrapped in each uniform surface tungsten particles precipitated , makes the material in the hydrogen reduction process occurs pre-alloyed for homogeneous distribution of rhenium tungsten rhenium alloy wire to provide an initial ingredients guaranteed.

Tungsten- rhenium alloys with rhenium solid solution strengthening effect now , alloy hardening speed, using a small compression ratio , the corresponding annealing point selection , the successful introduction of hydrogen tungsten rod 3.7mm induction annealing process and the protection of the filament is energized hydrogen annealing protection solution cause oxidation during annealing and tungsten- rhenium burning combustion phenomenon, determined from the whole of 17mm ~ 2mg/200mm tungsten thermal deformation process , a small compression ratio and 7 times the annealing process combination processing to the diameter 0.39mm tungsten single weight of not less than 2.8kg, has reached the international advanced level.


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Tungsten-Rhenium Alloy Wire Applications and Technical Principles

Since the late 1950s , tungsten rhenium alloy has been successfully in many fields of applications, such as high technology , electric vacuum industry, lamp industry, nuclear industry, analysis of technical, medical and chemical . Rhenium content with other tungsten rhenium wire compared to alloy wire doped W-3Re unique properties , high strength, good plasticity, doped W-3Re has the highest recrystallization temperature , 2500 ℃, coupled with a melting point of 3360 ℃, high temperature technology, electric vacuum industry, lamp industry, nuclear industry, analysis of technical, medical and chemical industries widely used, is a rare , hard to replace high-temperature materials.tungsten-rhenium

But today, many areas of our country used W-3Re alloy wire is still dependent on imports, such as CRT electron gun , gas chromatograph thermal conductivity detector , vacuum tube industry , electronics assembly and test probe card of tungsten rhenium wire . W-3Re alloy wire localization without bulk main reasons: one , tungsten rhenium wire in the process , quick hardening , annealing must be timely and difficult process ; Second, China's tungsten industry processing means rich enough , invested more than R & D funding , limiting the development speed . As China's tungsten industry leading enterprises, Hong Lu Xiamen postdoctoral workstation by the company and the National Engineering Research Center of tungsten tungsten rhenium wire proposed R & D project topics , research and development of high-performance tungsten- rhenium alloy wire , in order to meet the needs of domestic users , reduce business risk , enriching the company tungsten product categories.

Application areas and technical principles

Application: tungsten rhenium alloy wire is mainly used for the electron gun , TCD filament , packaging and testing probe cards , etc., as rhenium alloy element distribution uniformity and processing difficulty is high, products are mostly dependent on imports , the project by improving the level of technology and equipment level, successfully prepared tungsten rhenium alloy wire , and to achieve mass production, downstream manufacturers to meet domestic requirements , to replace imported tungsten rhenium wire.

Technical principle: tungsten rhenium alloy can be prepared by a variety of ingredients , tungsten rhenium alloy compared with pure tungsten , rhenium alloy elements added during deformation , is conducive to the formation of twin crystals , reducing the deformation process of stacking fault energy , reducing the grain boundary movement of dislocations impedance ( Pearce - Nabarro stress ) , resulting in increased mobility of dislocations , the alloy exhibits a high ductility. Tungsten- rhenium alloy uneven good plasticity and strength , high hardness, which is usually called " rhenium effect ." Since rhenium effect , tungsten rhenium alloy has a series of excellent performance , high melting point, high hardness, high strength, high ductility, high resistivity , high values ​​of thermoelectric power , high recrystallization temperature , low vapor pressure , low electron work function and low ductile-brittle transition temperature. Tungsten- rhenium alloy is an excellent high-temperature structural materials technology in electronics , thermal control , modern nuclear technology and Space Technology , temperature field , instrumentation , electrical , and other cutting-edge technology have been widely used.


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Tungsten-Rhenium Alloy Wire Compare The PerformanceIndicators and Parameters

Tungsten- Rhenium Alloy Wire Performance Indicatorstungsten-rhenium alloy wire

Production to meet the electron gun , traveling wave tubes , TCD hot wire probe card assembly and test requirements of the customer base W-3Re tungsten rhenium alloy wire :

1 ) tungsten rhenium wire distribution of rhenium , rhenium content fluctuations within 30.15% ;
2 ) billet Weight 3Kg;
3 ) to a diameter of 0.39mm, tungsten- rhenium alloy wire yield not less than 75% ;
4 ) tungsten- rhenium alloy wire filament wire diameter evenly.

Comparison with Other Similar Technologies

Tungsten- rhenium alloy wire and foreign well-known company performance parameters comparison:

Performance Parameter Name Domestic Companies Foreign Companies

Rhenium uniform uniform uniform distribution element
Wire rhenium content of 3% 0.15 3% 0.15
Resistivity ( room temperature ) cm 10 10 ~ 6> 10 ~ 6 10 10 ~ 6
b (49mg/200mm) MPa> 2265> 2570
Elongation > 1.6 > 3%
Billet single root weight , kg 64 1.5

Drawing tungsten alloys elongated grain structure of the close-packed crystal fibers , recrystallized grain structure of the grain structure of the dovetail -shaped lap , the grain aspect ratio greater than 12.
Promotion of technological achievements , the products have been authorized users downstream manufacturers at home and abroad , to replace imported products comprehensive performance indicators have reached the international advanced level of similar products .


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Seismic Features and Applications of Tungsten

Seismic tungsten filament according to its normal and has the characteristics of high seismic named, it is mixed with the tungsten powder potassium, sulfur and prepared from aluminum and other elements. It is the tungsten material has the special properties of a class of products, which not only has high resistance to sag tungsten normal performance, good around the system performance, but also has a high shock and vibration resistance performance.

Tungsten is mainly used in seismic vibration environment lighting systems, for example, various traffic lights, special light bulbs for military purposes, aerospace engine heating wire, etc., which is the largest amount of cars, motorcycles, tractors, aircraft lighting lights.

Another important seismic tungsten is a variety of application areas kinescope cathode heating wire, the annual consumption of at least 600 million meters. As the world's automotive, electronics and other industries, these figures every year extensions. According to statistics, in 1999 the domestic market demand is 214 million meters, at an annual growth rate of 8%, to 2005 domestic demand will reach 31.8 billion meters, its output will be 314 billion yuan in 1999 to 514 in 2005 billion.

However, with the development of society and the advancement of science and technology, but also on the quality of seismic tungsten proposed more stringent requirements. General production process seismic tungsten wire, high temperature work, the seismic performance is not satisfactory, tungsten formability poor wound easily broken when the double helix filament yarn, filament deformation and luminosity is unevenly distributed. Therefore, the optimization of production processes, improve production processes, high temperature performance with good preparation, processing and wire around the excellent performance of the seismic tungsten has important practical significance.


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Anti-Sag Tungsten Wire Performance

Tungsten at a certain temperature and a certain resistance to their sagging under load deformation capacity. Anti-sagging properties of the material is actually a reflection of high temperature creep resistance, which is doped with tungsten is a very important performance indicators.tungsten

Tungsten filament incandescent bulbs and a vacuum device, its working temperature is usually above 2000 ℃, so the effect of high temperature and tungsten weight, since the material strength is decreased and the grain boundary sliding and produce sag. To ensure that the shape of the filament at a high temperature and dimensional stability, requires tungsten must have good high temperature sag resistance capability. This capability and the recrystallization temperature of tungsten grains after recrystallization geometry closely related. For doped with potassium, aluminum, silicon, tungsten wire, because of its high recrystallization temperature, and recrystallized to form a large aspect ratio of recrystallized grains, and between the grains was dovetail lap, this structure makes the most of the grain boundary is parallel or nearly parallel axes wire, which significantly improves the ability of the tungsten filament temperature sag resistance.

Tungsten-doped high-temperature sag resistance capacity, mainly by the potassium tungsten bulb size, number, and distribution (dispersion state) is determined, and the dispersion state of the bubble in addition to potassium and potassium in the outside, suitable deformation and heat treatment system is essential, the former is the ability to obtain a prerequisite for sag resistance, and the latter is a necessary condition.

Determination of anti-sag tungsten wire performance in many ways, a common high-temperature creep test method, high flexural droop method (V-shaped test) and so on. Service conditions from the point of view of the filament, sagging test method than the creep test method using tungsten better meet the actual situation. Thus creep test method is gradually being replaced by sagging test for detecting anti-sag tungsten high temperature performance.


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Tungsten-Rhenium Wire Problems in Useing

1 Errors Introduced by Improper Installationtungsten-rhenium wire

Thermocouples should be mounted too close to the door and the heated places, insertion depth should be at least the diameter of the protective tube 8 to 10 times , and the insertion depth of the installation position does not reflect the true temperature of the furnace . Thermocouple protection tube with intramural interval Unfilled adiabatic material , resulting in overflow hot or cold air furnace , so the thermocouple protection tube and the gap between the furnace wall hole applications such as refractory cement or asbestos insulating material clogging rope to avoid hot and cold air convection and affect the accuracy of temperature measurement . Thermocouple should be installed as far as possible away from strong magnetic fields and strong electric field, thermocouple and power cables should not be wire-bound with a catheter in order to avoid the introduction of interference caused by errors. Thermocouples can not be installed in measured media rarely flows in the region, when measured with a thermocouple tube gas temperature must be going against the flow direction of the thermocouple installation , and full contact with the gas .

2 Error Introduced Insulation Deterioration

Such as thermocouple protection tubes and pull plates excessive dirt or salt residue resulting thermocouple very poor insulation between the wall of the furnace at high temperature is more serious , it will not only cause the loss of thermoelectric power but also the introduction of interference , resulting the error sometimes up on Baidu .

3 the Error Introduced by the Thermal Inertia

As the thermal inertia of the thermocouple indication value of the instrument behind the measured temperature changes , while a fast measurement of this effect is particularly prominent. It should be possible using the hot electrode smaller, smaller diameter thermocouple protection tube . Temperature environment permit, or even take away the protective tube . Because of measurement hysteresis , thermocouple temperature fluctuation of the detected temperature fluctuation amplitude is small amplitude . Measuring lag larger the smaller the amplitude of fluctuation thermocouple , the greater the difference between the actual oven temperature . When a large time constant thermocouple or temperature control , the instrument displays the temperature fluctuation is small though , but the actual oven temperature fluctuations may be significant. To accurately measure the temperature , time constant should be selected thermocouple . The time constant and the heat transfer coefficient is inversely proportional to the diameter of the thermocouple hot end , and the material density is proportional to the specific heat , such as to reduce the time constant , in addition to increasing the heat transfer coefficient , the most effective way is to minimize the size of the hot end . Use, usually good thermal conductivity materials, thin wall, small diameter protection tube . In the more precise temperature measurement, the use of non- bare wire thermocouple protection tube , but the thermocouple easily damaged, should be promptly corrected and replaced.


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Sapphire Tungsten Rhenium Alloy Wire Production Process

1.1 powder preparation and doping techniques

Preparation of low temperature pre-reduction of suitable phase composition of blue tungsten oxide , and tungsten blue oxide is doped tungsten powder acid , tungsten powder as needed , and control the ratio of rhenium powder .

Doping uniformity is the first element control , to be able to obtain a stable in terms of purity , scale, and the particle size requirements of the three indicators . tungsten-rhenium alloy wire

The use of advanced hydrogen reduction equipment, as well as doping , pickling, large capacity V-type mixed powder machine , especially for hydrogen production system optimization , for the implementation of powder technology to provide reliable protection .

1.2 sintering and molding processing technology cogging

Using isostatic round billet rolling through vertical melt after blooming , which is tungsten and molybdenum Solton most advanced processing technology , preparation of billet single weight 3 kg , the use of high-power -controlled vertical melt equipment, to stable obtain density , purity and grain size , etc. to meet the requirements of the master index tungsten rhenium billet .

Blooming accommodate large rolling method billet , to achieve quality and efficient, large-scale production of the best processing methods. Solton tungsten and molybdenum technology uses KDCKS three multi-stand rolling mill rolls and master its system technology. At present, most enterprises still use rotary forging billet made ​​to open , but open up technology and equipment, molds, auxiliary facilities and so has shrunk, with advanced rationality.

1.3 swaging and stretching techniques

Multimode string forging more with welding, high frequency continuous annealing , Big Wheel and multimode continuous drawing machine drawing machine applications, using a large compression rate processing, oxidation annealing , using condensate crystal drawing dies , etc., composed this section technical characteristics .

Using a large compression ratio stretched to the protection of tungsten rhenium wire has good high temperature performance with excellent positive significance. Has adopted pass compression rate specification , ¢ 3.7-0.7mm range of 30% -40%, ¢ 0.7-0.2mm range of 18% -28 % . Four to ten die mold sliding multimode drawing machine has been applied .

1.4 Electrochemical Processing Technology

Since sapphire tungsten rhenium alloy wire with multi- supplier status with white silk , so it is necessary to wash separately electrolytic corrosion , galvanic corrosion and electrolytic polishing reducing effect.

1.5 Control Management Technology

Because they have a better grasp of APT and ammonium perrhenate from raw materials to final products, all tungsten rhenium wire process control and management techniques to develop more scientific focus of the process measurement and control standards, and has a full range of advanced testing methods, Solton tungsten and molybdenum Technology is focused on creating ¢ 1.0-0.2mm range crack detection system .

1.6 Equipment Technology : mixer, reduction furnace , vertical melt equipment, rotary swaging machine, wire drawing machine, electrochemical etching equipment, testing equipment and packaging machines.


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