A green pretreatment process and on-line monitoring system for a wire with high lubrication and rust resistance

Abstract

The present application relates to the technical field of metal wire surface treatment and industrial online monitoring, and relates to a green pretreatment process and an online monitoring system for a card wire with high lubrication and rust resistance. The present application removes the oxide layer by using a composite organic acid and ultrasonic waves at 80-85 DEG C after the card wire is mechanically stripped by multi-stage reverse bending. A multi-parameter online monitoring system is established. During the pickling process, Fe 2+ , pH, conductivity and linear velocity are monitored online in real time, and the pickling parameters are adjusted adaptively to overcome the fluctuation of manual experience. Then, the card wire is neutralized, rinsed, sprayed with modified boron liquid to form a lubricating and rust-proof film, dried and wound to complete the pretreatment. The present application effectively solves the problems of large acid mist pollution, easy damage to the substrate, poor process consistency and insufficient rust-proof ability between processes in the traditional strong acid pickling. The surface friction coefficient of the pretreated card wire is less than or equal to 0.075, and the red rust time is greater than 72 hours, which provides high-quality raw material guarantee for subsequent high-precision drawing processing.

Description

Technical Field

[0001] This invention relates to the field of metal wire surface treatment and industrial online monitoring technology, and to a green pretreatment process and online monitoring system for needle cloth raw filaments with high lubrication and rust resistance. Background Technology

[0002] Card cloth is the "heart" of a carding machine, and its technological level directly determines the final quality of the textile. As the base material for card cloth manufacturing, the surface quality of the card cloth precursor yarn has a decisive impact on the processing stability of subsequent processes such as drawing, profile rolling, tooth punching, and heat treatment, as well as the service life of the finished card cloth. Card cloth precursor yarn typically uses high-carbon steel materials such as 70#, 80#, or T10. During hot rolling and storage, a dense layer of iron oxide scale forms on the surface of these materials, which must be thoroughly removed before drawing.

[0003] In current production, the removal of oxide scale from high-carbon steel wire commonly employs strong acid pickling processes using hydrochloric acid or sulfuric acid systems. While this type of process removes rust quickly, it has significant drawbacks under continuous production conditions: First, the severe volatilization of acid mist poses a significant hazard to production equipment, the workshop environment, and the health of operators, resulting in immense environmental pressure. Second, the process window is narrow; improper control of pickling solution concentration, temperature, and treatment time can easily lead to over-pickling, causing hydrogen embrittlement and pitting corrosion in the substrate, damaging the intrinsic mechanical properties of the material. Third, the aging process of the pickling solution and the accumulation of iron ions lack effective monitoring, relying heavily on manual experience. This results in inconsistent surface cleanliness and roughness between different batches, and even within the same batch of steel wire, directly affecting the lifespan of subsequent drawing dies and the uniformity of the finished wire diameter. In addition, the boronizing process in the traditional pickling line is mostly done by immersion, which has prominent problems such as uneven film, large fluctuations in lubrication performance and short rust prevention time between processes. It is difficult to meet the stringent requirements of high-performance card cloth for high surface finish (Ra ≤ 0.08 μm), high precision (diameter deviation ≤ 0.003 mm) and high lubrication (friction coefficient μ ≤ 0.075) of the raw yarn surface.

[0004] Therefore, there is an urgent need to develop a green pretreatment solution suitable for continuous production of needle cloth filaments, which can meet the requirements of efficient rust removal while taking into account substrate protection, process consistency, online intelligent monitoring and excellent film-forming lubrication performance. Summary of the Invention

[0005] Based on this, the purpose of this invention is to provide a green pickling process and online monitoring system for needle cloth raw yarn with high lubrication and rust resistance, so as to solve the technical problems of existing strong acid pickling processes, such as large acid mist pollution, easy damage to the substrate, poor process consistency, and insufficient lubrication and rust prevention performance.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: This invention provides a green pretreatment process for needle cloth raw yarn with high lubrication and rust resistance properties, comprising the following steps: S1, Mechanical pretreatment: Mechanical peeling and dust removal are performed on the high carbon steel needle cloth raw wire rod to obtain pretreated steel wire; S2, Online monitoring and adaptive adjustment of ultrasonic pickling: The mechanically pretreated steel wire described in S1 is subjected to ultrasonic organic acid cleaning. During the pickling process, the pickling solution parameters are monitored online in real time, and the state of the pickling solution is judged in combination with the steel wire linear speed. The replenishment and process parameters are adjusted to obtain the pickled steel wire. S3, Neutralization and rinsing: The pickled steel wire described in S2 is subjected to extrusion, neutralization and rinsing in sequence to obtain rinsed steel wire; S4, Atomization film formation: The surface of the rinsed steel wire described in S3 is sprayed with modified boron liquid to form a lubricating and rust-preventing film layer, thus obtaining a film-forming steel wire; S5, Drying and winding: The film-forming steel wire described in S4 is dried and then wound up to complete the pretreatment of the needle cloth raw yarn.

[0007] The green pretreatment pickling process for needle cloth raw yarn with high lubrication and rust resistance provided by this invention adopts a technical route combining mechanical peeling and organic acid cleaning. First, most of the loose iron oxide scale on the surface of the raw yarn is removed by a multi-stage reverse bending physical peeling method. Then, the residual oxide layer is precisely and greenly cleaned by using composite organic acid, ultrasonic cavitation effect, and online monitoring and control system. After pickling, the yarn is neutralized, rinsed in multiple stages, and atomized under high pressure to form a uniform and dense lubricating and rust-resistant film on the surface of the steel wire. The multi-stage rinsing is preferably four stages.

[0008] Furthermore, the mechanical peeling described in S1 is carried out in a mechanical peeling unit, where loose iron oxide scale on the surface is removed through multi-stage reverse bending and rotation peeling, and residual dust and particles are removed by circulating airflow.

[0009] Furthermore, during the ultrasonic organic acid cleaning described in S2, the mechanically pretreated steel wire is continuously introduced into the organic acid cleaning tank equipped with an ultrasonic transducer to complete the cleaning of the residual oxide layer; the parameters of the acid cleaning solution include Fe. 2+ Concentration, pH value, conductivity, and temperature; the ultrasonic organic acid cleaning temperature is 80~85℃, the ultrasonic frequency is 25~40 kHz, and the power density is 1.5~2.5 W / cm³. 2 The Fe 2+ The concentration is 0~35 g / L, the pH value is 1.5~2.5, the conductivity is 20~100 mS / cm, and the wire speed is 400~600 m / min. The online monitoring and adaptive adjustment control unit can adjust according to Fe... 2+ The concentration change compensates for and adjusts the amplitude of the ultrasonic output power.

[0010] Furthermore, the pickling solution used in the ultrasonic organic acid cleaning described in S2 comprises, by weight percentage: 10%~15% citric acid, 5%~8% acetic acid, 2%~4% tartaric acid, and the remainder is deionized water.

[0011] Furthermore, the pickling solution includes a chelating agent with a mass concentration of 1.5~5.0 g / L and a wetting and penetrating aid with a mass concentration of 0.6~1.5 g / L. The chelating agent includes tetrasodium iminodisuccinate (IDS-Na4), and the wetting and penetrating aid includes fatty acid methyl ester ethoxylate (FMEE).

[0012] Furthermore, the specific process of neutralization and rinsing described in S3 is as follows: the pickled steel wire is passed through a neutralization tank and a multi-stage countercurrent rinsing unit in sequence to reduce the amount of residual acid carried out from the surface, thereby obtaining rinsed steel wire.

[0013] Further, the modified boron solution in S4 comprises, by weight percentage: 10%~18% borax, 0.15%~0.30% polycarboxylate dispersant, 0.10%~0.20% organic corrosion inhibitor, and the balance being water; the organic corrosion inhibitor includes sodium benzotriazole, triethanolamine, sodium benzoate, or sodium sebacic acid; the average particle size of the borax is 8~12 μm; the modified boron solution is sprayed onto the surface of the rinsing steel wire through a high-pressure atomizing nozzle, the spray pressure of the high-pressure atomizing nozzle being 0.5~0.55 MPa and the spray distance being 180~250 mm.

[0014] Furthermore, in S5, the drying process is hot air drying, and the winding process uses constant tension winding.

[0015] Furthermore, the high-carbon steel needle cloth raw filament mentioned in S1 includes 70# steel, 80# steel or T10 steel; the friction coefficient μ of the steel wire surface after the needle cloth raw filament pretreatment mentioned in S5 is ≤0.075, and the time without red rust under unpackaged storage conditions is >72 h.

[0016] The present invention further provides an online monitoring system for the above-mentioned green pretreatment process of needle cloth raw yarn with high lubrication and rust resistance, comprising a full-dimensional sensing unit, an intelligent decision processing unit, a dynamic execution control unit, and a monitoring terminal connected by communication; the full-dimensional sensing unit is used to collect data signals in real time during the ultrasonic organic acid cleaning process, the intelligent decision processing unit is used to receive and process data signals and output control commands, the dynamic execution control unit is used to receive and execute the control commands, and the monitoring terminal is used to monitor data signals and issue control commands.

[0017] The online monitoring system provided by this invention is constructed based on Fe 2+The system employs a multi-parameter online monitoring and closed-loop control mechanism for concentration, pH value, conductivity, temperature, and linear velocity. The control unit determines the pickling solution activity and process load status based on real-time data, and adjusts the replenishment, temperature, ultrasonic output, and spraying parameters to ensure process stability and product consistency during continuous production.

[0018] Furthermore, the data signal includes Fe 2+ Concentration, pH value, conductivity, temperature, and wire speed data; the control commands include liquid replenishment, temperature control, ultrasonic power adjustment, and high-pressure atomization spraying pressure adjustment.

[0019] Furthermore, the omnidirectional sensing unit is composed of electrically connected Fe 2+ The system comprises an online sensor, a pH electrode, a conductivity electrode, a temperature sensor, and a linear velocity measuring wheel. The intelligent decision processing unit is preferably based on a PLC (Programmable Logic Controller) with a built-in process control model. The process control model includes a signal processing module, a control algorithm module, a quality traceability module, and an alarm management module that are logically or data-interactingly connected. The dynamic execution control unit includes a metering pump group, a temperature controller, an ultrasonic generator drive module, and a spraying pressure regulating valve.

[0020] Furthermore, the Fe 2+ Online sensor for Fe 2+ The concentration of Fe was collected. 2+ Concentration was collected using photoelectric colorimetric detection. The absorbance was measured after mixing the sample solution with the colorimetric reagent, and the Fe concentration was calculated based on the calibration curve. 2+ Mass concentration.

[0021] Furthermore, the signal processing module in the intelligent decision processing unit is used to receive and process data signals and output control commands, while the control algorithm module performs calculations and analyses according to preset logic to generate control commands.

[0022] Furthermore, the intelligent decision processing unit has a quality traceability function, wherein the quality traceability module is used to bind the processing parameters and pickling solution status data of each reel of needle cloth raw yarn with its unique identification code and generate a process record.

[0023] Furthermore, the alarm management module in the intelligent decision processing unit is used for Fe 2+ Concentration monitoring, when Fe is detected 2+ When the concentration reaches the preset warning value, the system enters the feeding (liquid replenishment) mode; when Fe 2+ When the concentration reaches the critical value, the system will activate the regeneration or bypass treatment device.

[0024] The beneficial effects of this invention are: 1. The green pretreatment process for needle cloth raw yarn provided by this invention has high lubrication and rust resistance properties and is environmentally friendly. It uses a low-volatility pickling solution system (i.e., a composite organic acid system) to replace traditional hydrochloric acid and sulfuric acid, reducing acid mist generation at the source; combined with mechanical peeling pretreatment, it significantly reduces the consumption of chemical reagents and the difficulty of waste liquid treatment, achieving clean production.

[0025] 2. The green pretreatment process for needle-cloth filaments provided by this invention possesses high lubrication and rust-resistant properties, and also provides substrate protection. Through the synergistic effect of physical peeling and precise organic acid cleaning, it effectively avoids over-corrosion and hydrogen embrittlement damage to the high-carbon steel substrate caused by strong acids. Testing shows that the substrate dissolution rate is as low as 0.22 g / m³. 2 It is far lower than the 1.45 g / m³ produced by traditional hydrochloric acid processes. 2 This ensures the intrinsic mechanical properties of the raw silk.

[0026] 3. This invention establishes a multi-parameter online monitoring and closed-loop control system that links the pickling solution state, linear velocity, and process parameters in real time, overcoming the fluctuations of manual experience control, ensuring a high degree of consistency in product surface quality, and improving the stability of the pickling process.

[0027] 4. The green pretreatment process for needle-cloth raw materials provided by this invention, which offers high lubrication and rust resistance, results in needle-cloth raw materials with excellent lubrication and rust resistance. This invention utilizes high-pressure atomized spraying of modified boron liquid to form a uniform and dense lubricating and rust-resistant film layer on the steel wire surface. The coefficient of friction of the treated steel wire is reduced to below 0.075, a reduction of over 50% compared to the traditional impregnation method, significantly extending the life of the drawing die; the time without red rust is increased to over 72 hours, providing a reliable guarantee for inter-process transfer. Attached Figure Description

[0028] To more clearly illustrate the technical solution of the present invention, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0029] Figure 1 This is a schematic diagram of the green pretreatment process for needle cloth raw yarn of the present invention; Figure 2 This is a schematic diagram of the hardware structure and data flow of the online monitoring system of the present invention; Figure 3 Fe in this invention 2+ Schematic diagram of online concentration detection process. Detailed Implementation

[0030] The technical solution of the present invention will now be clearly and completely described in conjunction with the accompanying drawings.

[0031] like Figure 1 As shown, the green pickling process for needle cloth raw yarn with high lubrication and rust resistance provided by this invention mainly includes mechanical pretreatment, online monitoring and adaptive adjustment ultrasonic pickling, neutralization and multi-stage countercurrent rinsing, high-pressure atomized spraying of modified boron liquid (atomized film formation), and hot air drying and constant tension winding steps. The online monitoring and adaptive adjustment ultrasonic pickling step is a process that combines ultrasonic-assisted organic acid cleaning with online monitoring and adaptive adjustment. The specific implementation process of each step is as follows: (1) Mechanical pretreatment High-carbon steel needle cloth raw yarn is fed into a mechanical descaling unit. This invention preferably employs a spiral-type physical descaling device. Its principle lies in utilizing the difference between the good plasticity of the raw yarn matrix and the high brittleness of the iron oxide scale. The raw yarn is subjected to small-radius bending and tangential friction in both forward and reverse directions within two specially staggered descaling rollers, causing the oxide scale to peel off and detach along the interface, achieving efficient physical removal. Afterwards, a circulating airflow thoroughly removes any remaining dust and particles. Preferably, the oxide scale removal rate reaches over 95%, resulting in mechanically pretreated steel wire.

[0032] (2) Ultrasonic-assisted organic acid cleaning The mechanically pretreated steel wire is continuously introduced into an organic pickling tank equipped with an ultrasonic transducer. The pickling tank contains a composite organic pickling solution, the preferred formula by weight percentage being: 10%–15% citric acid, 5%–8% acetic acid, 2%–4% tartaric acid, with the remainder being deionized water. In this composite system, citric acid and tartaric acid have a strong complexing effect on iron ions, while acetic acid is used to adjust the acidity of the system and improve penetration conditions. 1.5–5.0 g / L of tetrasodium iminodisuccinate (IDS-Na4) is also added to the pickling solution as a chelating agent to stabilize iron ions and extend the service life of the pickling solution; simultaneously, 0.6–1.5 g / L of fatty acid methyl ester ethoxylate (FMEE) is added as a wetting and penetrating aid to reduce surface tension and allow the pickling solution to better wet microscopic gaps.

[0033] The pickling temperature is controlled at 80~85℃. The preferred operating frequency of the ultrasonic transducer is 25~40 kHz, and the power density is 1.5~2.5 W / cm². 2 The cavitation effect generated by ultrasound can effectively remove oxides remaining in micro-pits and tiny crevices after mechanical peeling, significantly improving cleaning efficiency and uniformity.

[0034] (3) Online monitoring and adaptive adjustment During the pickling process, an online monitoring system is used to monitor the Fe content in the pickling solution in real time. 2+ The state of the pickling solution is comprehensively judged by considering concentration, pH value, conductivity, temperature, and wire speed.

[0035] (4) Neutralization and multi-stage rinsing After pickling, the steel wire is preferably first passed through a squeezing roller to remove most of the carryover liquid, and then sequentially enters a neutralization tank and a multi-stage countercurrent rinsing unit. The neutralization tank contains a weakly alkaline solution to neutralize residual acid on the surface; the multi-stage countercurrent rinsing uses a step-by-step dilution principle to achieve efficient removal of residual acid and salts from the steel wire surface with minimal water consumption, reducing the risk of contamination in subsequent processes. The multi-stage rinsing is preferably performed in four stages.

[0036] (5) High-pressure atomization film formation The cleaned steel wire is fed into a film-forming box. The box is equipped with multi-directionally arranged high-pressure atomizing nozzles for uniformly spraying modified boron solution onto the steel wire surface. The modified boron solution preferably comprises, by weight percentage: 10%–18% borax, 0.15%–0.30% polycarboxylate dispersant, 0.10%–0.20% organic corrosion inhibitor, and the balance being water. The average particle size of the borax is controlled at 8–12 μm to ensure uniform dispersion; the polycarboxylate dispersant prevents borax particle agglomeration; and the organic corrosion inhibitor enhances the rust-preventive properties of the film. The preferred spray pressure of the high-pressure atomizing nozzles is 0.5–0.55 MPa, and the spray distance is 180–250 mm. This process can rapidly form a uniformly thick, strongly adherent boron-based lubricating and rust-preventive film layer on the steel wire surface.

[0037] (6) Drying and winding After film formation, the steel wire enters a hot air drying oven to quickly remove moisture from the film and solidify the boron film. Subsequently, the steel wire enters a constant tension winding machine to complete winding, obtaining needle cloth filaments that can be directly used in the next drawing process.

[0038] like Figure 2 and Figure 3 As shown, the online monitoring system provided by the present invention includes a full-dimensional sensing unit, an intelligent decision processing unit, a dynamic execution control unit, and a monitoring terminal, all connected by communication.

[0039] The omnidirectional sensing unit is used to acquire data signals in real time during the ultrasonic organic acid cleaning process, and is electrically connected to Fe 2+ The system consists of an online sensor, a pH electrode (pH sensor), a conductivity electrode (conductivity sensor), a temperature sensor, and a linear velocity measuring wheel. It is responsible for real-time acquisition of key process parameters within the pickling tank, including Fe. 2+ Concentration, pH value, conductivity, temperature, and wire linear speed data. Preferably, Fe... 2+The online sensors are connected to the side of the pickling tank via bypass sampling lines. The pH electrode, conductivity electrode, and temperature sensor are physically installed inside the pickling tank by direct immersion, and their signal lines are connected to the signal processing module of the intelligent decision-making unit. The linear velocity measuring wheel is mechanically pressed against the steel wire reference surface at the front end of the drying and take-up unit, rotating synchronously with the steel wire as it travels, transmitting its pulse signals to the intelligent decision-making unit in real time.

[0040] The intelligent decision processing unit (IMF) is centered around a PLC (Programmable Logic Controller) and incorporates a process control model. This model includes an electrically connected signal processing module, a control algorithm module, a quality traceability module, and an alarm management module. The signal processing module receives and processes data signals and outputs control commands. The control algorithm module performs calculations and analysis based on preset logic to generate control commands, including liquid replenishment, temperature control, ultrasonic power adjustment, and high-pressure atomization spraying pressure adjustment. The unit also features quality traceability; the quality traceability module binds the processing parameters and pickling solution status data of each reel of needle cloth filament to its unique identification code, generating a complete process record. The alarm management module is used for Fe... 2+ Concentration monitoring, when Fe is detected 2+ When the concentration reaches the preset warning value, the system enters the feeding (liquid replenishment) mode; when Fe 2+ When the concentration reaches the critical value, the system will activate the regeneration or bypass treatment device.

[0041] The dynamic execution control unit includes a metering pump set, a temperature controller, an ultrasonic generator drive module, and a spray pressure regulating valve. It receives and executes control commands from the intelligent decision processing unit to achieve liquid replenishment, temperature regulation, ultrasonic power regulation, and spray pressure regulation. The input of the metering pump set is connected to a fresh organic acid / chelating agent storage tank, and the output is directly connected to the mixing zone of the pickling tank via a dosing pipeline. The temperature controller's control loop is connected to the electric heating element at the bottom of the pickling tank, achieving closed-loop power control. The ultrasonic generator drive module is connected to an ultrasonic transducer array fixed to the pickling tank wall via a high-frequency shielded cable. The regeneration or bypass treatment device is connected in parallel to the pickling tank side via inlet / outlet pipelines with electric switching valves, and its opening and closing are controlled by relay signals from the PLC. The spray pressure regulating valve is installed on the main inlet pipeline leading to the high-pressure atomizing nozzle of the film-forming box. Its electrical control terminal is connected to the analog output signal of the PLC to dynamically adjust the atomized particle size and flow rate of the spray in the air.

[0042] The monitoring terminal is used for data signal monitoring and issuing control commands, and displays the production line operating status, process parameter curves and alarm information, which facilitates remote monitoring and scheduling by managers.

[0043] During the pickling process, an online monitoring system is used to monitor the Fe content in the pickling solution in real time.2+ The state of the pickling solution is comprehensively judged by considering concentration, pH value, conductivity, temperature, and wire speed.

[0044] Fe 2+ Concentration is a core indicator for judging the degree of aging of pickling solution. This invention uses Fe... 2+ The online sensor uses photoelectric colorimetric detection. The absorbance is measured after the sample solution is mixed with the colorimetric reagent, and the Fe content is converted based on a standard curve. 2+ Mass concentration. When Fe is detected... 2+ When the concentration reaches the preset warning value of 15 g / L, the system automatically enters the feeding mode to replenish chelating agents or compound acid agents; when Fe 2+ When the concentration reaches the critical value of 35 g / L, the system activates the regeneration or bypass treatment device. This device is located on the pickling tank side and connected to it via piping. When replenishment is insufficient to maintain pickling performance, acid is introduced into this device for independent recovery, ensuring the acid in the pickling tank achieves the desired effect. Simultaneously, the intelligent decision-making unit will adjust the Fe... 2+ Changes in concentration and linear velocity compensate for and adjust the ultrasonic output amplitude and pickling solution temperature to ensure the cleaning effect is always within the optimal range. The compensation adjustment process specifically involves: based on "Fe..." 2+ The dynamic changes in "concentration" and "linear velocity" are dynamically compensated bidirectionally through a combined feedforward and feedback control algorithm. When Fe 2+ When the concentration increases (increased solution complexation load) or the linear velocity increases (increased total amount of oxide scale introduced per unit time), the intelligent decision processing unit controls the ultrasonic generator drive module at 1.5~2.5 W / cm². 2 The system increases the output power density within the adjustment range to compensate for the decrease in chemical activity by enhancing the physical peeling effect. The system dynamically adjusts the heating power through a temperature controller to lock the reaction temperature at 80~85℃. If a temporary decrease in linear speed is detected due to process switching, the system will automatically and proportionally reduce the pickling solution temperature to prevent over-pickling, hydrogen embrittlement, or matrix dissolution of the high-carbon steel filament due to relatively prolonged residence time in the acid bath.

[0045] Figure 3 The figure gives Fe 2+ Online concentration detection process. First, a micro-peristaltic pump continuously draws acid samples from the pickling tank at a constant flow rate, and then filters them through an online filter to remove suspended solid particles to prevent clogging of subsequent pipelines and the detection cell. Then, as the filtered acid passes between the online filter and the mixing reactor, a colorimetric reagent (e.g., 1,10-phenanthroline solution) is mixed in a specific ratio as the colorimetric agent. Under specific pH conditions (typically 3.5-5.5), 1,10-phenanthroline reacts with Fe... 2+A selective chelation reaction occurs, forming a stable orange-red complex [Fe(phen)3]. 2+ The mixture is thoroughly mixed and reacted in a mixing reactor until it turns orange-red. Finally, the colored acid solution enters a photoelectric detection cell. A green light beam with a wavelength of 510 nm, which can be absorbed by the orange-red complex, is incident into the flow cell. The intensity of the transmitted light is detected by a detector below, and the Fe is calculated using Lambert-Beer's law. 2+ The concentration is then adjusted, and the waste liquid is subsequently recycled in a waste pool.

[0046] pH value is a key control indicator for assessing the degree of free acid consumption in pickling solutions and the system's anti-precipitation buffering capacity. This invention uses a pH sensor with electrode detection to collect the acidity electrical signal of the pickling solution in real time. When the pH value is monitored to be stable within the optimal steady-state cleaning range of 1.5 to 2.5, the system maintains closed-loop operation. When the pH value rises with reaction consumption and exceeds the preset upper limit threshold, it indicates insufficient free acid in the system. The intelligent decision-making unit automatically switches to the feeding mode, coordinating with the metering pump group to add fresh composite acid solution proportionally to restore washing activity and prevent iron ions from hydrolyzing and precipitating due to insufficient acidity.

[0047] Electrical conductivity is an immediate physical indicator reflecting the total ion mobility, total electrolyte concentration, and overall aging of the pickling solution. This invention employs an electrode-based conductivity sensor to continuously monitor the conductivity of the reaction solution. When the conductivity is within the normal steady-state range of 20–100 mS / cm, the system operates normally; when the conductivity deviates from the current steady-state range due to material imbalance, the system continues to operate normally. 2+ When the concentration is above ±15% of the calibrated steady-state curve, the intelligent decision processing unit uses algorithms to comprehensively identify whether the concentration passively increases due to high-temperature evaporation of water or consumption of organic acid ions, and issues dynamic water replenishment or dynamic acid replenishment commands accordingly.

[0048] Temperature is a core process indicator for controlling the chemical reaction kinetics of complex organic acids, the adsorption and complexation efficiency of chelating agents, and the intensity of ultrasonic cavitation. This invention uses a real-time resistance temperature detector (RTD) to directly acquire the actual reaction temperature inside the pickling tank. When the pickling solution temperature is detected to be below 80°C, the system adaptively increases the heating output power of the temperature controller to accelerate the chemical stripping of the residual dense oxide layer by the organic acids. When the temperature reaches the upper limit of 85°C, the system dynamically reduces the heating output to maintain a constant temperature, preventing excessive boiling of the reaction solution and excessive vaporization and loss of volatile components (such as acetic acid), ensuring that the cleaning effect is within the optimal window.

[0049] The linear velocity of the steel wire is a core feedforward indicator that determines the effective residence time of a single coil of needle-cloth precursor yarn in the pickling tank and the real-time production load of the entire production line. This invention uses a mechanical speed-measuring wheel sensor to dynamically acquire the traveling speed of the needle-cloth precursor yarn. When the linear velocity fluctuates within a steady-state range of 400~600 m / min, the central controller synchronously feeds forward to adjust the ultrasonic power and the high-pressure atomization spraying pressure of the subsequent process, achieving adaptive tracking between multiple processes. When the linear velocity is detected to have temporarily decreased due to reasons such as coil switching, the system automatically slightly reduces the pickling temperature and ultrasonic power to prevent over-pickling, hydrogen embrittlement, or pitting damage to the high-carbon steel precursor yarn due to prolonged residence time.

[0050] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to specific embodiments. All mentioned embodiments are implemented based on the technical solutions of this invention, and detailed implementation processes are provided. However, it should be stated that the scope of protection of this invention is not limited to the following embodiments. Unless otherwise specified, the experimental methods used in the following experimental examples are conventional methods; the materials and reagents used, unless otherwise specified, are commercially available.

[0051] Example 1

[0052] The material being processed is 80# high-carbon steel wire with a diameter of 3.9 mm. (1) Mechanical pretreatment: The steel wire is treated by a spiral physical peeling equipment, and the oxide scale removal rate reaches 98.5%, resulting in mechanically pretreated steel wire; (2) Ultrasonic-assisted organic acid cleaning: The mechanically pretreated steel wire from step (1) is continuously introduced into an organic acid cleaning tank equipped with an ultrasonic transducer for acid cleaning. The acid cleaning solution formula is 10% citric acid, 6% acetic acid, 4% tartaric acid, with the addition of 2.5 g / L IDS-Na4 and 0.8 g / L FMEE. The acid cleaning temperature is 82℃, the ultrasonic frequency is 28 kHz, and the power density is 2.0 W / cm³. 2 Linear velocity: 400 m / min; (3) Online monitoring and adaptive adjustment: During the pickling process, this process uses a multi-parameter collaborative acquisition system through a full-dimensional sensing unit, and a composite adaptive adjustment logic is implemented by an intelligent decision processing unit: When the pH value is detected to exceed the preset upper limit threshold of 2.5 due to the consumption of the acid washing reaction, the intelligent decision processing unit will automatically add fresh compound acid agent in conjunction with the metering pump group to accurately maintain the pH value in the optimal activity range of 1.5~2.5, so as to ensure the acid washing rate and effectively prevent the hydrolysis of iron ions into colloidal precipitation. The intelligent decision processing unit uses linear velocity as the system's feedforward input. If the linear velocity fluctuates within the steady-state range of 400~600 m / min, the central controller PLC will adjust the input based on the linear velocity. 2+ The coupling change of concentration and linear velocity dynamically controls the ultrasonic generator drive module and temperature controller; when the linear velocity increases or Fe... 2+ When the concentration increases, the system automatically adjusts to 1.5~2.5 W / cm². 2 Within the adjustment range, the ultrasonic output power density is dynamically increased, and the pickling temperature is stably controlled at 80~85℃ by dynamically adjusting the heating power. When the linear speed is detected to decrease briefly due to reasons such as the switching of the coil, the system automatically and proportionally reduces the pickling temperature and ultrasonic power to prevent the high carbon steel wire from being over-pickled, hydrogen embrittled or matrix dissolved due to the longer effective residence time, and to ensure that the cleaning effect is always at the best window. Based on the above maintenance, the system utilizes Fe 2+ The online sensor uses photoelectric colorimetric detection to collect Fe in the pickling solution in real time. 2+ Mass concentration (detection cycle is 30 seconds / time), the absorbance is measured after mixing the sample solution with the colorimetric reagent, and the Fe is converted according to the standard curve. 2+ Mass concentration is used as the core indicator for determining the degree of complexation aging in the pickling system. Based on this real-time monitoring data, the system executes the following hierarchical control logic: When Fe was detected 2+ When the concentration is ≤15 g / L, the system determines that the bath solution is in a highly active state and maintains the conventional adaptive self-tracking adjustment process; When the system detects Fe 2+ When the concentration rises to the preset warning threshold of 15g / L (and <35g / L), the intelligent decision processing unit combines the current wire speed and pickling tank solution to automatically calculate the fine replenishment requirement, and links the metering pump group to replenish fresh composite organic acid and chelating agent to the pickling tank in proportion to maintain the ratio balance and complexing rust removal activity of the pickling solution. When Fe was detected 2+ When the concentration reaches the critical value of 35 g / L, the intelligent decision-making and processing unit determines that the aging degree of the pickling solution has exceeded the adjustment limit of a single replenishment. It then activates the bypass treatment device located on the side of the pickling tank through the alarm management module, and introduces the severely aged acid solution into an independent recovery circuit for iron reduction and regeneration treatment to ensure that the acid solution efficiency in the main pickling tank always meets the expected requirements.

[0053] (4) Neutralization and multi-stage rinsing: The pickled steel wire is first passed through the squeezing roller to remove most of the carry-out liquid, and then passed through the neutralization tank and the multi-stage countercurrent rinsing unit in sequence. After 4 stages of countercurrent rinsing, the pH of the rinsing tank is 6.5~8.0, and the rinsed steel wire is obtained. (5) High-pressure atomization film formation: The rinsed steel wire from step (4) is fed into the film formation box, and the modified boron liquid is sprayed onto the surface of the steel wire through a high-pressure atomizing nozzle. The wet film adhesion amount is 18 g / m 2 After drying, a lubricating and rust-preventing film with a thickness of 2.6 μm is formed, resulting in a film-forming steel wire. The modified boron solution contains 14% borax with an average particle size of 10 μm, and includes 0.20% polycarboxylate dispersant and 0.15% sodium benzotriazole. Real-time adjustments are made to maintain a spraying pressure of 0.52 MPa and a spray distance of 200 mm to ensure the uniformity and consistency of the film thickness, thus guaranteeing the long-term rust-preventing effect of the needle cloth filament.

[0054] (6) Drying and winding: After the film-forming steel wire in step (5) is dried by hot air, it is wound up under constant tension to complete the pretreatment of 80# high carbon steel wire.

[0055] Comparative Example 1 The same batch of 3.9 mm 80# high carbon steel wire was treated with a traditional hydrochloric acid pickling process. The acid solution was 15% HCl, the pickling temperature was 55℃, and the linear speed was 250 m / min. Boring was then performed using an immersion method. The borosilicate solution used was a traditional mixed salt type, with the following mass fractions: 50% borax, 30% sodium chloride and 10% barium chloride as diluents, and 10% silicon carbide as an activator.

[0056] Comparative Example 2 The same batch of steel wires was treated with a pickling process using only citric acid (15% concentration) without ultrasonic assistance, without an online monitoring system, and other conditions were the same as in Example 1.

[0057] The properties of the needle cloth filaments obtained in Example 1 and Comparative Examples 1 and 2 were tested, and the results are shown in Table 1.

[0058] Table 1 Properties of needle cloth raw yarn after different processing techniques

[0059] As shown in Table 1, the process of Example 1 of this invention is significantly superior to the traditional hydrochloric acid process (Comparative Example 1) and the single acid process without ultrasonic assistance (Comparative Example 2) in terms of oxide scale removal rate, substrate protection, surface finish, lubrication performance, and rust prevention capability. In particular, the extremely low coefficient of friction and its stability under long-term drawing can be directly translated into an extension of die life and a reduction in the drawing breakage rate.

[0060] Example 2 This embodiment differs from Embodiment 1 in that it uses T10 high-carbon steel wire with a diameter of 1.7 mm as the substrate. To address the characteristics of fine wires having a large specific surface area and being more susceptible to the effects of over-pickled treatment, the total acid concentration was increased to 22% (13% citric acid, 6% acetic acid, and 3% tartaric acid), and the IDS-Na4 concentration was increased to 4.0 g / L. Ultrasonic-assisted pickling was performed using a 33-40 kHz sweep frequency mode, and the linear velocity was increased to 550 m / min. An online monitoring system was introduced to link the linear velocity with the acid temperature: when the linear velocity briefly decreased, the system automatically slightly reduced the acid temperature to avoid over-treatment. Testing showed that no obvious pitting corrosion was observed on the surface of the steel wire treated in this embodiment, and the breakage rate during subsequent drawing was reduced by more than 40% compared to the traditional process, with the friction coefficient remaining stable between 0.070 and 0.073.

[0061] Example 3 The difference between this embodiment and Embodiment 1 is that T10 steel was used as the substrate, and while maintaining the total acid concentration at 22%, the FMEE was adjusted to 1.5 g / L to enhance the penetration effect at high linear velocities. The online monitoring system focused on monitoring conductivity and Fe. 2+ The synergistic change in concentration serves as a basis for judging the overall activity of the acid solution. When conductivity and Fe... 2+ When the concentration ratio exceeds the preset range, the system issues an early warning and automatically adjusts the replenishment strategy. The steel wire treated in this embodiment can remain rust-free for over 90 hours between processes, greatly facilitating long-cycle production scheduling.

[0062] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A green pretreatment process for needle cloth raw yarn with high lubrication and rust resistance, characterized in that, Includes the following steps: S1, Mechanical pretreatment: Mechanical peeling and dust removal are performed on the high carbon steel needle cloth raw wire rod to obtain pretreated steel wire; S2, Online monitoring and adaptive adjustment of ultrasonic pickling: The mechanically pretreated steel wire described in S1 is subjected to ultrasonic organic acid cleaning. During the pickling process, the pickling solution parameters are monitored online in real time, and the state of the pickling solution is judged in combination with the steel wire linear speed. The replenishment and process parameters are adjusted to obtain the pickled steel wire. S3, Neutralization and rinsing: The pickled steel wire described in S2 is subjected to extrusion, neutralization and rinsing in sequence to obtain rinsed steel wire; S4, Atomization film formation: The surface of the rinsed steel wire described in S3 is sprayed with modified boron liquid to form a lubricating and rust-preventing film layer, thus obtaining a film-forming steel wire; S5, Drying and winding: The film-forming steel wire described in S4 is dried and then wound up to complete the pretreatment of the needle cloth raw yarn.

2. The green pretreatment process for needle cloth filaments with high lubrication and rust resistance as described in claim 1, characterized in that, The mechanical peeling described in S1 is carried out in a mechanical peeling unit.

3. The green pretreatment process for needle cloth filaments with high lubrication and rust resistance as described in claim 1, characterized in that, The pickling solution parameters mentioned in S2 include Fe 2+ Concentration, pH value, conductivity, and temperature; the ultrasonic organic acid cleaning temperature is 80~85℃, the ultrasonic frequency is 25~40 kHz, and the power density is 1.5~2.5 W / cm³. 2 The Fe 2+ The concentration is 0~35 g / L, the pH value is 1.5~2.5, the conductivity is 20~100 mS / cm, and the wire speed is 400~600 m / min.

4. The green pretreatment process for needle cloth filaments with high lubrication and rust resistance as described in claim 1, characterized in that, The ultrasonic organic acid cleaning solution described in S2 comprises, by weight percentage: 10%~15% citric acid, 5%~8% acetic acid, 2%~4% tartaric acid, and the remainder is deionized water.

5. The green pretreatment process for needle cloth filament with high lubrication and rust resistance as described in claim 4, characterized in that, The pickling solution includes a chelating agent with a mass concentration of 1.5~5.0 g / L and a wetting and penetrating aid with a mass concentration of 0.6~1.5 g / L. The chelating agent includes tetrasodium iminodisuccinate, and the wetting and penetrating aid includes fatty acid methyl ester ethoxylate.

6. The green pretreatment process for needle cloth filaments with high lubrication and rust resistance as described in claim 1, characterized in that, The modified boron solution in S4 comprises, by weight percentage: 10%~18% borax, 0.15%~0.30% polycarboxylate dispersant, 0.10%~0.20% organic corrosion inhibitor, and the balance being water; the organic corrosion inhibitor includes sodium benzotriazole, triethanolamine, sodium benzoate, or sodium sebacic acid; the average particle size of the borax is 8~12 μm; the modified boron solution is sprayed onto the surface of the rinsing steel wire through a high-pressure atomizing nozzle, the spray pressure of the high-pressure atomizing nozzle being 0.5~0.55 MPa and the spray distance being 180~250 mm.

7. An online monitoring system applied in the green pretreatment process of needle cloth raw yarn with high lubrication and rust resistance as described in any one of claims 1 to 6, characterized in that, It includes a full-dimensional sensing unit with communication connectivity, an intelligent decision processing unit, a dynamic execution control unit, and a monitoring terminal; the full-dimensional sensing unit is used to collect data signals in real time during the ultrasonic organic acid cleaning process, the intelligent decision processing unit is used to receive and process data signals and output control commands, the dynamic execution control unit is used to receive and execute the control commands, and the monitoring terminal is used to monitor data signals and issue control commands.

8. The online monitoring system according to claim 7, characterized in that, The omnidirectional sensing unit is electrically connected to Fe 2+ The system comprises an online sensor, a pH electrode, a conductivity electrode, a temperature sensor, and a linear velocity measuring wheel; the intelligent decision processing unit is based on a PLC and has a built-in process control model, which includes a signal processing module, a control algorithm module, a quality traceability module, and an alarm management module with logical or data interaction connections; the dynamic execution control unit includes a metering pump group, a temperature controller, an ultrasonic generator drive module, and a spraying pressure regulating valve.

9. The online monitoring system according to claim 8, characterized in that, The Fe 2+ Online sensor for Fe 2+ The concentration of Fe was collected. 2+ Concentration was collected using photoelectric colorimetric detection. The absorbance was measured after mixing the sample solution with the colorimetric reagent, and the Fe concentration was calculated based on the calibration curve. 2+ Mass concentration.

10. The online monitoring system according to claim 8, characterized in that, The quality traceability module in the intelligent decision-making processing unit is used to bind the processing parameters and pickling solution status data of each reel of needle cloth raw yarn with its unique identification code and generate process records.

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