目的 针对TC4钛合金在超精密加工中因硬度高、相结构复杂导致的抛光效率低和表面质量均匀性差的问题,提出一种石墨烯辅助的化学磁流变抛光方法。方法 在含有过氧化氢和羰基铁粉的芬顿反应体系中引入单层石墨烯,配制新型磁流变抛光液。通过氧化还原电位测量、浸液实验、X射线光电子能谱分析以及抛光力实时监测,探究石墨烯对芬顿反应的催化机理及对抛光过程的润滑作用;并通过单因素实验分析加工间隙和主轴转速对材料去除率与表面粗糙度的影响。结果 实验表明,石墨烯促进了芬顿反应体系的进行,30 min时氧化还原电位值从337 mV提升至347 mV;XPS分析证实石墨烯增强了表面氧化,使抛光后工件表面氧化层的高价态Ti4+含量（原子数分数）从54.81%提升至60.13%。此外,石墨烯的引入使平均抛光力降低了50%（从0.26 N降至0.13 N）,且提升了抛光力的稳定性。在加工间隙1.0 mm、主轴转速400 rad/min的优化条件下,TC4钛合金表面粗糙度Sa从初始的350 nm在15 min内降至75 nm。结论 石墨烯在化学磁流变抛光中具有催化氧化与润滑减摩的双重功能,能够实现TC4钛合金的高效高质量抛光,为复杂难加工材料的超精密表面处理提供了新思路。
Abstract
TC4 titanium alloy is a representative α+β type titanium alloy widely utilized in aerospace, marine engineering, and biomedical implants due to its high specific strength, excellent corrosion resistance, and superior biocompatibility. However, its inherent characteristics such as high chemical reactivity, low thermal conductivity, and the complex mechanical properties of its dual-phase structure make it a typical "difficult-to-machine" material. Traditional polishing methods often suffer from low material removal rates and poor surface consistency. To address these challenges, the work aims to propose a novel graphene-assisted chemical magnetorheological polishing method. By integrating the catalytic properties and lubricating effects of graphene into a magnetorheological Fenton-based system, it is expected to achieve a synergistic equilibrium between enhanced chemical oxidation and stable mechanical abrasion, thereby realizing high-efficiency and high-integrity surface finishing of TC4 alloy.
A customized magnetorheological polishing fluid was formulated, consisting of 0.40wt.% monolayer graphene flakes, 15wt.% carbonyl iron powder, 5wt.% alumina abrasives, and a 3.0wt.% hydrogen peroxide solution as the primary oxidant. The catalytic mechanism of graphene on the Fenton reaction was firstly investigated. The oxidation-reduction potential was monitored in real time to evaluate the generation of hydroxyl radicals. To verify the chemical modification of the TC4 surface, immersion tests and X-ray photoelectron spectroscopy were performed to analyze the evolution of titanium oxides. Furthermore, the mechanical behavior of the polishing process was scrutinized by measuring the tangential polishing force with a Kistler dynamometer. A series of single-factor experiments were conducted to evaluate the effect of critical process parameters, specifically the machining gap (ranging from 0.4 mm to 1.6 mm) and the spindle speed (varying from 200 rad/min to 600 rad/min), on the material removal rate and surface roughness.
The experimental results demonstrated that the addition of graphene significantly accelerated the electron transfer during the Fe2+/Fe3+ cycle, thereby enhancing the Fenton reaction's efficiency. The ORP values in the graphene-assisted system increased from 337 mV to 347 mV within 30 minutes, indicating a higher oxidative capacity. XPS analysis revealed that graphene promoted the transition of titanium from lower valence states to higher valence states. Specifically, the concentration of Ti4+ on the workpiece surface increased to 60.13%, while the metallic Ti content significantly decreased. This chemical transformation resulted in a thicker, relatively loose sacrificial oxide layer that was more susceptible to mechanical removal. Regarding mechanical stability, the introduction of graphene as a solid lubricant led to a 50% reduction in the average polishing force (from 0.26 N to 0.13 N). More importantly, graphene suppressed the force attenuation typically caused by the degradation of the MR fluid's structure, ensuring a consistent removal rate throughout the process. Under the optimized conditions of a 1.0 mm machining gap and a 400 rad/min spindle speed, the surface roughness Sa of the TC4 workpiece was successfully reduced from an initial 350 nm to a final 75 nm within 15 minutes. The surface morphology analysis showed a significant reduction in typical defects such as micro-pits, scratches, and phase-boundary relief, yielding a mirror-like finish.
It is concluded that graphene plays a dual-functional role in the CMRP process. It acts as a heterogeneous catalyst that intensifies the Fenton-based chemical softening of the TC4 surface, and simultaneously functions as a high-performance lubricant that stabilizes the mechanical shear force of the MR flexible "brush". The synergy between graphene-enhanced chemical oxidation and stabilized mechanical removal effectively overcomes the polishing resistance of TC4 titanium alloy. This G-CMRP technique provides a theoretically grounded and practically effective strategy for the ultra-precision manufacturing of complex titanium components, offering significant potential for applications requiring extreme surface integrity.
关键词
石墨烯 /
化学磁流变抛光 /
TC4钛合金 /
芬顿反应 /
表面粗糙度 /
材料去除率
Key words
graphene /
chemical magnetorheological polishing /
TC4 titanium alloy /
Fenton reaction /
surface roughness /
material removal rate
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基金
温州市应用基础研究（基础研究）项目（GK20250148）; 国家自然科学基金（面上）（52475446）; 安徽省自然科学基金项目（面上）（2308085ME170）; 安徽省科技创新攻坚计划重大重点项目（202423i08050035）; 浙江省教育厅一般科研项目（Y202454613）; 温州市重大科技创新攻关项目（ZG2022029）; 浙江省大学生科技创新活动计划（新苗人才计划）（2025R444C066）
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