Mechanisms of Grain Growth Inhibition

The grain growth inhibitors primarily influence WC grain growth through the following approaches:

Solute Drag Effect

Principle:grain growth Inhibitor elements (e.g., V, Cr) dissolve into the WC or Co phase, adsorb at WC/Co phase boundaries or WC/WC grain boundaries, hindering atomic diffusion and grain boundary migration.

Elemental Solid Solution

Inhibitors such as VC and Cr?C? decompose during sintering, with V and Cr atoms dissolving into the WC lattice or Co binder phase.

Example: V substitutes W sites in WC (forming (V,W)C solid solution), while Cr dissolves into the Co phase (forming (Co,Cr) solid solution).

Grain Boundary Segregation

Solute atoms (e.g., V, Cr) enrich at WC grain boundaries or WC/Co interfaces, forming a “solute atmosphere.”

These segregated atoms pin grain boundaries, increasing the energy barrier for migration.

Drag on Grain Boundary Movement

When grain boundaries attempt to migrate, solute atoms must move along, but their slower diffusion rate impedes boundary motion.

Analogous to “viscous drag,” this suppresses WC grain coalescence and growth.

Applicable grain growth Inhibitors: VC, Cr?C? (primarily rely on solute drag).

Second-Phase Pinning Effect (Zener Pinning)

Principle: grain growth inhibitors form nanoscale carbide particles (e.g., (V,W)C, (Cr,W)C) that physically obstruct WC grain growth at boundaries.

Nanoparticle Precipitation

During sintering, decomposed VC or Cr?C? reprecipitate as nanoscale carbides (e.g., 5–50 nm (V,W)C particles), typically located at WC/WC or WC/Co interfaces.

Grain Boundary Pinning

Migrating boundaries must overcome the restraint of these nanoparticles, requiring additional energy.

According to the Zener equation, pinning force (F?) correlates with particle volume fraction (f) and size (r). Finer, denser particles yield stronger inhibition.

Suppression of WC Dissolution-Reprecipitation

Nanoparticles hinder WC dissolution in liquid Co and redeposition, reducing Ostwald ripening (“large grains consuming small ones”).

Applicable grain growth Inhibitors: VC (strongest pinning), Cr?C? (moderate), TaC/NbC (weaker).

Common Grain Growth Inhibitors and Their Characteristics

Selection and Optimization of grain growth Inhibitors

Ranking of Inhibition Effectiveness

VC > Cr?C? > TaC ≈ NbC

Key Influencing Factors

Sintering Temperature and Time:

High temperatures or prolonged sintering may weaken inhibitor effectiveness (e.g., VC particle coarsening).

Co Content

Alloys with higher Co require greater grain growth inhibitor content (due to enhanced WC dissolution in liquid Co).

Carbon Balance

Inhibitors may consume free carbon, necessitating carbon potential adjustment to avoid η-phase formation (e.g., Co?W?C).

Detailed Industrial Application Cases of Cemented ????? Grain Growth Inhibitors

Grain growth inhibitors (e.g., VC, Cr?C?, TaC) are widely used in the cemented carbide industry, primarily in cutting tools, mining tools, and wear-resistant components. The selection of different inhibitors directly affects the alloy’s hardness, toughness, wear resistance, and high-temperature stability. Below is an in-depth analysis of several typical application cases.

Ultra-Fine Grain Cemented Carbide Cutting Tools (VC + Cr?C? Composite Inhibition)

Application Background

Requirement: High-speed cutting and precision machining (e.g., automotive engine blocks, aerospace titanium alloys) demand tools with both high hardness (>90 HRA) and chipping resistance.

Issue

Conventional WC-Co alloys have coarse grains (1–3 μm), exhibiting high hardness but low toughness, leading to edge chipping.

Solution

Ultra-fine grain cemented carbide (grain size 0.2–0.5 μm) achieved through VC (0.3–0.5 wt%) + Cr?C? (0.5–1.0 wt%) composite addition.

Inhibition Mechanism

VC: Nano-sized (V,W)C particles pin WC grain boundaries (Zener pinning), suppressing grain coalescence.

Cr?C?: Cr dissolves into the Co phase, reducing WC dissolution rate (solute drag) while enhancing oxidation resistance.

Representative Products

Sandvik GC4325: For titanium alloy machining, using VC+Cr?C? inhibition (0.3 μm grains).

Kennametal KCS10B: For stainless steel finishing, incorporating nano-VC.

Mining Cemented Carbide Drill Bits (TaC/NbC High-Temperature Inhibition)

Application Background

Requirement: Oil drill bits and tunnel boring machine cutters operate under high temperatures (>800°C) and impact loads, requiring thermal fatigue resistance and wear resistance.

Issue

Conventional WC-Co alloys experience rapid grain growth at high temperatures, reducing strength.

Solution

TaC (1–3 wt%) or NbC (1–2 wt%) addition to leverage their high-temperature stability for grain growth suppression.

Inhibition Mechanism

TaC/NbC: Form (Ta,W)C or (Nb,W)C solid solutions at high temperatures, pinning grain boundaries (Zener effect) and reducing boundary mobility.

Synergy with Co binder: Ta/Nb dissolution into Co increases liquid Co viscosity, slowing WC dissolution-reprecipitation.

Representative Products

Atlas Copco Button Bits: TaC-containing drill bits for granite drilling.

Sumitomo Electric DX Series: Oil drilling alloys with NbC for thermal stability.

Wear-Resistant Sealing Rings (Cr?C? Inhibition + Rare Earth Optimization)

Application Background

Requirement: Mechanical seals and bearing sleeves require high wear resistance + corrosion resistance (e.g., chemical pumps, seawater environments).

Issue

WC-Co suffers from selective corrosion of the Co phase in corrosive media, causing WC grain detachment.

Solution

Cr?C? (1.0–1.5 wt%) + rare earth oxides (Y?O? 0.1–0.3 wt%) composite addition.

Inhibition Mechanism:

Cr?C?: Forms (Cr,W)C particles to refine grains while improving corrosion resistance via Cr dissolution in Co.

Y?O?: Rare earth elements segregate at grain boundaries, purifying interfaces and strengthening boundary cohesion.

Representative Products

Mitsubishi Materials EX Series: Chemical pump seals with Cr?C? + rare earth modification.

Oerlikon Durit CR: Corrosion-resistant alloys with Cr?C?.

PCB Micro-Drills (Ultra-Fine VC + Sintering Process Optimization)

Application Background

Requirement: PCB micro-drills (diameter 0.1–0.3 mm) demand ultra-high precision (roundness <1 μm) and fatigue resistance.

Issue

Grain coarsening causes drill edge blunting and fracture during drilling.

Solution

Ultra-fine VC (0.2–0.4 wt%) + low-temperature sintering (1350°C, vs. conventional 1450°C).

Inhibition Mechanism

Nano-VC: Prepared via high-energy ball milling (<50 nm particles) for enhanced pinning.

Low-temperature sintering: Reduces Ostwald ripening time, preserving inhibitor efficacy.

Representative Products

Toshiba Tungaloy DLC-Coated Micro-Drills: Nano-VC inhibition technology.

TaeguTec PCB Drill: Optimized for high-layer PCBs.

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Grain growth inhibitors in cemented carbides control grain size through solute drag and second-phase pinning mechanisms. Their selection must be optimized based on material composition, sintering processes, and performance requirements. Future trends favor nano-composite inhibitors and multi-component synergistic regulation to further enhance comprehensive material properties.

At present, the regions in China that are most active in the recycling and regeneration of waste cemented carbide include Jinan City in Shandong Province, Qinghe County in Hebei Province, Mudanjiang City in Heilongjiang Province, and Zhuzhou City and Changsha City in Hunan Province.

Economic Benefits of Recycling Waste Carbide

Tungsten is the main component of cemented carbide, accounting for almost 50% of the total tungsten usage in its production, with China’s share being around 40%. Relevant data indicate that the demand for cemented carbide in various countries will rise significantly from the end of this century to the beginning of the next. It is estimated that by 2000, the demand could reach 40,000 tons, about 1.5 times the current production. However, tungsten is a rare element, with a crustal abundance of only 1×10?%, and the currently exploitable tungsten is only sufficient for 50 years.

Although China is a major producer of tungsten, both its reserves and recoverable quantities are showing a decreasing trend. Therefore, the rational utilization and recycling of tungsten resources should be placed on our agenda as an urgent issue to be seriously studied. Assuming that China’s recycling rate of waste alloy increases from 10% to 20%, it would mean an annual increase of several hundred tons of tungsten production. This would require the provision of several thousand tons of tungsten concentrate (containing 65% WO?) as raw material, equivalent to the tungsten content of 220,000 tons of raw ore (with a grade of 0.5% WO?). Thus, vigorously recycling cemented carbide is of great significance for the rational utilization and protection of existing tungsten resources.

Another major component of cemented carbide is cobalt. Due to the lack of cobalt resources in China, a large amount of cobalt needs to be imported annually to meet production needs. At the current level, recycling several hundred tons of cemented carbide in China each year could recover several tens of tons of cobalt, thereby saving a significant amount of foreign exchange for?our?country.

Processing Techniques of Recycling Waste Carbide

It is reported that there are currently about 30 different processing techniques used for the recycling of waste cemented carbide. Below is a brief introduction to several of the most commonly used and effective techniques in production.

Nitrate Fusion Method

This method involves melting waste cemented carbide together with nitrate at temperatures ranging from 900°C to 1200°C, resulting in the formation of soluble sodium tungstate. The reaction equation is as follows:

At this stage, the cooled melt is crushed and then leached with water to obtain a sodium tungstate solution and cobalt residue, which are then processed through normal procedures.

The advantages and disadvantages of this method are as follows: it has a large processing capacity and a wide range of applications, but it suffers from low recovery rates, high costs, poor working conditions, and significant pollution.

High-Temperature Oxidation Method

This method involves placing the cemented carbide in a temperature range of 700–950°C to oxidize it in air or oxygen. During this process, oxygen reacts with the alloy through the following chemical reaction:

The oxidized product is a brittle substance that, when treated with sodium hydroxide or a mixture of sodium hydroxide and sodium carbonate in a high-pressure leaching device, yields a sodium tungstate solution. The cobalt remaining in the residue is separated out according to conventional processes.

Phosphoric acid leaching method

Immerse the waste carbide?in a phosphoric acid solution and leach at a temperature of 50-60°C. Phosphoric acid reacts with cobalt in the carbide?to form cobalt phosphate, which enters the solution and separates from tungsten carbide. The advantages and disadvantages are: since phosphoric acid is a weak acid, the problem of equipment corrosion is easily solved, making it suitable for processing various waste carbides. However, the recovered tungsten carbide has a high oxygen content, and the subsequent process flow is long.

Zinc melting method

React waste carbides with zinc at a temperature close to 900°C. The cobalt in the alloy forms a zinc-cobalt low-melting-point alloy, causing the tungsten carbide in the waste alloy to lose the cobalt’s bonding effect and become loose. Then, vacuum distillation is used to evaporate and recover the metal zinc.

After the zinc melting process, the waste carbide?consists of layers of tungsten carbide and cobalt layers arranged in a multi-layered and interlocking pattern. It is a loose bulk material, which, after crushing, becomes a recycled carbide?mixture.

The advantages and disadvantages of the zinc melting method are: the process and equipment are relatively simple, the actual recovery rate is high, the production process causes less pollution, and the recovered mixture can be used directly for the production of tungsten products. However, this method consumes a lot of energy, with an electricity consumption of 4000-10000 degrees for processing 1 ton of waste carbide, and the recovered material contains a small amount of zinc, which has a certain impact on product quality.

Sodium sulfate fusion method

This method involves reacting waste carbides with sodium sulfate at a temperature of 900-1000°C to form a molten tungstic acid. After cooling, it is then leached with hot water to obtain a sodium tungstate solution and cobalt slag. The reaction equation is as follows: (The specific reaction equation is not provided in the original text, so it cannot be translated here.)

Its advantages and disadvantages are: wide adaptability and large production capacity. The drawback is that sulfur dioxide gas is emitted during the production process.

Electrolysis fusion method of recycling waste carbide

This method involves placing the waste carbide?in an electrolytic cell as the anode, nickel plate as the cathode, and dilute hydrochloric acid as the electrolyte. After electrolysis, the cobalt in the carbide?enters the solution in the form of COCl?. The washed and ground WC can be directly used to produce alloys. This method yields pure products, is highly efficient, has simple equipment, and is easy to operate. It is particularly suitable for processing with high cobalt content and has high value for promotion and application.

Cold embrittlement method

The cold embrittlement method involves crushing the waste carbide?coarsely, removing impurities, and then using a high-speed air stream to inject the coarsely crushed carbide?into a vacuum chamber equipped with a carbide?paddle, followed by further crushing to obtain a mixture.

This method has a wide range of processing and treatment, and the production process does not cause environmental pollution, but the equipment cost is relatively high.

According to reports, the zinc dissolution method is widely used for the recycling of waste carbides in China at the current stage. Overseas, the most economical method is considered to be a combination of the zinc dissolution method and the cold embrittlement method. In summary, there are many methods for recycling and processing waste carbides, each with its own pros and cons. When selecting a method in practice, a comprehensive analysis and comparison should be conducted based on the type of waste carbide, the size of the production scale, equipment capacity, technical level, and the source of raw and auxiliary materials, to choose an advanced, reasonable, and economically significant process for production practice.

Technical and Economic Preliminary Evaluation of Several Process Methods for Recycling Waste Carbides

As mentioned earlier, the zinc fusion method, electrolysis dissolution method, and mechanical crushing method have all become the main industrial methods for recycling and regenerating waste carbides. The recycled and regenerated powders can be used to produce carbides through conventional processes, which undoubtedly promotes the full utilization of non-ferrous metal resources such as tungsten and cobalt, saves energy, reduces manufacturing costs, promotes the development of small and medium-sized enterprises, and provides employment for the unemployed. Among them, the powder produced by the electrolysis dissolution method is particularly good in quality with low impurity content, low energy consumption, moderate processing costs, and good economic benefits (the selling price of WC powder is only 60% to 70% of the conventional product). It is one of the main methods being vigorously developed in many regions of our country.

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It should be pointed out that the recycling and regeneration of waste carbides is a new venture and an emerging industrial sector in the field of carbides, which should be affirmed and supported. At the same time, great attention must be paid to product quality in the work of recycling and utilizing waste carbides, especially since most enterprises are still at a relatively low level of manual workshop production. Many enterprises often focus only on economic benefits while neglecting the control and testing of the recycling process and powder quality, which is incorrect. In the future, enterprises engaged in this kind of production should continuously improve and enhance the recycling process and product quality, strengthen the recognition of the importance of “product quality is the life of the enterprise,” and must not be careless. Otherwise, it will be difficult to maintain a firm foothold in the fierce market competition for a long time, let alone continue to develop and grow.

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Cryogenic treatment usually adopts liquid nitrogen cooling, which can cool the workpiece to below – 190 ℃. The microstructure of the treated material changes at low temperature, and some properties are improved. Cryogenic treatment was first proposed by the former Soviet Union in 1939. It was not until the 1960s that the United States applied the cryogenic treatment technology to the industry and began to use it mainly in the aviation field. In the 1970s, it expanded to the machinery manufacturing field.

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The gas principle is to cool by the gasification latent heat of liquid nitrogen (about 199.54kJ/kg) and the heat absorption of low-temperature nitrogen. The gas method can make the cryogenic temperature reach – 190 ℃, so that the cryogenic nitrogen can contact the materials. Through convection heat exchange, the nitrogen can be vaporized in the cryogenic box after being ejected from the nozzle. The workpiece can be cooled by the latent heat of gasification and the heat absorption of cryogenic nitrogen. By controlling the input of liquid nitrogen to control the cooling rate, the cryogenic treatment temperature can be automatically adjusted and accurately controlled, and the thermal shock effect is small, so is the possibility of cracking.

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?? ???? ???? ?? ?? ??? ?? WC ???? ?? ??? ????? ????????? ?? ???? ????????? ?? ???? ????? ???, ?? η ??? ?? ??? ?? ???? ????????? ??? Co ?? ??? ???? ??? ???? ??? ??? ?? ??????? ?? ??? ?? ??????? ?? ????? ????? ?????? ??? ???? ??, ?? ???????? ?? ???? ?? ??????? ??? ?????? ?? ????????? ?? ????? ?????? ?? ??? ???? ??? ????? ?????? ??? ?????? ?? ????, ????? ?? ??? ????????? ?? ??? ?????? ??? ???? ??; ????? ?? ???? ?? ????? ?? ???????? ?? ???? ?????? ?????? ??? ????? ??? ??? ?????? ?? ????? ?? ?? ??????????? ????? ?? ???, Co ?? ??????? ?? ????? ?? ????, WC ???? ?? ???? ???? ??? Co ?? ???? ?????? ????? ???? ??? ?????????? ?? ????? ?? ?? ??? ?????? ?? ?????? ?? ???????? ?? ????? ?? ?????? ?? ??? ???? ???

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(2) Start the cryogenic tempering integrated furnace, open the liquid nitrogen, reduce it to – 60 ℃ at a certain rate, and keep the temperature for 1h;

(3) Reduce to – 120 ℃ at a certain rate, and keep the temperature for 2h;

(4) Reduce the temperature to – 190 ℃ at a certain cooling rate, and keep the temperature for 4-8h;

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?? ???? ?? ???? ?? ?? ??????????? ????? ?? ???? ?? ????? ???, ??????????? ????? ?? ??? YG20 ??? ????? ???????? ??????? ??????? (fcc) ???? ?? ?? ??? ??, ε- Co (hcp) ?? ?????? ?????? ?? ????? ?? ???????? ??? ????? ?? ???? ?? ?? ?????? ???????? ?? ?????? ????

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??????? ????? ??????? ??? ?? ??? ??? ??? ????? ?? ?????????? ????????? ?????? ????? ??? ?? ????? ?? ??? ???????? ???????? ?????? ?? ???? ???? 2 ~ 8 ???? ??? ???? ??, ???? ???????? ???????? ???? ??????? ?? ???????? ???? ?? ?????? ?? ????? ?? ??? ?? ???? ??? ?? ?????? ??? 1990 ?? ??? ???, ???????? ???????? ?? ??????????? ????? ?? ????? ??? ???? ??? ??, ?? ??? ??? ?????? ??????? ??? ???

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Edge radius processing is an indispensable process after fine grinding of CNC tools and before coating. The purpose is to make the cutting edge smooth and smooth, and extend the tool life. There are 9 methods of edge radius treatment of CNC tools introduced by Meetyou. Let’s get to know it.

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This is a edge radius processing that applies a magnetic field in the direction perpendicular to the axis of the cylindrical surface of the workpiece, and adds magnetic abrasive between the magnetic field S and N poles. The magnetic abrasive will be adsorbed on the magnetic pole and the workpiece surface, and will be arranged into a flexible “abrasive brush” along the direction of the magnetic line of force. The cutter rotates and vibrates axially at the same time to remove the metal and burrs on the workpiece surface.

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Etching is a technology that uses chemical strong acid corrosion, mechanical polishing or electrochemical electrolysis to treat the surface of objects. In addition to enhancing aesthetics, it also increases the added value of objects. From traditional metal processing to high-tech semiconductor manufacturing, they are all within the scope of application of etching technology.

Metal etching is a technology to remove metal materials through chemical reaction or physical impact. Metal etching technology can be divided into wet etching and dry etching. Metal etching consists of a series of chemical processes. Different etchants have different corrosion characteristics and strength for different metal materials.

Metal etching, also known as photochemical etching, refers to the removal of the protective film of the metal etching area after exposure, plate making, development and contact with the chemical solution in the process of metal etching, so as to achieve dissolution corrosion, formation of bumps, or hollowing out. It was first used to manufacture printed concave convex plates such as copper plate and zinc plate. It is widely used to reduce the weight of instrument panel or process thin workpieces such as nameplate. Through the continuous improvement of technology and process equipment, etching technology has been applied to aviation, machinery, chemical industry and semiconductor manufacturing processes for the processing of precision metal etching products of electronic thin parts.

Types of etching technology

Wet etching:

Wet etching is to immerse the wafer into a suitable chemical solution or spray the chemical solution onto the wafer for quenching, and remove the atoms on the surface of the film through the chemical reaction between the solution and the etched object, so as to achieve the purpose of etching During wet etching, the reactants in the solution first diffuse through the stagnant boundary layer, and then reach the wafer surface to produce various products through chemical reactions. The products of etching chemical reaction are liquid or gas phase products, which are then diffused through the boundary layer and dissolved in the main solution. Wet etching will not only etch in the vertical direction, but also have the effect of horizontal etching.

Dry etching:

Dry etching is usually one of plasma etching or chemical etching. Due to different etching effects, the physical atoms of ions in the plasma, the chemical reaction of active free radicals and the surface atoms of devices (wafers), or the combination of the two, include the following contents:

physical etching: sputtering etching, ion beam etching

chemical etching: plasma etching

physicochemical composite etching: reactive ion etching (RIE)

Dry etching is a kind of anisotropic etching, which has good directivity, but the selectivity is worse than wet etching. In plasma etching, plasma is a partially dissociated gas, and gas molecules are dissociated into electrons, ions and other substances with high chemical activity. The biggest advantage of dry etching is “anisotropic etching”. However, the selectivity of dry etching is lower than that of wet etching. This is because the etching mechanism of dry etching is physical interaction; Therefore, the impact of ions can remove not only the etching film, but also the photoresist mask.

Etching process

According to the type of metal, the etching process will be different, but the general etching process is as follows: metal etching plate → cleaning and degreasing → water washing → drying → film coating or silk screen printing ink → drying → exposure drawing → development → water washing and drying → etching → film stripping → drying → inspection → finished product packaging.

1. Cleaning process before metal etching:

The process before etching stainless steel or other metals is cleaning treatment, which is mainly used to remove dirt, dust, oil stains, etc. on the material surface. The cleaning process is the key to ensure that the subsequent film or screen printing ink has good adhesion to the metal surface. Therefore, the oil stain and oxide film on the metal etching surface must be completely removed. Degreasing shall be determined according to the oil stain of the workpiece. It is best to degrease the silk screen printing ink before electric degreasing to ensure the degreasing effect. In addition to the oxide film, the best etching solution shall be selected according to the type of metal and film thickness to ensure surface cleanliness. It must be dry before screen printing. If there is moisture.

2. Paste dry film or silk screen photosensitive adhesive layer:

According to the actual product material, thickness and the exact width of the figure, it is determined to use dry film or wet film silk screen printing. For products with different thicknesses, factors such as the etching processing time required for product graphics should be considered when applying the photosensitive layer. It can make a thicker or thinner photosensitive adhesive layer with good coverage performance and high definition of patterns produced by metal etching.

3. Drying:

After the completion of film or roll screen printing ink, the photosensitive adhesive layer needs to be thoroughly dried to prepare for the exposure process. At the same time, ensure that the surface is clean and free of adhesion, impurities, etc.

4. Exposure:

This process is an important process of metal etching, and the exposure energy will be considered according to the thickness and accuracy of the product material. This is also the embodiment of the technical ability of etching enterprises. The exposure process determines whether the etching can ensure better dimensional control accuracy and other requirements.

5. Development:

After the photosensitive adhesive layer on the surface of the metal etching plate is exposed, the pattern adhesive layer is cured after exposure. Then, the unwanted part of the pattern, that is, the part that needs corrosion, is exposed. The development process also determines whether the final size of the product can meet the requirements. This process will completely remove the unnecessary photosensitive adhesive layer on the product.

6. Etching or etching process:

After the product prefabrication process is completed, the chemical solution will be etched. This process determines whether the final product is qualified. This process involves etching solution concentration, temperature, pressure, speed and other parameters. The quality of the product needs to be determined by these parameters.

7. Removal:

The surface of the etched product is still covered with a layer of photosensitive adhesive, and the photosensitive adhesive layer on the surface of the etched product needs to be removed. Because the photosensitive adhesive layer is acidic, it is mostly expanded by acid-base neutralization method. After overflow cleaning and ultrasonic cleaning, remove the photosensitive adhesive layer on the surface to prevent photosensitive adhesive residue.

8. Test:

After the film is taken, the following is testing, packaging, and the final product is confirmed whether it meets its specifications.

Precautions in etching process

reduce side corrosion and protruding edges and improve metal etching processing coefficient: generally, the longer the printed board is in the metal etching solution, the more serious the side etching is. Undercutting seriously affects the accuracy of printed wire, and serious undercutting will not make thin wire. When the undercut and edge decrease, the etching coefficient increases. The high etching coefficient indicates that the thin line can be maintained and the etched line is close to the size of the original image. Whether the plating resist is tin lead alloy, tin, tin nickel alloy or nickel, the excessively protruding edge will lead to short circuit of the conductor. Because the protruding edge is easy to break, an electric bridge is formed between two points of the conductor.

improve the consistency of etching processing rate between plates: in continuous plate etching, the more consistent the metal etching processing rate, the more uniform etching plate can be obtained. In order to maintain the best etching state in the pre etching process, it is necessary to select an etching solution that is easy to regenerate and compensate and easy to control the etching rate. Select technologies and equipment that can provide constant operating conditions and automatically control various solution parameters. It can be realized by controlling the amount of copper dissolved, pH value, solution concentration, temperature, uniformity of solution flow, etc.

improve the uniformity of the metal etching processing speed of the whole plate surface: the etching uniformity of the upper and lower sides of the plate and each part of the plate surface is determined by the uniformity of the flow rate of the metal etching solution on the plate surface. In the etching process, the etching rates of the upper and lower plates are often inconsistent. The etching rate of the lower plate surface is higher than that of the upper plate surface. Due to the accumulation of solution on the surface of the upper plate, the etching reaction is weakened. The uneven etching of the upper and lower plates can be solved by adjusting the injection pressure of the upper and lower nozzles. The spray system and the oscillating nozzles can further improve the uniformity of the whole surface by making the spray pressure of the center and edge of the plate different.

Advantages of etching process

Because the metal etching process is etched by chemical solution.

maintain high consistency with raw materials. It does not change the properties, stress, hardness, tensile strength, yield strength and ductility of the material. The base processing process is etched in the equipment in an atomized state, and there is no obvious pressure on the surface.

no burrs. In the process of product processing, there is no pressing force in the whole process, and there will be no crimping, bumping and pressing points.

it can cooperate with the post process stamping to complete the personalized molding action of the product. The hanging point method can be used for full plate electroplating, bonding, electrophoresis, blackening, etc., which is more cost-effective.

it can also cope with miniaturization and diversification, short cycle and low cost.

Application field of etching processing

consumer electronics

filtration and separation technology

Aerospace

medical equipment

precision machinery

car

high end crafts

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introductionSteel is quenched by heating the steel to a temperature above the critical temperature Ac3 (hypo-eutectoid steel) or Ac1 (hypereutectoid steel), holding it for a period of time so as to be austenitized in whole or in part, and then cooled at a temperature greater than the critical cooling rate Rapid cooling to below the Ms (or Ms near the isothermal) martensitic (or bainite) heat treatment process. The solution treatment of materials such as aluminum alloys, copper alloys, titanium alloys, toughened glass, etc., or heat treatment processes with rapid cooling is also commonly referred to as quenching. Quenching is a common heat treatment process, mainly used to increase the hardness of the material. Usually from the quenching medium, can be divided into water quenching, oil quenching, organic quenching. With the development of science and technology, some new quenching processes have emerged.1 high-pressure air-cooled quenching methodWorkpieces in the strong inert gas flow quickly and evenly cooling, to prevent surface oxidation, to avoid cracking, reduce distortion, to ensure that the required hardness, mainly for tool steel quenching. This technology has recently progressed rapidly and the range of applications has also expanded considerably. At present, the vacuum gas quenching technology developed rapidly, and the negative pressure (<1 × 105 Pa) high flow rate gas cooling followed by gas cooling and high pressure (1 × 105 ~ 4 × 105 Pa) 10 × 105 Pa) air-cooled, ultra-high pressure (10 × 105 ~ 20 × 105 Pa) air-cooled and other new technologies not only greatly enhance the vacuum quenching ability of air-cooled, and quenched the workpiece surface brightness is good, small deformation, but also A high efficiency, energy saving, pollution-free and so on. The use of vacuum high-pressure gas-cooled quenching is the quenching and tempering of materials, the solution, aging, ion carburizing and carbonitriding of stainless steel and special alloys, as well as vacuum sintering, cooling and quenching after brazing. With 6 × 105 Pa high pressure nitrogen cooling quenching, the load can only be cooled loose, high-speed steel (W6Mo5Cr4V2) can be hardened to 70 ~ 100 mm, high alloy hot work die steel up to 25 ~ 100 mm, gold Cold work die steel (such as Cr12) up to 80 ~ 100 mm. When quenched with 10 × 10 5 Pa of high pressure nitrogen, the cooled load can be intensive, increasing the load density by about 30% to 40% over cooling of 6 × 10 5 Pa. When quenched with 20 × 10 5 Pa of ultra-high pressure nitrogen or a mixture of helium and nitrogen, the cooled loads are dense and can be bundled together. The density of 6 × 105 Pa nitrogen cooling 80% to 150%, can be cooled all high-speed steel, high alloy steel, hot work tool steel and Cr13% chromium steel and more alloy oil quenched steel, such as more Large-size 9Mn2V steel. Dual-chamber air-cooled quench furnaces with separate cooling chambers have better cooling capacity than the same type of single chamber furnaces. The 2 × 105 Pa nitrogen cooled double chamber furnace has the same cooling effect as the 4 × 105 Pa single chamber furnace. However, operating costs, low maintenance costs. As China’s basic materials industry (graphite, molybdenum, etc.) and ancillary components (motor) and other levels to be improved. Therefore, to improve the 6 × 105 Pa single-chamber high-pressure vacuum care while maintaining the development of dual-chamber pressure and high-pressure air-cooled quenching furnace more in line with China’s national conditions.Figure 1 high-pressure air-cooled vacuum furnace2 strong quenching methodConventional quenching is usually with oil, water or polymer solution cooling, and strong quenching rule with water or low concentrations of salt water. Strong quenching is characterized by extremely fast cooling, without having to worry about excessive distortion of steel and cracking. Conventional quench cooling to the quenching temperature, the steel surface tension or low stress state, and strong quenching in the middle of cooling, the workpiece heart is still in the hot state to stop cooling, so that the formation of surface compressive stress. Under the severe quenching condition, the supercooled austenite on the surface of the steel is subjected to compressive stress of 1200 MPa when the cooling rate of the martensitic transformation zone is higher than 30 ℃ / s, so that the yield strength of the steel after quenching is increased by at least 25%.Principle: Steel from austenitizing temperature quenching, the temperature difference between the surface and the heart will lead to internal stress. Phase change of the specific volume of phase change and phase change plastic will also cause additional phase transformation stress. If the thermal stress and phase transition stress superposition, that is, the overall stress exceeds the yield strength of the material will be plastic deformation occurs; if the stress exceeds the tensile strength of hot steel will form a quenching crack. During intensive quenching, the residual stress caused by the phase change plasticity and the residual stress increase due to the specific volume change of austenite-martensite transformation. In the intense cooling, the workpiece surface immediately cooled to the bath temperature, the heart temperature almost unchanged. Rapid cooling causes a high tensile stress that shrinks the surface layer and is balanced by the heart stress. The increase of temperature gradient increases the tensile stress caused by the initial martensitic transformation, while the increase of the martensite transformation start temperature Ms will cause the surface layer to expand due to the phase transition plasticity, the surface tensile stress will be significantly reduced and transformed into compressive stress, Surface compressive stress is proportional to the amount of surface martensite produced. This surface compressive stress determines whether the heart undergoes martensitic transformation under compressive conditions or, on further cooling, reverses the surface tensile stress. If the martensitic transformation of the heart volume expansion is large enough, and the surface martensite is very hard and brittle, it will make the surface layer due to stress reversal rupture. To this end, the steel surface should appear compressive stress and heart martensitic transformation should occur as late as possible.Strong quenching test and steel quenching performance: The strong quenching method has the advantage of forming compressive stress in the surface, reducing the risk of cracking and improve the hardness and strength. Surface formation of 100% martensite, the steel will be given the largest hardened layer, it can replace the more expensive steel carbon steel, a strong quenching can also promote uniform mechanical properties of steel and produce the smallest distortion of the workpiece . Parts after quenching, the service life under alternating load can be increased by an order of magnitude. [1]Figure 2 strong quenching crack formation probability and cooling rate relationship3 water-air mixture cooling methodBy adjusting the pressure of water and air and the distance between the atomizing nozzle and the surface of the workpiece, the cooling capacity of the water-air mixture can be varied and the cooling can be uniform. Production practice shows that the use of the law on the shape of complex carbon steel or alloy steel parts induction hardening surface hardening, which can effectively prevent the generation of quenching cracks.Figure 3 water-air mixture4 boiling water quenching methodUsing 100 ℃ boiling water cooling, can get a better hardening effect, for quenching or normalizing steel. At present, this technology has been successfully applied to the ductile iron quenching. Taking aluminum alloy as an example: According to the current heat treatment specifications for aluminum alloy forgings and forgings, the quenching water temperature is generally controlled below 60 ° C, the quenching water temperature is low, the cooling speed is high, and a large residual stress after quenching occurs. In the final machining, the internal stress is out of balance due to the inconsistency of the surface shape and size, resulting in the release of residual stress, resulting in deformed, bent, oval and other deformed parts of the machined part becoming irreversible final wastes with serious loss . For example: propeller, compressor blades and other aluminum alloy forging deformation after machining obvious, resulting in parts size tolerance. Quenching water temperature increased from room temperature (30-40 ℃) to boiling water (90-100 ℃) temperature, the average forging residual stress decreased by about 50%. [2]Figure 4 boiling water quenching diagram5 hot oil quenching methodThe use of hot quenching oil, so that the workpiece before further cooling at a temperature equal to or near the temperature of Ms point in order to minimize the temperature difference, can effectively prevent quenching the workpiece distortion and cracking. The small size of the alloy tool steel die cold 160 ~ 200 ℃ in hot oil quenching, can effectively reduce distortion and avoid cracking.Figure 5 hot oil quenching diagram6 Cryogenic treatment methodThe quenched workpiece is continuously cooled from room temperature to a lower temperature so that the retained austenite continues to be transformed into martensite, the purpose of which is to improve the hardness and abrasion resistance of the steel, improve the structural stability and the dimensional stability of the workpiece, and effectively Improve tool life.Cryogenic treatment is liquid nitrogen as a cooling medium for material processing methods. Cryogenic treatment technology was first applied to the wear tools, mold tool materials, and later extended to alloy steel, carbide, etc., using this method can change the internal structure of metal materials, thereby improving the mechanical properties and processing properties, which is currently One of the latest toughening processes. Cryogenic treatment (Cryogenictreatment), also known as ultra-low temperature treatment, generally refers to the material below -130 ℃ for processing to improve the overall performance of the material. As early as 100 years ago, people began to cold treatment applied to watch parts, found to improve the strength, wear resistance, dimensional stability and service life. Cryogenic treatment is a new technology developed on the basis of ordinary cold treatment in the 1960s. Compared with the conventional cold treatment, cryogenic treatment can further improve the mechanical properties and stability of the material, and has a broader application prospect.Cryogenic treatment mechanism: After cryogenic treatment, the residual austenite in the internal structure of the metal material (mainly mold material) is transformed to martensite, and the precipitated carbide is also precipitated in the martensite, so that the martensite can be eliminated In the residual stress, but also enhance the martensite matrix, so its hardness and wear resistance also will increase. The reason for the increase in hardness is due to the transformation of part of the retained austenite into martensite. The increase in toughness is due to the dispersion and small η-Fe3C precipitation. At the same time, the carbon content of the martensite decreases and the lattice distortion decreases, Plasticity improvement.Cryogenic treatment equipment mainly consists of liquid nitrogen tank, liquid nitrogen transmission system, deep cold box and control system. In the application, cryogenic treatment is repeated several times. Typical processes such as: 1120 ℃ oil quenching + -196 ℃ × 1h (2-4) deep cryogenic treatment +200 ℃ × 2h tempering. After the treatment of the organization there has been the transformation of austenite, but also precipitated from the quenched martensite dispersion of highly coherent relationship with the matrix of ultrafine carbides, after subsequent low temperature tempering at 200 ℃, the growth of ultrafine carbides Dispersed ε carbides, the number and dispersion significantly increased. The cryogenic treatment is repeated a number of times. On the one hand, the superfine carbides are precipitated from the martensite transformed from the retained austenite at the time of the previous cryogenic cooling. On the other hand, fine carbides continue to be precipitated in the quenched martensite. Repeated process can make the matrix compressive strength, yield strength and impact toughness increased, improve the toughness of steel, while making the impact wear resistance was significantly improved.Figure 6 cryogenic treatment device schematicSome of the workpiece on the strict size requirements, does not allow processing due to thermal stress caused by excessive deformation, cryogenic treatment should be controlled cooling rate. In addition, in order to ensure the uniformity of the temperature field inside the equipment and reduce the temperature fluctuation, the design of the cryogenic treatment system should take into account the system temperature control accuracy and the rationality of the flow field arrangement. In the system design should also pay attention to meet the less energy consumption, high efficiency, easy operation and other requirements. These are the current development trend of cryogenic treatment system. In addition, some developing refrigeration systems whose refrigeration temperature extends from room temperature to low temperature are also expected to develop into liquid-free cryogenic treatment systems with the decrease of their minimum temperature and the improvement of refrigeration efficiency. [3]References:[1]樊東黎. 強(qiáng)烈淬火——一種新的強(qiáng)化鋼的熱處理方法[J]. 熱處理, 2005, 20(4): 1-3[2]宋微, 郝冬梅, 王成江. 沸水淬火對鋁合金鍛件組織與機(jī)械性能的影響[J]. 鋁加工, 2002, 25(2): 1-3[3]夏雨亮, 金滔, 湯珂. 深冷處理工藝及設(shè)備的發(fā)展現(xiàn)狀和展望[J]. 低溫與特氣, 2007, 25(1): 1-3
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First, the molecular beam epitaxial profileIn the ultra-high vacuum environment, with a certain thermal energy of one or more molecules (atoms) beam jet to the crystal substrate, the substrate surface reaction processMolecules in the “flight” process almost no collision with the ambient gas, in the form of molecular beam to the substrate, the epitaxial growth, hence the name.Properties: A vacuum deposition methodOrigin: 20th century, the early 70s, the United States Bell laboratoryApplications: epitaxial growth atomic level precise control of ultra-thin multi-layer two-dimensional structure materials and devices (super-character, quantum wells, modulation doping heterojunction, quantum yin: lasers, high electron mobility transistors, etc.); combined with other processes, But also the preparation of one-dimensional and zero-dimensional nano-materials (quantum lines, quantum dots, etc.).Typical features of MBE:(1) The molecules (atoms) emitted from the source furnace reach the substrate surface in the form of a “molecular beam” stream. Through the quartz crystal film thickness monitoring, can strictly control the growth rate.(2) molecular beam epitaxy growth rate is slow, about 0.01-1nm / s. Can achieve single atomic (molecular) layer epitaxy, with excellent film thickness controllability.(3) By adjusting the opening and closing of the baffle between the source and the substrate, the composition and the impurity concentration of the film can be strictly controlled, and selective epitaxial growth can be achieved.(4) non-thermal equilibrium growth, the substrate temperature can be lower than the equilibrium temperature, to achieve low temperature growth, can effectively reduce the interdiffusion and self-doping.(5) with reflective high-energy electron diffraction (RHEED) and other devices, can achieve the original price observation, real-time monitoring.Growth rate is relatively slow, both MBE is an advantage, but also its lack, not suitable for thick film growth and mass production.Second, silicon molecular beam epitaxy1 basic profileSilicon molecular beam epitaxy includes homogeneous epitaxy, heteroepitaxy.The silicon molecular beam epitaxy is the epitaxial growth of silicon (or silicon-related materials) on a suitably heated silicon substrate by physical deposition of atoms, molecules or ions.(1) during the epitaxial period, the substrate is at a lower temperature.(2) Simultaneous doping.(3) the system to maintain high vacuum.(4) pay special attention to the atomic clean surface.Figure 1 Schematic diagram of the working principle of silicon MBE2 Development history of silicon molecular beam epitaxyDeveloped relative to CVD defects.CVD defects: substrate high temperature, 1050oC, to the doping serious (with high temperature). The original molecular beam epitaxy: the silicon substrate heated to the appropriate temperature, vacuum evaporation of silicon to the silicon substrate, the epitaxial growth.Growth Criteria: The incident molecules move sufficiently to the hot surface of the substrate and are arranged in the form of a single crystal.3 The importance of silicon molecular beam epitaxyThe silicon MBE is carried out in a strictly controlled cryogenic system.(1) can well control the impurity concentration to reach the atomic level. The undoped concentration is controlled at <3 × 1013 / cm3.(2) The epitaxy can be carried out under the best conditions without defects.(3) The thickness of the epitaxial layer can be controlled within the thickness of the single atomic layer, superlattice epitaxy, several nm ~ several tens of nm, which can be designed manually, and the preparation of excellent performance of the new functional materials.(4) Homogeneous epitaxy of silicon, heteroepitaxy of silicon.4 epitaxial growth equipmentDevelopment direction: reliability, high performance and versatilityDisadvantages: high prices, complex, high operating costs.Scope: can be used for silicon MBE, compound MBE, III-V MBE, metal semiconductor MBE is developing.Basic common features:(1) basic ultra-high vacuum system, epitaxial chamber, Nuosen heating room;(2) analysis means, LEED, SIMS, Yang EED, etc .;(3) injection chamber.Figure 2 Schematic diagram of silicon molecular beam epitaxial system(1) electron beam bombardment of the surface of the silicon target, making it easy to produce silicon molecular beam. In order to avoid the radiation of the silicon molecular beam to the side to cause adverse effects, large area screen shielding and collimation is necessary.(2) resistance to heating the silicon cathode can not produce strong molecular beam, the other graphite citrus pots have Si-C stained, the best way is to electron beam evaporation to produce silicon source. Because, some parts of the silicon MBE temperature is higher, easy to evaporate, silicon low evaporation pressure requirements of the evaporation source has a higher temperature. At the same time, the beam density and scanning parameters to control. Making the silicon melting pit just in the silicon rod, silicon rods become high-purity citrus.There are several kinds of monitoring molecular beam:(1) Quartz crystal is often used to monitor beam current, beam shielding and cooling appropriate, can be satisfied with the results, but the noise affects the stability. After several μm, the quartz crystal loses its linearity. Frequent exchange, the main system is often inflated, which is not conducive to work.(2) small ion table, measured molecular beam pressure, rather than measuring the molecular beam flux. Due to the deposition on the system components leaving the standard.(3) low-energy electron beam, through the molecular beam, the use of electrons detected by the excitation fluorescence. The atoms are excited and quickly degrade to the ground state to produce uv fluorescence, and the optical density is proportional to the beam density after optical focusing. Do the feedback control of the silicon source. Inadequate: cut off the electron beam, most of the infrared fluorescence and background radiation will make the signal to noise ratio deteriorated to the extent of instability. It only measured atomic class, can not measure molecular substances.(4) Atomic absorption spectra, monitoring the beam density of doped atoms.With the intermittent beam current, Si and Ga were detected by 251.6nm and 294.4nm optical radiation respectively. The absorption intensity of the beam through the atomic beam was converted into atomic beam density and the corresponding ratio was obtained.Molecular beam epitaxy (MBE) substrate base is a difficult point.MBE is a cold wall process, that is, silicon substrate heating up to 1200 ℃, the environment to room temperature. In addition, the silicon wafer to ensure uniform temperature. Hill resistance refractory metal and graphite cathode, the back of the radiation heating, and the entire heating parts are installed in liquid nitrogen cooled containers, in order to reduce the thermal radiation of the vacuum components. The substrate is rotated to ensure uniform heating. Free deflection, can enhance the secondary implantation doping effect.
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1, ???????? ?????? ???????? ?? ??????? - ??????? ?????????????? ??? ????????? ???? 1 ?????????? ?????? ?? ???? ??????????? ????? ?????????? ?? ????? ??????????????????? ???????? ??? ?????? ??? ?? ???? ???? ??? ??????????? ?? ??? ??? ?????? ??????? ?? ??????????? ??? ??????? ???????? ?????????????? ??? ?????? ??? ?? ?????? ???????? ??????? ?? ?????????????? ?? ??? ?????????? ?? ?????? ?? ???????? ???? ???? ??? ?? ??? ?????? ??????????? ?? ?????? ??? ???????? (?????????????) ???????? ???? ?????? ?????????? ??????? ?? ??????? ?? ??????? ????? ?? ?????? ???? ??? ??? ?? ??????? ?? ?? ?? ????????? ?? ??? ??????? ?????? ?? ??? ???? ????? ???, ?? ?? ??? ????? ?????? ?? ???????? ?? ???? ???????? ???? ???? ???? ?????, ??? ?? ????? ??? ?? ???????, ????????, ?????? ?????, ???? ??????? ?? ??? ????? ??? ???????? ??????? ?? ??????? ????? ????? ?? ?? ???????? ????? ?????????? ?????? ???????????? ?? ??????????? ?? ??????? ??? Optoelectronic ???????? ?? ??? ????????? （Adv.Mater? 2017, ?????: 10.1002 / adma.201700764 Advanced 2, ????? ??????? ??????: ????? ??????? ?? 2 ?? Optoelectronic ??????????? ?????? 2 ?? ????? ???????? ??????? ?? ????? ??? ?? ?????????? ??? ?????? ???? ?????? ?? photoelectronron ????? ?? ??? 2 ?? ??????? ?? ???? ?? ??????? ???? ?? ?????????????? ?? ????????????????? ?? ??? 2 ?? ??????? ?? ???? ???? ??? ??????????? ???? ?????, ????? ??? ????????? ?? ????-????? ??????? ???????? ?? ??? ???, 2 ?? ??? ??? ?????? ???????? ???????? ?? ????? ???????, ???????, ?????????? ??? ?????, ????? ??? ??? ?????? ???? ??, ????????????????? ??????????? ?? ??? ?? ??????? ??????? ?????? ???? ??? ??? ?? ???, ???????? ?????????????, ???????? ?? ???????, ??? ?????? ????? ???????? (?? ?????????) ?? ???? ?? ????????????????? ??????? ??? ???????? ?? ????? ??????? ?? ????? ?? ??????? ??? ?????????? ?? ???????? ??? 2 ??, ????????, ??????????, ???? ???, ??????, ???-???????? ???????? ????? ????? ???? 2D ???????? ???????? ?????????? ?? ????????? ????? ?? ????????? ?? ?? ????? ?? ?? ??? ?? ????????????????? ??????? ?? ????? ?? ??????? ?? ??? ???? ???? ??, ?? 2 ?? ??????? ?? ??????? ?? ??????? ??? ????? ?? ???? ??? ????????????????? ??????????? ?? ??? ???????? ??????? Organic ??? ???????? Adv.Mater?, 2017, DOI: 10.1002 / adma.201702415） 3, ????? ??????? ?? ???????: 2D? ?????????-???? ???????? ????????? 3 ?? ?? 2 ?? ?????????? ???????? ?? 3 ????????? ????? ???????? 3 ?? ????????-?????????? ????? ??????? ?? ??? ?? ??? ????????? ???? ?? ????? ???? ??? ???????, ???, ?????? ?? ?????? ??? ???? ?????????? ???????? ???????????? ?? ???? ?? ?????????? ?????? ??? ??? ??? ???? ??????, ????? ??-????? ?????????-???? ???????? ?? ???? ?????????? ??????? ?? ???? ????? ??? ????? ???? ??? ???????, 2 ?? ??????????? ???????? ??? ???? ??? ??? ??? ?? ???, ???? ?????????????, ?????? ????? (????????? ????) ??? ?? ?? ??????? ???????? ?? ?????? ???? ??? ?? ??????? ????? ??? 2 ?? ??????????? ?? 3 ?? ???????? ??? ???? ???? ?? ??? ????-????? perovskite ???????? ?????? cationic ??????????? ?? ????? ??? ????, 3 ?? ?? 2 ?? ??????????? ?? ??? ????-????-????? ???????? ?? ?????? ?? ????? ?? ??? ???? ?????, 2 ?? ?????????? ???????? ???????? ???, ??????????-???? ?????? ?? ??????? ?? ????? ???? ???? ??? ???, ???? ???????? ???????????? ??????? ??? 2 ?? ?????????? ?? ?????? ??????, ????? ???????? ?? ??????????? ???????? ?? ?? ???? ?????? ???????? ???? ??? ??? Optoelectronics .M Adv.Mater?, 2017, DOI: 10.1002 / adma.201703487） 4 ?? ???? , ??????? ?????? ??????: ??? ????? ????????: ????????-??????? ??????, ????? ????? ???????????? ???????? ?? ????? ?????? ???????? ????????? ???? 4 CH3NH3PbX3 perovskite ??????Leaded anodized perovskite ??? ???????? ?? ?????? ???????? ??????? ??? ?? ???? ???????? ??????? ????? ??? ??? ?? ?????????? ?? ?????????? ?????????? ?? ???????? ?????? ???? ?????? ?? ??????? ??, ??? ?? ??? ?? ?????? ??? ??????????? ?? ???? ?? ???????? ?? ??? ?? "????????-???" ??????? ?? ???? ?? ?? ??? ????? ?????????? ????? ????? ?????????? ???????? ?? ??????? ??? - ??????????????? ?????????? ?? ?? ???? ?? ???? ???? ???? ???? ??? ??? ?? ???, ???????? ????????????? ?? ?????????? (????? ????) ??? ?? ????????-??? ??????? ?? ??????? ??, ????? ???????????? ???? ??????? ?? ??? ?? ??? ?? ??? ????????? ?????? ??? ??????????? ???? ??, ?? ??? ?????????, ???? ???????? ?? ????? ?? ??????? ???????? ?? ??? ???????? ?? ???? ???? ??? ?????? ??? ???? ??????? ??? ?? ???? ????? ????????? ?? ?? ?????????? ??? ???? ???? ???? ??? ?????????? ??? ?? ???????? ?? ???? ???? ???? ??????????: ????????-??? ?????, ???? ????? ?????????? ???????? ?? ???? ??????? ??? ph ???????? Adv, 2017, DOI: 10.1126 / Sciadv.1701469 Pro 5, ?????? ??????? ?? ?????? ??? ??????: ??????? ????? ????? ????????????? ?? ??????????? 5 diblock copmermermerRecently, ????? Tsinghua ????????????? ????-???? ?? (?????????) ?? ??? ???? ???? ???????? ????? ???????? (??????) ????? ?? ?????? ?? ?????? ?? ??????? ?????? ?? ?? ?????? ???????? ???? ??? ??, ?????? ?????????? ??????????? ?? ??? ??? ??????? ????? ?????? ?? ????? ?? ????? ???????? ???? ??? ??? ??-????? ??????? ?? ?????? ?? ???, ?? ?????? ??? ???? ???? ???????????, ???? ????? ?? ??????? ?? ???? ????? ????????? ?? ???? ???? ???? ???? ???? ???? ?? ????? ??? ?? ???? (?????????????????) (????????) ?? ?????? ??? ?? ??-????? ?????? ??? ?????? ???? ??? ??, ???????? ????? ?????? ?? ????? ???? ?????????????? ?? ??????? ????? ?? ?? ??? ???????? ?? ?????? ?? ????????? ?? ?? ??? ???? ??? ?? ??? ????? ????????? ?? ????? ???????? ?? ????? ???? ???? ??????????? ????????? ????????? ?? ?? ????????? ?? ?????????????? ???? ?? ????? - ??????? ?? ????? ???? ???? ?????? - ?????? ?????? ????? ???, ?? ?? ????? ?? ?? ??? ??? ???, ?????? ?????????? ?? ???????? ?? ??????? ??? ?? ?? ??? ?????-????????? ?? ??? ??????-????? ????? ?????????? ers ?????? Polym? ???????, 2017, ?????: 10.1016 / j.progpolymsci.2017.10.002, 6, Angewandte Chemie International Edition ??????: CH3NH3PbI3 perovskite ??? ??? ?????????? ?????? ????????? ???? ???????????? ????? ?????????? ???????? ?????? (PCEs) 22% ?? ???? ???????? ???????????? ??? ???????? (PSCs) ?? ???? ????? ??????? ???? ??? ??????? ?????? ?? ?????? ??? ???????? ?? ?????????? ?????? ???? ??, ????? ???????? ?? ??? ????? ???????? ???????? ??????? ???? ???? ??? ?? ???, ???? ??????????? ??? ??????????? ??? ?????????? ?? ???????? ???? ?????? (??????????? ???) ??, ???? ???????? ?? ??????, ?????? ?? ???????????? ?????, ?????, ??? ?????? ?? CH3NH3PbIB ????????, ?? ??? ?????? ?????? ?? ??????? ???????? ?? ????????? ????? ?????? ???? ?? - ??????? ???? ???????????? ??????? ????????????????? ?? ????? ?????? ???? ?? ?? ????? ?? ???? ??? ?? CH3NH3PbI3 Perovskite Solar Cells ew Angew ?? PSCs.Theoretical Treatment ?? ??? ???, ????????? ?? ?????? ?? ??? ???? ??? ?????? ???? ???, 2017, ?????: 10.1002 / aie.201702660 Chemical 7, ?????? ??????? ?????? ??????: ????? ??????????? ?? ??? ????????????????? ?????? ??????? ?? ??? ???????? ???????? 7 ???-??? RFBA ?? ??? ??????? ???????? ?? ??? ????? ??????????? ?? ?????????? ???? ????? ?????? ???????, ??????? ????? (RFBs) ??? ???? ???????? ?? ???????? ????? ?? ????? ???????? ???????? ???? ???????, ???????? RFB ????????? ???? ?????? ??????? ???????? ?? ????? ?? ????? ???? ???? ?? ?????????? ??????? ?? ???????? ?? ?????? ?? ???? ???? ??? ?? ???, ??????? ????????????? ??? ?????? ????? ?? (????? ????) ??? ?? ?? ?? ??????? ?????? ??????? ????? ??????????? ????????? ?? ?????? ?? ???????? ???? ??? ??? ?????????, ????????-??? ?????? ?? ????? ???? ?? ?????? ??? ?????????????? ?? ?????????????? ??????? ???????? ?? ??????? ???? ?? ??? ?? ??????? ???????? ?????? ?????? ?? ???? ??? ?? ??? ???? ????? ??????, ??????? ????????????? ??????? ?? ??????? ???????? ????? ?????? ???????? ??????? ?????????? ?? ??????????? ????? ?? ??? ???? ???? ??? ?? ???????? ?? ??? ????? ??? ???, ???? ?? ????? ??? ???????? ??????? ?? ?????? ?? ????? ?? ???? ?? ?????? ?? ???????? ???? ??? ??????? ???? ????? flow Chem.Soc.Rev?, 2017, DOI: 10.1039 / C7CS00569E） 8, ?????? ??????? ?????? ?? ??? ????? ????????? ?????? ???????? ?? ????? ???????????? ????? ?????? ?? ???????? ?? ??? ?????? ????? ???-?????? ???????? ???????? ????????? 8 ??????-????? ?????? ?? ???-?????? ???????? ???????? ??????? ?? ??? ?? ???, ?? ??????-????? ???? ???? ?????? ????? ?? ???? ??????? ???? ???? ???? ??????? ??? ??????? ?? ???? ??????? ?????? ??? ???? ???? ???? ???????????? ?????? ?? ?????? ????? ?? ???????? ???? ??? ?? ???, ???????????? ??????????? ???? ??????????? ????????? (????? ????) ??? ?? ???? ?????? ?? ???-?????? ????-??????? ?????? ???? ?? ?????? ????? ?? ????????? ????, ???? ???? ???????????? ??????, ???????????? ?????? ?????? ?????? ?? ?????? ?? ?????? ????, ?? ???? ????? ?????? ?? ???????? ??????????? ?? ??????? ????? ??? ?????? ??? ?????, ?????? ??? ?????, ???????, ??? 2 ???, ??? ???????? ??????????? ?? ????? ??? ???? ?? ???? ??? ???, ??????? ??? ?????? ?? ???? ??, ?????? ?? ???? ?? ??? ?????? - ???????? ?? ?? ???????? ?? ?????? ?? ??? ?????????? ????????? ???? ????? ?????? ?? ???????? ?? ??? ??????? ??? ?? ???? ???-?????? ?????????????? .S Chem.Soc.Rev?, 2017, DOI? : 10.1039 / C7CS00418D Chemical 9, ???????? ??????? ??????: Heterocyclic ?????? ?? ???????? ??? ??????????????? ????????? ?????????-??????? cationic ???????? ??????????? ?? 9 ????? ?? ????????? ????? ??????????? ?? ?? ?? ???? ???? ???????? ??????? ??? ?? ?? ??, ?? ?????????????? ???????? ?? ?????? ?? ???????? ???? ??? ??? ???????? ?????????? ?? ?????????? ?? ??? ???? ????????? ????? ??? ?? ?????? ????????? ????????, ???????? ????????, ????????????? ?? ?????? ??? ?????? ??? ?? ??????? ????????? ???????? ??? ???? ???? ?? ??? ????? ???? ??? ?? ??? ????? ?? ????????????? ??? ?? ???? 70% ??? ?? ?? ?? ?? ???? ???? ??, ?? ??? ???? ????? ?? ?????? ???? ?? ???? ???? ??? ?? ???, ?????? ???????????? ????????????? (????????? ????) ??? ?? ???????? ????? ??????? ?? 2000 ?? ??? ?? ???????????????? ?? ?????????????? ??????? ?????? ???????? ?????????????? ??????? ?? ??????? ??????? ?? ?????? ?? ??????? ??? ???????????? ???????? ?? ???????? ??? ??????????????????? ?? of ?????? ???, 2017, ?????: 10.1021 / acs.chemrev.7b00271)
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???? ????, ?? ????????? ?????? ?? ?????? ???? ???: 1945 ?? 1951 ??, ?????? ??????? ?????? ?? ???????? ?? ???? ?? ?????????? ?? ????????? ???? ????: ???? (?????????? ???????????, ???? ??????? ?????? ??? ????? ???) ?? ?????? (???????? ???????????, ??????? ??????? ?????? ??? ???? ???) ????? ???? ??????? ????? ????? ???: ????? ?? ???? ?? ??? 1951 ?? 1960, ?????????? ?? ?????????????? ?????? ???? ??????, ?? ?????????? ???????? ?? ?? ???? ?? ??? ??????? ???????? 1953 ???? 30 ?????????? ?????? ??????? ?????? ?????????????? ??? ????? ????; 1958 ?? 60MHz ?? ????? ???, 100MHz ?????? 1950 ?? ??? ?? ???? ???, 1H-NMR, 19F-NMR ?? 31P-NMR ?? ?????? ???? ??? ??? ????? ???: 60 ?? 70 ????, NMR ???????????? ??? ????? ???? ?????? ???????? ???????????? ??????????? ?? ?????? ??? ????? ???? ?? ???, ?????? ??? ?? 13C ?????? ???? ?? ???? ??; ????? ??????? ?? ??? ??????? ?????? ????????????; ???? ???: 1970 ?? ??? ?? ??? ??? ???????? ?? ???????????? ????? ???????? 1200, 300, 500 ?????????? ?? 600 ?????????? ????????????? ?????? ??????????????; 2; ??????? ?????? ?? ???? ???????? ?? ????????? ?? ?????????? ??? ????; ?????; 3, 2 ??-?????? ????? ????; 4; ?????-??? ??????, ??? ??????? ??? ?? ???? ???? ?? ???? ??; 5, "?????? ??????? ?????? ??????? ????????????" ?? ???? ?? ???? ?????? ??? ???? ????? ????????: 1? ???????? ?? ?????? ?? ??????, ?? ???-??? ????????????, conformation2 ????????? ?? ???? ???? ????? ??????? ????????, ???? ?? ???????????, ???? ?????????????? ???? 3? ?????? ????????, ???? ?? ????? ????? ?????? ???? ???? ??, ???? ????? ?????? ?? ?????? ?? ????????? ?? ???? ?? ?4? ??????? ????????, ?? ??? ???? ?? ??????, ?????? ?? ???????? ?? ???????? 1 ?? ??? ??? ???? ???????? ????????? ??? ?????? ?? ??????????? ?? ????? ?? ????? ?? ???? ???, ????? ?? ???? ??? ??? ????? ??? ???? ??? ?? ????? ????? ?????? ??????? ?????? ?? ????? ???? ????? ???????: ????? ?? ????? ??? ?? ????? ???? ???? ??????? ???????? ?? ??????, ?? ?? ????????, ?? ??? ???????? ?? ?? ????? ?? ???? ??? ???????? ????? ?????? ?????? ??? C, H, O, N ???? ?????????? ???? ??? ???? ??????? ???, 12C, 16O ???-??????? ???? ??? ?? ????? ?????? ??????? ?????? ?? ???? ?????? ???? 1 ?? ?? ????????? ???????, ????? ???????, ????????? ???? ???? ??, ????? ?????? ?????? ????? ??? ?? ??????? ?? ??? ??? 13C ??????? ???? ??, ???? 12C 1.1%, ?? ????? ??????????? 1/64 ??????? ???? ?? ??? ???? ?? ??????? ??? ?? 1H ?? ???? 1/6000 ?? ??? ???????????, ????????? ???? ???? ???? ??? ????? ????? 30 ?????? ???, ?????? ??????? ?????? ???? ??? ???? ????? ??? ??, ??? ??? ?? ??? ??? 13C ?????????? ??? ???? ?? ???? ??, ?? ???? ??????? ?? ?? ???? ??, NMR ?? ????? ???? ?? ??? ??? 1H, 19F, ????, ????? ??????? ?? ??????? ?? ?????? ??????? ????? ?? 31P ????????? ???????, ???? ???? ???????? ???? ?? ??? ?2? ??????? ??????? ?????? ??????: ?????-???: ?? ??????? ???????? ???? ?? ??? ????? ????? ???????? ??????? H0 ?? ?????? ?? ???, ?? ??? ???? ??? ?? ??? ??? ??????: ???????? ???? ??? ??, ?? H0 (????? ??????? ??????? ?????) ?? ????????? ??? ????? ??????? ??????? ?????????? ??? ????? ??????: ??? ????? ??????? ??????? ???? ??, ????? ??????? ?????????? ????? ??? ??????? ??? ????? ??????? ??????? H0 ??? ??, (2I + 1) ?????????? ?? ???? ????? ??????? ??????? ??? ??????? ??? ?? ????? ????????????? ??????? ??? ?????????? ?? ????? ?????? (???????, ??????) ?? ?????? ?? ???? ??? ?????? ??????? ?????? ?? ??????? ??????? ?????? ??????? ??????? ??? ??????? ?????, ????? ??????? ??????? ???? ????? ?? ???? ??????? ???????? RF ??????? ??????? ?? ??????? ????? ????? ?? ?????????? ??????? ?? ????? ???? ??, ?? ?????????? ????? ????? ?????? ?? ???? ????? ?????? ?? ???? ??? ?????? ??????? ?????? ????: ????? ??????? ??????? H0 ?? ????????? ???? ???? ?? ?????? ??????? ??????? H1 ?? ???????? ????? ?? ???? ???? ???? ??? ??? H1 ?? ?????? ??????? ????? ?? ?????? ?????????? ??????? ?? ????? ???? ??, ?? ????????? ????? H1 ?? ????? ?? ??????? ?? ???? ?? ?? ????? ????? ????? ?? ???? ????? ????? ?????? ??????? ?????? ??? ????????? ?? ???? ?? ?3? ???????? ?? ??????? ?? ????? ?????? ???? ????? ?????? ?? ???? 0.001% ???? ??? ?????, ?? ????? ????? ??? ????? ???? ????? ?????? ?? ???? ???? ??, ??????? ?? ??? ?? ?? ???? ?? ??????, ????? ??????? ??????? ?????? ?? ?????? ?? ???????? ?? ???? ???? ??? ??????? ???????? ?????? ?? ?????? ?????? ??????, ??? ?? ????? ?????? ????-???? ?? ?? ???? ??, ?? ?????? ?????? ?? ??????? ????? ?? ?????, ?? ????? ???? ??? ?? ???? ?? ?????, ?? ???? ?? ???????? ??? ???? ??? ?? ???????? ???? ??, ?? ?? ????? ??????? ??? ??? ?? ?????? ??????? ???? ???? ??? ????? ??????? ??????? ???, ?? ????? ???? ????? ?? ??? ?? ????-????? ????? ?? ????? ??? ???? ?????? ???? ???, ??????? ???????? ???? ????? ?? ??????? ???? ??? ?? ????? ?? ??????? ??????? ?????? ??? ?? ????-????? ???? ????? ??? ??? ???? ???, ?? ??? ?? ????? ?? ?????? ??? ?????, ?? ????????? ?? ??????? ??? ???? ?? ?4? ????? ?????? - ???????? ??????? ?? ????? ?????? ?????? ?? ??? ????, ???? ?????, --E = (?? / 2γ) π · ??; ??? ??????? H0 ?? ???, ?? ????? ??? ???? ?? ΔEΔE = E ???? ???? ??? ???? νEly ???? ??????? ?? ?????? ???? ?? ν = H35 = 2.3500 ?? ??? ??? ??, 100 ?????????? ?? 1H ?????? ???????, 25.2 ?????????? ???????? ??? ?? 13C ?????? ???????: ?????????? ?? ???? ???????? ?????? (??? ????, ????? ????) ??????? ???: ???? ???????? ???? (??????) ???????? ????, ????????? ???? ???? ???-??? ???? ???? , ???????????????? ?????????, ?????????????? ????????????: H0 = 2.3500 T ???, ??? ?? ????? ???????????? ?? ????, ?????? ?????? ???, ???????? ??????? ??????? 2.3500 TResonance ?? ??????? ?? ????? ??? ????? ???? ?? ?? 100 ?????????? ?? ???? ??? 1H 0 ?? 10 ??, ?? 13C 0 ?? 250 ??? ????????? ?? ????? ?? ???? ?????????? ???? ???, ?? ?? ??????? ??????? ?? ??????? ??????? ?????? ?? ???? ??? ???? ???? ????? ?? ???, ????? ?? ???????????? ?? ??? ???? ???? ?? (????????) ??????? ??? ?? ????? ?? ?????????? ???? ?? ????? ????? ???? ???? ??, ???? ?? ???? ???????? ?????? ???? ??, ??????? ??????? ?? ???? ??? ???? ?????? ?????? ???? ??? ????? ?? ????? ?? ?????????? ?????? ????? ????? ?????? ?? ???????? ???? ??, ????? ??????? ???????? ????????? ?? ?????, ?? ???-??? ???????? ???????? ?? ?????? ???? ???, ???? ?????? ??????? ?????? ????? ?? ??????? ??????? ??? ????? ???? ???? ??? ????? 60MHz ?? ??? ???? ???? ?? 100 ?????????? ?????, ???????? ????? ??????? ?? ??????? ???????? ???? ??????? ???? 1000 ?????? ?? 1700 ?????? ??? ?????? ?? ???????? ???? ???, ??? ???????? ??????? ?? ????????? ???? ?? ???????? ???? ??, ????? ????????? ??????? ????????? ???? ?? ??? ???? ?? ??? ??? ??????? ????? ?? ???, ????? ?? ?? ?????? ?????? ?? ???????? ???? ??? ???? ????? ?? ???????? ??????? ?? ?? ??????? ?? ???????? ??????? ?? ??? ???? ?? ???????? ????? ??? ???? ?? ?5? H NMR ???????????????? ???????? ??????? ?? ??????: ????? ??????? ?????? ?? ??????? ??? ??? ????? ???? ?????? ?? ??????: ???????? ??????? ?? ???????????? ???????, ???????? ????? ?????? ?? ???????: ???????? ??????? ?? ?????? ?? ??????: ????? ??????? ??????? ????? ???? ???????? ??????? ?? ??????? ???????? ?? ???????? ????? ?????????? ??????? ??????? ???????? ?????? ????? ?? ?? ??????? ???????? ?????? ?????? ???? ??, ?? ③ ???????????? ???????????? ?????? ?? ???????? ?? ???? ???? ??? ??-???????????? ?? ????? ??? ?? ?? ???????? ???? ?? ?????? ??????? ??? , ?? ???????????????????? ?? ????? ?????????, 0.5-5 ??? ?????? 2, 4-7 ??? ????, ???????? ?? ????, ?? ?????? ?? ?????? ?? ???????? ???? ??????? ??; ??????, ??????, ???????? ?? ??? ????????? ????? ???? ??? ???? ??, ?? ????????? ???? ?? ??????? ?????? ?? ?????????? ?? ??? ???? ???? ?????? ???????????? DMF ?? ??? ?? ???? ????? ??? ?????? ???? ?? ?????????? ???? ?????? ?? ????????? ???? ?? ??????? ???? ??, ????????? ???? ?? ????? ???? ??? α ?????? ???????? ??????? ??? ??, ?????? ???? ??????? ??? ???? ??; ??, ?????? ???????? ??????? ??? ??, ?????? ?????? ????? ??????? ??? ???? ??, ?? ???? ?????? ?? ?? ?? ?? ?????? ???? ????? ?????? ????? ???? ????
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