Environment-friendly cleaning agent for degreasing metal surface

Abstract

The present application relates to the technical field of metal material chemical cleaning, and discloses an environment-friendly cleaning agent for degumming of a metal surface, comprising: tert-butyl hydrogen peroxide, diethylene glycol monobutyl ether, polyoxyethylene polyoxypropylene copolymer with a multi-branched structure, and deionized water, wherein the diethylene glycol monobutyl ether forms an associated structure with the tert-butyl hydrogen peroxide through hydrogen bonds; after the cleaning agent penetrates into the gap between the oxide film and the gum layer on the metal surface, the Lewis acid center of the oxide film competitively cuts the hydrogen bonds, induces in-situ decomposition of the tert-butyl hydrogen peroxide to release oxygen, and the interface pressure generated by the oxygen converts chemical energy into normal mechanical work, realizes whole peeling of the gum layer from the interface root, suppresses diffusion loss of the solvent in the gum layer body phase, and shortens the cleaning period without damaging the metal matrix.

Description

Technical Field

[0001] This invention relates to an environmentally friendly cleaning agent for degumming metal surfaces, belonging to the field of chemical cleaning technology for metal materials. Background Technology

[0002] Current chemical cleaning of metal materials mainly utilizes surfactants for wetting and emulsification or organic solvents for physical dissolution to remove surface organic contaminants. By increasing the chemical affinity of the solvent for the contaminants, the contaminants swell and dissolve from the substrate surface and diffuse into the cleaning bulk phase.

[0003] For cured sealant residues, such as epoxy resin or polyurethane adhesive layers, on the surface of precision metal irregularly shaped parts, existing environmentally friendly cleaning agents mostly employ a dissolution-penetration path. The cured adhesive layer has a dense structure, and the metal surface exhibits microscopic geometric features. The resistance to capillary penetration of environmentally friendly solvent molecules into the interfacial gaps increases with depth. This dissolution-diffusion method consumes the solvent's chemical potential energy in the bulk phase swelling of the adhesive layer, rather than acting at the interface root, leading to rapid saturation of the adhesive concentration in the cleaning solution. This shortens the online service life and increases wastewater treatment costs. Improvement approaches such as increasing solvent polarity or introducing penetrating components are limited by the kinetic obstacles within the confined interfacial space, making it difficult to solve the wetting saturation problem. Increasing cleaning intensity can easily trigger intergranular corrosion or micro-corrosion of the oxide film on the metal substrate surface. Texture damage disrupts the stability of part dimensional tolerances. Overcoming the energy conversion limitations of the dissolution-diffusion model without sacrificing the safety of the substrate has become the fundamental contradiction restricting the improvement of cleaning quality. For example, Chinese invention patent CN108677195B discloses a method for degumming adhesive metals, which accelerates degumming through a combination of dichloromethane, sulfuric acid, and alumina. This method does not deviate from the chemical corrosion-diffusion dissolution method. Dichloromethane has high environmental and toxicological pressures, and its volatilization causes fluctuations in the composition of the bath solution. Strong acid components such as sulfuric acid can easily cause intergranular corrosion of the oxide film, damaging the dimensional tolerances and fatigue strength of parts. Colloidal components dissolve in the cleaning solution, saturating the bath solution and forming a viscous waste liquid, shortening the online service life and increasing the processing cost.

[0004] Therefore, how to construct a stripping mechanism based on in-situ conversion of interface energy, and use the inherent catalytic properties of the metal surface to drive the stripping action, so as to achieve non-destructive stripping of the adhesive from the root of the metal interface, has become the technical problem to be solved by this invention. Summary of the Invention

[0005] To address the problems mentioned in the background art, the technical solution of the present invention is as follows: An environmentally friendly cleaning agent for degumming metal surfaces, comprising 100 parts by total weight of the environmentally friendly cleaning agent, and consisting of the following components:

[0006] 5 to 15 parts of tert-butyl hydrogen peroxide;

[0007] 25 to 40 parts of diethylene glycol monobutyl ether;

[0008] 0.5 to 3 parts of a polyoxyethylene-polyoxypropylene copolymer with a multi-branched structure;

[0009] And the remainder of deionized water; wherein, the total molar amount of ether bond oxygen atoms and hydroxyl oxygen atoms in the diethylene glycol monobutyl ether molecule Molar amount of peroxyhydroxyl hydrogen atoms in tert-butyl hydrogen peroxide molecule ratio for to ;

[0010] The weight-average molecular weight of polyoxyethylene-polyoxypropylene copolymers with multi-branched structures is to And the mass fraction of its branched terminal hydroxyl groups is to ;

[0011] Environmentally friendly cleaning agents Value to And environmentally friendly cleaning agents The surface tension below is to ;

[0012] Diethylene glycol monobutyl ether forms an associated structure with tert-butyl hydrogen peroxide via hydrogen bonds;

[0013] After the environmentally friendly cleaning agent penetrates into the gap between the oxide film and the adhesive layer on the metal surface, the Lewis acid centers of the oxide film on the metal surface competitively adsorb hydrogen bonds, causing tert-butyl hydrogen peroxide to decompose and release oxygen in the gap. The interfacial pressure generated by the oxygen is used to achieve the peeling of the adhesive layer from the metal surface.

[0014] Preferably, in the polyoxyethylene-polyoxypropylene copolymer with a multi-branched structure, the mass ratio of the polyoxyethylene segment to the polyoxypropylene segment is: to The equilibrium adsorption capacity of polyoxyethylene-polyoxypropylene copolymers with multi-branched structures on the oxide film of aluminum alloy surfaces is greater than that of diethylene glycol monobutyl ether on the oxide film of aluminum alloy surfaces, thus enabling the polyoxyethylene-polyoxypropylene copolymers with multi-branched structures to preferentially form an adsorption layer on the metal surface; the kinematic viscosity of the polyoxyethylene-polyoxypropylene copolymers with multi-branched structures is... Below is to .

[0015] Preferably, the pressure of the gas released by the decomposition of tert-butyl hydrogen peroxide under the catalysis of the oxide film on the aluminum alloy surface is greater than the adhesion strength between the adhesive layer and the aluminum alloy surface.

[0016] Preferably, it also includes portion to Benztriazole; the conductivity of deionized water is lower than .

[0017] Preferably, the polyoxyethylene-polyoxypropylene copolymer with a multi-branched chain structure is anchored to the surface of the metal oxide film through multi-point hydrogen bonds.

[0018] Preferably, the mixing stability of environmentally friendly cleaning agents is determined by the coating coefficient. Characterization, Coverage Coefficient Satisfy the following formula: ,in, This represents the molar amount of ether bonds in a unit volume of diethylene glycol monobutyl ether molecule. This represents the molar amount of hydroxyl groups in a unit volume of diethylene glycol monobutyl ether molecule. This represents the molar amount of peroxy bonds in a tert-butyl hydrogen peroxide molecule per unit volume.

[0019] Preferably, the environmentally friendly cleaning agent penetrates the epoxy resin layer on the aluminum alloy surface at a rate greater than [missing value]. .

[0020] Preferably, it also includes portion to A portion of triethanolamine.

[0021] Preferably, the environmentally friendly cleaning agent also includes diethylene glycol monohexyl ether, wherein the weight ratio of diethylene glycol monohexyl ether to diethylene glycol monobutyl ether is [missing information]. to .

[0022] Preferably, the gaseous products released by the decomposition of tert-butyl hydrogen peroxide within the gap between the oxide film and the adhesive layer on the aluminum alloy surface cause a peeling displacement, the peeling displacement being... to .

[0023] Compared with the prior art, the beneficial effects of the present invention are:

[0024] 1. In environmentally friendly cleaning agents, the Lewis acid active sites of the oxide film on the metal surface are used as reaction triggers to induce the hydrogen-bonded associative expansion precursors that penetrate into the nano-gap of the interface to undergo transient decomposition within a confined space. This directly converts chemical energy into peeling stress pointing towards the metal surface normal, switching the industry's conventional layer-by-layer swelling mode from the outside to the inside to a whole-piece peeling mode from the root of the interface outward. This avoids the meaningless diffusion loss of environmentally friendly solvents in the dense colloidal bulk phase and shortens the cleaning cycle of precision parts on complex irregular surfaces.

[0025] 2. The interface anchoring agent constructs a nanoscale elastic barrier layer on the metal surface through a multi-branched chain structure, which constrains the gas phase pressure released by the precursor decomposition within the extremely narrow interface between the adhesive layer and the metal, preventing the pressure from dissipating into the interior of the colloid. This allows the microscopic volume work generated by the chemical reaction to be highly focused on overcoming the interface anchoring force. This kinetic synergy among multiple components transforms the originally disordered chemical decomposition into a directional mechanical peeling action, enabling the low-toxicity and environmentally friendly components to have the technical ability to treat ultra-thick or high-toughness sealant residues.

[0026] 3. By driving the stripping reaction through the inherent catalytic sites on the metal surface, the stripping action is self-feedback adjusted and the substrate is self-adaptive protected. When the adhesive layer detaches from the metal substrate and exposes the catalytic sites to excessive cleaning liquid, the local reactant concentration is diluted, causing the decomposition reaction to terminate. This ensures that the oxide layer on the surface of precision parts is not damaged by excessive reaction, preserving the original micro-texture and geometric precision of the metal substrate, and avoiding intergranular corrosion or stress damage that is prone to occur during traditional heavy cleaning processes. Attached Figure Description

[0027] Fig. 1 This is a flowchart illustrating the in-situ peeling mechanism of the environmentally friendly cleaning agent in confined spaces according to the present invention.

[0028] Fig. 2 This is a graph showing the influence of the coating coefficient S on degumming time and the stability threshold analysis of the present invention.

[0029] Fig. 3 This is a structural diagram of the degumming system integrating waste liquid recycling and gas phase treatment according to the present invention. Detailed Implementation

[0030] The present invention will be described in detail below through specific embodiments. It should be understood that the following embodiments are only used to explain the present invention and do not constitute a limitation on the scope of protection of the present invention. Non-substantial substitutions made by those skilled in the art based on the technical essence of the present invention are all within the scope of protection of the present invention.

[0031] This invention provides an environmentally friendly cleaning agent for degumming metal surfaces, composed of tert-butyl hydrogen peroxide, diethylene glycol monobutyl ether, a polyoxyethylene-polyoxypropylene copolymer with a multi-branched structure, and deionized water. It constructs a confined space micro-bursting system within the extremely narrow interface between the metal surface oxide film and the adhesive layer, utilizing the Lewis acid centers of the metal surface oxide film to catalyze the in-situ decomposition of the effective components, achieving complete peeling of the adhesive from the root of the metal substrate. In the cleaning process of precision metal irregularly shaped parts, the polar bonding force between the cured sealant and the metal oxide film makes it difficult for conventional environmentally friendly solvents to achieve rapid wetting within the confined space. The resistance of solvent molecules penetrating into the interface gaps through capillary action increases with depth. To solve this technical challenge, this invention configures a peeling system containing a hydrogen-bonded association structure, with the total weight of the environmentally friendly cleaning agent being... It is composed of the following components per serving: portion to tert-butyl hydroperoxide; portion to Amount of diethylene glycol monobutyl ether; portion to A portion of a polyoxyethylene-polyoxypropylene copolymer with a multi-branched structure; and the balance of deionized water; diethylene glycol monobutyl ether forms an associative structure by forming hydrogen bonds between the ether oxygen atoms and hydroxyl oxygen atoms in the molecule and the peroxy hydroxyl hydrogen atoms in the tert-butyl hydrogen peroxide molecule; the total molar amount of ether oxygen atoms and hydroxyl oxygen atoms in the diethylene glycol monobutyl ether molecule Molar amount of peroxyhydroxyl hydrogen atoms in tert-butyl hydrogen peroxide molecule ratio Set at to Within the specified range; this molar ratio ensures that diethylene glycol monobutyl ether fully coats tert-butyl hydrogen peroxide in the bulk state, inhibiting uncontrolled decomposition of tert-butyl hydrogen peroxide during storage and transportation; to evaluate the mixing stability of environmentally friendly cleaning agents, the coating coefficient is used. Quantitative characterization, coverage coefficient The following relationship must be satisfied: ,in, This represents the molar amount of ether bonds in a unit volume of diethylene glycol monobutyl ether molecule. This represents the molar amount of hydroxyl groups in a unit volume of diethylene glycol monobutyl ether molecule. The molar amount of peroxy bonds in a tert-butyl hydrogen peroxide molecule per unit volume; when When the value is not less than 1.5, the system exhibits a uniform and transparent state, and the latency period of the effective components at room temperature is not less than 6 months.

[0032] To address the differences in Lewis acid center activity across oxide films on different metal substrates, a calibration procedure for the dosage of tert-butyl hydrogen peroxide based on pyridine adsorption infrared spectroscopy was established, measuring 1450... area of ​​characteristic absorption peak at Lewis acid sites Determine the catalytic potential of the matrix. The corresponding Lewis acid concentration is lower than At that time, the amount of tert-butyl hydroperoxide added was set to 12 to 15 parts, and the molar ratio of diethylene glycol monobutyl ether to tert-butyl hydroperoxide was simultaneously adjusted. The value was lowered to 1.2 to 1.5 to reduce the hydrogen bond association energy and compensate for insufficient matrix catalytic activity; electrochemical impedance spectroscopy was used to monitor the interfacial charge transfer resistance online at the cleaning site. The decay pattern, after immersion for 120 seconds Change value If the oxygen release pressure does not reach 50% of the initial value, it is determined that the oxygen release pressure has not exceeded the peeling threshold. Therefore, 0.5% tert-butyl hydrogen peroxide is added to the cleaning tank until the pressure sensor monitors the interface peeling stress. Achieving a strength of over 0.8 MPa; addressing the extremely strong adhesion between the oxide layer and the adhesive layer on the metal surface, this invention introduces a polyoxyethylene-polyoxypropylene copolymer with a multi-branched structure as an interface anchoring agent, with a weight-average molecular weight of... to And the mass fraction of its branched terminal hydroxyl groups is to The equilibrium adsorption capacity of the polyoxyethylene-polyoxypropylene copolymer with a multi-branched structure on the oxide film of aluminum alloy surface is greater than that of diethylene glycol monobutyl ether on the oxide film of aluminum alloy surface, thus preferentially forming an adsorption layer with a nanometer-thickness on the metal surface. This copolymer is anchored to the oxide film on the metal surface through multi-point hydrogen bonds, and its multi-branched structure constructs a layer with a thickness of [missing information - likely a number] at the interface. to The elastic barrier layer; when the environmentally friendly cleaning agent penetrates into the gap between the oxide film and the adhesive layer on the metal surface, the Lewis acid center of the oxide film on the metal surface competitively adsorbs the original hydrogen bonds, breaking the connection between diethylene glycol monobutyl ether and tert-butyl hydrogen peroxide, causing tert-butyl hydrogen peroxide to be released instantly in the gap and decompose to release oxygen.

[0033] Furthermore, the branching degree of polyoxyethylene and polyoxypropylene copolymers with multi-branched structures is determined by the number of core branches of the initiator. Using pentaerythritol, xylitol, or sorbitol as initiators, four-armed, five-armed, or six-armed star-shaped branched structures can be constructed. The mass fraction of hydroxyl groups at the branch ends has an inverse relationship with their weight-average molecular weight and branching point density. Hydroxyl value was measured according to GB / T12008.3-2009. The conversion formula is: The unit is During preparation, the thickness of the copolymer adsorbed layer on the target metal surface is monitored using liquid phase atomic force microscopy. If the surface roughness of the substrate is... Exceed Insufficient adsorption leads to the addition of polyoxyethylene-polyoxypropylene copolymer with a multi-branched structure to 2.5 to 3 parts by mass. This forms a continuous elastic barrier layer with a thickness of not less than 10 nm on the metal surface oxide film, providing physical boundary constraints for the subsequent restricted decomposition of tert-butyl hydrogen peroxide. Because the elastic barrier layer forcibly confines the interfacial pressure generated by oxygen within the extremely narrow capillary gap between the metal and the adhesive layer, preventing pressure dissipation into the colloid or the cleaning bulk phase, this interfacial pressure is ultimately converted into a peel stress pointing towards the metal surface. The pressure of the gas released from the decomposition of tert-butyl hydrogen peroxide under the catalysis of the aluminum alloy surface oxide film is greater than the adhesion strength between the adhesive layer and the aluminum alloy surface, resulting in a peel displacement. This peel displacement is... to This process directly converts chemical energy into mechanical work, causing the adhesive layer to peel off completely from the substrate, avoiding the diffusion loss of environmentally friendly solvents within the dense adhesive layer; the penetration rate of the environmentally friendly cleaning agent into the epoxy resin adhesive layer on the aluminum alloy surface is set to be greater than... This is to ensure the stability of the cleaning cycle.

[0034] To maintain the system's chemical environment and wetting properties, environmentally friendly cleaning agents... The value is set to to And in Surface tension under certain conditions is maintained at to Furthermore, the mass ratio of the polyethylene oxide segment to the polypropylene oxide segment in a multi-branched polyethylene oxide-polypropylene copolymer is [missing information]. to And it is in The kinematic viscosity under the given conditions is to This viscosity characteristic, combined with low surface tension, ensures spontaneous penetration of the cleaning agent into the minute geometric features of complex, irregular surfaces. Under specific conditions, to enhance penetration into high-toughness sealants, the cleaning agent may also contain diethylene glycol monohexyl ether, wherein the weight ratio of diethylene glycol monohexyl ether to diethylene glycol monobutyl ether is [missing information]. to To prevent microscopic electrochemical corrosion of the metal substrate during cleaning, environmentally friendly cleaning agents also include... portion to Benzotriazole and portion to A portion of triethanolamine, wherein the triethanolamine is used to maintain the system's... Stability; the conductivity of deionized water should be lower than [value missing]. This reduces the shielding effect of impurity ions on the catalytic sites on the metal surface; since the adhesive remains in a solid block form after detaching from the metal substrate, the stripped material can be... Eyes reach The objective is to continuously remove the physical filtration device from the cleaning tank solution, achieving a constant concentration of effective components and maintaining a low viscosity in the cleaning solution. This invention constructs an interfacial energy conversion system based on the catalytic properties of the native oxide film on the metal surface, utilizing a specific branched copolymer to establish a pressure-maintaining zone within nanoscale gaps. This concentrates the chemical energy released from the decomposition of tert-butyl hydrogen peroxide into mechanical work directed towards the root of the adhesive layer, achieving a high coating coefficient. When maintained at 1.8 to 2.2, the system at 40 With a chemical latency of over 180 days in the environment, upon contact with the surface of aluminum or titanium alloys with Lewis acid activity, it induces a peeling displacement of 200nm to 450nm in the adhesive layer within 180s to 300s. The peeling method avoids the risk of intergranular corrosion that may be caused to the metal substrate by traditional solvent swelling processes, and preserves the original micro-texture and dimensional accuracy of the workpiece.

[0035] Example 1: The environmentally friendly cleaning agent for degumming metal surfaces provided by this invention operates as follows in the scenario of degumming precision aluminum alloy irregular parts for aerospace applications: For workpieces with blind hole structures with a depth-to-width ratio of not less than 3, and epoxy resin sealant residue deposited at the bottom of the holes after high-temperature curing, the physical properties of such dense cross-linked adhesive layers tend to harden after high-temperature service. When traditional solvent-based cleaning agents penetrate into the confined space at the bottom of the blind hole, the solvent molecules reach wetting saturation after contacting the adhesive layer surface due to the physical expulsion caused by the swelling of the colloidal phase. This makes it difficult for the effective ingredients to reach the root of the metal-adhesive layer interface where the strongest bonding force is located. If strong mechanical stirring or physical scraping is used, there is a risk of scratching the original alumina film on the inner wall of the blind hole, which in turn affects the fatigue strength and dimensional tolerance of the parts.

[0036] To prepare the finished product required for this embodiment, tert-butyl hydroperoxide, diethylene glycol monobutyl ether, A polyoxyethylene-polyoxypropylene copolymer with a multi-branched chain structure and A portion of deionized water is placed in a mixing vessel, and... Under the condition of Stirring speed The resulting environmentally friendly cleaning agent is then injected into a cleaning tank, completely immersing the workpiece. At this point, the coating coefficient within the system is... Stable at Diethylene glycol monobutyl ether encapsulates tert-butyl hydrogen peroxide via hydrogen bonds, maintaining the chemical inertness of the precursor during diffusion into the depths of the blind pores. As the cleaning agent contacts the oxide film on the aluminum alloy surface, the multi-branched polyoxyethylene-polyoxypropylene copolymer, with its end-mass fraction of [missing information], [missing information]. The hydroxyl groups preferentially anchor to Lewis acid sites on the alumina surface, prior to solvent molecules, constructing a layer with a thickness of [missing information]. Elastic retardant layer; coverage coefficient Satisfying the formula: ,in, This represents the molar amount of ether bonds in a unit volume of diethylene glycol monobutyl ether molecule. This represents the molar amount of hydroxyl groups in a unit volume of diethylene glycol monobutyl ether molecule. The molar amount of peroxy bonds in a unit volume of tert-butyl hydrogen peroxide molecule; the molar amount of peroxy bonds in this sample group was calculated. Value To meet its requirement of not less than The chemical stability requirement is obtained through pre-designed titration experiments and molecular weight distribution calculations.

[0037] As diethylene glycol monobutyl ether carries tert-butyl hydrogen peroxide deep into the gap between the metal and the adhesive layer via capillary action, the Lewis acid centers on the surface of the aluminum alloy oxide film competitively adsorb onto the hydrogen bond network. This causes the tert-butyl hydrogen peroxide to decompose in situ within the gap, releasing oxygen. At this point, due to the presence of a pre-anchored elastic retardation layer at the interface, the newly generated oxygen molecules are confined within the restricted space at the bottom of the metal matrix and the adhesive layer, unable to dissipate into the viscoelastic colloidal phase. Consequently, peel stress accumulating at the root of the interface, pointing towards the metal surface normal, is generated. The peeling stress It directly overcomes the bonding force between the sealant and the oxide film, allowing the adhesive layer to... The adhesive layer inside the blind hole peeled off completely, starting from the bottom and lifting upwards. It was eventually observed that the residual adhesive layer inside the blind hole precipitated as solid lumps. The cleaned metal surface retained the original oxide film morphology, with no pitting corrosion. Testing showed that the contact angle of the aluminum alloy surface increased from before adhesive removal. Reduce to .

[0038] Example 2: This experiment addresses the technical challenge of penetration kinetics barriers in dense cross-linked adhesive layers on the surface of precision irregular-shaped parts, establishing a verification system to quantify the correlation between interfacial peel stress and debonding efficiency. The experimental platform includes a cleaning tank with zoned precision temperature control, the temperature control accuracy of which is set to... The bottom of the tank is equipped with a sampling frequency of A thin-film piezoelectric force sensor is used to monitor the normal mechanical work output generated at the interface in real time. The sampling frequency is set to balance the real-time performance of data acquisition with the data throughput load of the signal processing unit. Under the operating conditions of this experiment, the sampling time interval is set to [value missing]. The preparation procedure for the finished cleaning agent is as follows: Add the following ingredients sequentially to the mixing vessel: The conductivity is lower than Deionized water diethylene glycol monobutyl ether, tert-butyl hydroperoxide and A polyoxyethylene-polyoxypropylene copolymer with a multi-branched chain structure, in The following Speed ​​homogenization To eliminate bulk concentration gradients and simulate data fluctuations under industrial electromagnetic environments, the experimental acquisition system actively superimposed a signal-to-noise ratio of [value missing]. Gaussian white noise.

[0039] Table 1: Summary Table of Performance Test Results for Environmentally Friendly Cleaning Agents

[0040]

[0041] As shown in Table 1, when the content of each component is within the specified range, such as in the experimental group... to The data shows that their degumming time is all within Within, and the observed interfacial peeling stress The content of tert-butyl hydrogen peroxide showed a gradient trend with increasing concentration; control group The polyoxyethylene-polyoxypropylene copolymer with a multi-branched structure was removed, and the results showed its interfacial peel stress. Down to And the degumming time is extended to The above confirms that the lack of an interface anchoring agent leads to the disordered dissipation of gases generated during decomposition into the colloidal bulk phase, making it impossible to construct effective mechanical peeling work at the metal root; control group The tert-butyl hydroperoxide content is lower than In the control group, the generated gas pressure was insufficient to overcome the polar bonding force between the adhesive layer and the oxide film, resulting in a decrease in degumming efficiency. of The ratio is Below the lower limit of the specified range Because the number of ether oxygen atoms and hydroxyl oxygen atoms in the diethylene glycol monobutyl ether molecule is insufficient to achieve complete hydrogen bond coating of tert-butyl hydroperoxide, the coating coefficient is low. Down to This causes the cleaning agent to remain in storage. Spontaneous decomposition subsequently occurred; trend analysis of the experimental data revealed that as the tert-butyl hydrogen peroxide content increased from... Upgraded to Part, interfacial peel stress It continues to rise, but exceeds... The growth rate slowed down and approached saturation after a certain concentration, indicating that the Lewis acid catalytic sites on the aluminum alloy surface were nearing full capacity, and further increases in concentration had a diminishing marginal contribution to cleaning efficiency; control group Although the degumming speed was slightly improved, the system stability decreased due to the excessively high concentration of peroxy bonds.

[0042] Example 3: This example combines Figs. 1 to 3 Instructions for an environmentally friendly cleaning agent for removing adhesive from metal surfaces, such as... Fig. 1As shown, the process begins with the raw material compounding stage, where tert-butyl hydrogen peroxide, diethylene glycol monobutyl ether, and a polyoxyethylene-polyoxypropylene copolymer with a multi-branched structure are mixed. Subsequently, diethylene glycol monobutyl ether and tert-butyl hydrogen peroxide form a stable aggregate through hydrogen bonding to complete the hydrogen bond association structure formation step. The cleaning agent then enters the interfacial gap penetration stage, penetrating into the confined gap between the metal surface oxide film and the adhesive layer. At this point, competitive adsorption occurs at Lewis acid centers, that is, the Lewis acid sites of the metal oxide film competitively cleave the original hydrogen bond association, thereby inducing tert-butyl hydrogen peroxide to decompose and release gas within the interfacial gap to achieve in-situ decomposition and release of oxygen. The oxygen generated creates interfacial pressure and inhibits solvent diffusion in the bulk phase of the adhesive layer, converting chemical energy into normal mechanical work. Ultimately, this leads to the adhesive layer peeling off from the root of the interface without damaging the metal substrate, achieving the effect of peeling off the entire adhesive layer.

[0043] like Fig. 2 As shown in the figure, the top of the chart is labeled with legends: a solid line representing the degumming time *s* and a dashed line representing the coating coefficient *S* threshold. The horizontal axis represents the coating coefficient *S*, ranging from 1 to 2.6. The left vertical axis indicates the degumming time *s*, ranging from 100 to 1000. The right vertical axis corresponds to the coating coefficient *S*, ranging from 1.0 to 2.6. The figure shows that the degumming time decreases as the coating coefficient *S* increases. Once the coating coefficient *S* exceeds the threshold indicated by the dashed line, the degumming time stabilizes at a low level, revealing the influence of the component coating state on the reaction efficiency. Fig. 3 As shown, starting from the raw material storage and supply unit, which includes a stainless steel storage tank and a metering pump to supply a compound homogeneous cleaning agent containing peroxide, solvent and additives, this unit is connected to the core operation terminal, namely an industrial-grade immersion cleaning tank with temperature control and circulation functions. The metal components to be degummed are immersed in the working fluid and form a micro-reaction interface in the gaps of the metal oxide film adhesive layer. The workpieces generated by the cleaning operation are transferred to the finished product collection and post-processing area, which includes rinsing and drying tables. The volatile gases enter the exhaust ventilation system composed of a gas collection hood and a fan, while the waste liquid is discharged to the waste liquid circulation filtration system containing physical filters and separators for reuse or treatment.

[0044] Example 4: Maintaining the ambient temperature at Furthermore, in industrial conditions accompanied by temperature fluctuations, the hydrogen bond stability between diethylene glycol monobutyl ether and tert-butyl hydroperoxide decreases, and the coating coefficient within the system decreases. The threshold shifts; to prepare the finished product required in this embodiment, the following are added sequentially to the mixing vessel: The conductivity is lower than Deionized water diethylene glycol monobutyl ether, tert-butyl hydroperoxide and The mass fraction of terminal hydroxyl groups is Polyoxyethylene-polyoxypropylene copolymers with multi-branched chain structures, in Under the condition of speed mixing The finished product is obtained; the core target of the finished environmentally friendly cleaning agent is the adhesion of a thickness of The aluminum alloy components with polyurethane sealant, the ultrasonic-assisted cleaning equipment used has a cavitation power density set at... to ; with tert-butyl hydrogen peroxide content as The part is used as an input parameter, and the temperature field conditions are used to determine the input parameters. The ratio is from the room temperature state Adjust to The coverage coefficient at this point can be calculated from this. for ;in, This refers to the total molar amount of ether bond oxygen atoms and hydroxyl oxygen atoms in the diethylene glycol monobutyl ether molecule. The coating coefficient is the molar amount of peroxyhydroxyl hydrogen atoms in a tert-butyl hydrogen peroxide molecule. The value is obtained through Titration tests under constant temperature conditions determined that this method is used to suppress the pre-dissociation of effective components before they penetrate to the interface.

[0045] During the cleaning process, the polyoxyethylene-polyoxypropylene copolymer component with a multi-branched structure constructs a layer with a thickness of [thickness missing] on the oxide film on the aluminum alloy surface through a multi-point anchoring mechanism at the branch ends. An elastic retardant layer, the thickness of which was measured using liquid phase atomic force microscopy, exhibits characteristics of adhesion force on the metal surface from... Reduce to The interface shielding effect; during the in-situ decomposition of tert-butyl hydrogen peroxide at the Lewis acid center of the oxide film on the aluminum alloy surface to produce oxygen, the elastic barrier layer acts as a physical boundary constraint, locking oxygen molecules in the microscopic gaps between the metal and the adhesive layer, thus reducing local peel stress. Increase to Peel stress The pressure sensor installed at the bottom of the cleaning tank monitors the value in real time and its correlation with the coating coefficient. The calibration values ​​are positively correlated; And the cavitation power density is Under suitable conditions, the finished environmentally friendly cleaning agent remains transparent without any bubbles. When the cleaning agent penetrates to the root of the polyurethane adhesive layer, the interfacial peeling displacement is within... Time to reach This causes the adhesive to precipitate out in whole sheets, reducing the surface roughness of the aluminum alloy. Maintain at No intergranular corrosion spots were found.

[0046] Example 5: In a scenario where pre-degumming adjustments are performed to address differences in surface morphology between different batches of aluminum alloy substrates, the porosity and Lewis acid site density of the oxide film on the workpiece surface fluctuate with the processing steps. A standardized baseline calibration procedure is used to determine the trigger threshold for effective components; the thickness of the oxide layer on the surface of the sample to be cleaned is measured. Immerse the sample in water made of diethylene glycol monobutyl ether and Electrochemical impedance spectroscopy was used to measure the interfacial charge transfer resistance in a substrate solution composed of deionized water. ;by The amount of tert-butyl hydroperoxide added in increments was increased until the interfacial peel stress was detected by the pressure sensor. achieve The initial release point is recorded, and the amount added at this point is taken as the catalytic triggering amount on the surface of the substrate for that batch. ;according to and The linear mapping relationship determines the set value of tert-butyl hydroperoxide for this specific batch of matrix. .

[0047] When the oxide layer thickness of the workpiece for to And the interface charge transfer resistance Greater than At that time, thermal stability compensation for hydrogen bond coating strength was achieved by adjusting the molar ratio of diethylene glycol monobutyl ether to tert-butyl hydroperoxide; the baseline calibration procedure was used to determine... for Using this as input data, the tert-butyl hydrogen peroxide content in the finished environmentally friendly cleaning agent was adjusted to... The amount of polyoxyethylene-polyoxypropylene copolymer with multi-branched structure was increased to [amount missing]. A portion is used to cover catalytic sites created by increased surface roughness; once the formulation parameters are locked, the penetration rate of the finished environmentally friendly cleaning agent during the cleaning process is maintained at [value missing]. ,exist The amount of displacement of the interface peeling reaches The design specifications; this procedure eliminates the interference of raw material surface condition fluctuations on peeling performance, maintains the integrity of the oxide film morphology after cleaning and the stability of part geometric tolerances.

[0048] Example 6: In a scenario involving the degumming of precision aluminum alloy irregularly shaped parts under continuous operation, the system executes a dynamic replenishment procedure based on component concentration monitoring and sound pressure feedback to address the consumption of tert-butyl hydrogen peroxide in the interfacial reaction. The industrial cleaning line selected for this scenario includes an online component analysis module with a concentration detection resolution of [missing information]. When the system is Continuous operation at temperature up to During each cleaning batch, an automatic titration device measures the residual mass fraction of peroxy bonds in the tank solution and transmits this measurement value as an input parameter to the replenishment control unit. Simultaneously, a sound pressure monitoring device located on the side wall of the cleaning tank acquires the sound pressure level signal. When the measured local sound pressure decrease reaches a preset percentage... When the concentration of the active ingredient is determined to be lower than the peel stress, To maintain the required critical value, the control unit drives the metering pump to perform a replenishment operation based on the input parameters, restoring the tert-butyl hydroperoxide content from the decayed value to the required level. The product is prepared in portions, and diethylene glycol monobutyl ether is added simultaneously to ensure that the total molar amount of ether bond oxygen atoms and hydroxyl oxygen atoms in the diethylene glycol monobutyl ether molecule is equal. Molar amount of peroxyhydroxyl hydrogen atoms in tert-butyl hydrogen peroxide molecule ratio Return to The flow control accuracy during the replenishment operation is: After completion, the tank solution is driven by a circulating pump to... Equivalent speed flow This eliminates local concentration deviations, thereby maintaining the stability of the interface mechanical peeling work output intensity during long-cycle production.

[0049] In the scenario of debonding correction for non-uniform sound field energy distribution in a confined space, the mass ratio of the polyethylene oxide segment to the polypropylene segment in a polyoxyethylene-polyoxypropylene copolymer with a multi-branched structure is... It has a regulating effect on the physical shielding effectiveness of the elastic retardation layer; by preparing a mass ratio They are respectively , and The sample group and its measurement Kinematic viscosity under certain conditions was observed to change with... Increase presentation by Towards The increasing trend reflects the changing pattern of interbranch entanglement strength; at a cavitation power density of Under high-frequency disturbances, the mass ratio will be Locked in The range ensures that the protective barrier formed by the elastic barrier layer on the aluminum alloy surface is in a preset state, ultimately maintaining the peel stress. While increasing output strength, the depth of intergranular corrosion on the metal surface is controlled within... the following.

[0050] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the present invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the present invention.

[0051] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims

1. An environmentally friendly cleaning agent for removing adhesive from metal surfaces, characterized in that, The environmentally friendly cleaning agent, with a total weight of 100 parts, consists of the following components: 5 to 15 parts of tert-butyl hydrogen peroxide; 25 to 40 parts of diethylene glycol monobutyl ether; 0.5 to 3 parts of a polyoxyethylene-polyoxypropylene copolymer with a multi-branched structure; And the remainder of deionized water; wherein, the total molar amount of ether bond oxygen atoms and hydroxyl oxygen atoms in the diethylene glycol monobutyl ether molecule Molar amount of peroxyhydroxyl hydrogen atom in tert-butyl hydrogen peroxide molecule ratio for to ; The weight-average molecular weight of polyoxyethylene-polyoxypropylene copolymers with multi-branched structures is to And the mass fraction of its branched terminal hydroxyl groups is to ; Environmentally friendly cleaning agents Value to And environmentally friendly cleaning agents The surface tension below is to ; Diethylene glycol monobutyl ether forms an associated structure with tert-butyl hydrogen peroxide via hydrogen bonds; After the environmentally friendly cleaning agent penetrates into the gap between the oxide film and the adhesive layer on the metal surface, the Lewis acid centers of the oxide film on the metal surface competitively adsorb hydrogen bonds, causing tert-butyl hydrogen peroxide to decompose and release oxygen in the gap. The interfacial pressure generated by the oxygen is used to achieve the peeling of the adhesive layer from the metal surface.

2. The environmentally friendly cleaning agent for degumming metal surfaces according to claim 1, characterized in that, In a polyoxyethylene-polyoxypropylene copolymer with a multi-branched structure, the mass ratio of the polyoxyethylene segment to the polyoxypropylene segment is: to The equilibrium adsorption capacity of polyoxyethylene-polyoxypropylene copolymers with multi-branched structures on the oxide film of aluminum alloy surfaces is greater than that of diethylene glycol monobutyl ether on the oxide film of aluminum alloy surfaces, thus enabling the polyoxyethylene-polyoxypropylene copolymers with multi-branched structures to preferentially form an adsorption layer on the metal surface; the kinematic viscosity of the polyoxyethylene-polyoxypropylene copolymers with multi-branched structures is... Below is to .

3. The environmentally friendly cleaning agent for degumming metal surfaces according to claim 1, characterized in that, The pressure of the gas released by the decomposition of tert-butyl hydrogen peroxide under the catalysis of the oxide film on the aluminum alloy surface is greater than the adhesion strength between the adhesive layer and the aluminum alloy surface.

4. The environmentally friendly cleaning agent for degumming metal surfaces according to claim 1, characterized in that, Also includes portion to Benztriazole; the conductivity of deionized water is lower than .

5. The environmentally friendly cleaning agent for degumming metal surfaces according to claim 1, characterized in that, Polyoxyethylene and polyoxypropylene copolymers with multi-branched chain structures are anchored to the surface of metal oxide films through multi-point hydrogen bonds.

6. The environmentally friendly cleaning agent for degumming metal surfaces according to claim 1, characterized in that, The mixing stability of environmentally friendly cleaning agents is determined by the coating coefficient. Characterization, Coverage Coefficient Satisfy the following formula: ,in, This represents the molar amount of ether bonds in a unit volume of diethylene glycol monobutyl ether molecule. This represents the molar amount of hydroxyl groups in a unit volume of diethylene glycol monobutyl ether molecule. This represents the molar amount of peroxy bonds in a tert-butyl hydrogen peroxide molecule per unit volume.

7. The environmentally friendly cleaning agent for degumming metal surfaces according to claim 1, characterized in that, Environmentally friendly cleaning agents penetrate the epoxy resin layer on aluminum alloy surfaces at a rate greater than [missing information]. .

8. An environmentally friendly cleaning agent for degumming metal surfaces according to claim 1, characterized in that, Also includes portion to A portion of triethanolamine.

9. An environmentally friendly cleaning agent for degumming metal surfaces according to claim 1, characterized in that, Environmentally friendly cleaning agents also include diethylene glycol monohexyl ether, wherein the weight ratio of diethylene glycol monohexyl ether to diethylene glycol monobutyl ether is [missing information]. to .

10. An environmentally friendly cleaning agent for degumming metal surfaces according to claim 1, characterized in that, The gaseous products released from the decomposition of tert-butyl hydrogen peroxide within the gaps between the oxide film and the adhesive layer on the aluminum alloy surface cause a peeling displacement, the amount of which is... to .

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