CN104032293A

CN104032293A - Highly corrosion-resistant environment-friendly black phosphatizing liquid without nickel single component

Info

Publication number: CN104032293A
Application number: CN201410257260.7A
Authority: CN
Inventors: 王成林
Original assignee: Anhui Jiangnan Machinery Co Ltd
Current assignee: Anhui Jiangnan Machinery Co Ltd
Priority date: 2014-06-11
Filing date: 2014-06-11
Publication date: 2014-09-10
Anticipated expiration: 2034-06-11
Also published as: CN104032293B

Abstract

The invention discloses highly corrosion-resistant environment-friendly black phosphatizing liquid without nickel single component. Each liter of the treatment liquid consists of the following raw materials: 25-50g of main film forming agent, 5-25g of film forming aid, 0.1-3g of accelerant, 60-80g of grain refiner, 0.5-2g of stabilizer, 0.05-1g of blackening agent and 0.1-0.5g of blackening aid. The phosphatizing liquid disclosed by the invention can form a black phosphatized film on a steel surface by a one-step process. The phosphatized film has high blackness and high corrosion resistance, is uniform and avoids stripping; a copper sulfate spot test can reach 40min which is much longer than the national standard (2min); the phosphatizing liquid does not contain toxic and harmful substances such as nickel, nitrite and the like and causes little environmental pollution.

Description

A kind of not nickeliferous single component high anti-corrosion environmental protection black phosphating solution

Technical field

The present invention relates generally to surface chemistry field, relates in particular to a kind of not nickeliferous single component high anti-corrosion environmental protection black phosphating solution.

Background technology

Phosphatization is conventional metal surface treatment technology, belongs to chemical transformation film and process in principle, is mainly used in steel surface phosphatization, and non-ferrous metal (as aluminium, zinc) part also can be applied phosphatization.Phosphatization is the process that a kind of chemistry and electrochemical reaction form phosphate chemical conversion film, and formed phosphate conversion film is referred to as phosphatize phosphate coat.The object of phosphatization is mainly: to matrix metal, provide protection, prevent that to a certain extent metal is corroded; The front bottoming that is used for painting, improves sticking power and the anti-corrosion capability of paint film layer; In metal cold complete processing, play antifriction lubrication.It is a kind of process for treating surface of high quality and at a reasonable price being widely adopted that black phosphating is processed, and as appearance component, phosphatize phosphate coat blackness is had relatively high expectations.Black phosphating has a wide range of applications, as auto pedal series, clutch coupling product, bearing, oil nozzle etc.The black film phosphating process of iron and steel is broadly divided into 2 kinds: a kind of is single stage method, do not need the preimpregnation can direct phosphating, existing single stage method black phosphating mostly is manganese salt high temperature phosphorization, but the problems such as crystallization is thick, Phosphating Solution sediment is more that this rete is prone to, adjust comparatively complicated, and technological operation temperature is high, generally at 90～98 ℃, power consumption is large.Another kind is two step method, it is first preimpregnation phosphatization again, how black agent in this presoak is comprised of sub-selenium salt, the shortcoming of this technique is that pre-blackening process liquid is unstable, easily falls film, will cause like this solution easily to change, degradation problem under solution repetition rate, and selenous acid is toxic substance, and price is more expensive in addition, this has just caused the problems such as the processing of waste liquid and recovery.Current domestic black phosphating is processed the poor shortcoming of ubiquity solidity to corrosion, general indoor placement got rusty by tens days for several days, copper-bath spot test is variable color (testing by GB GB6807 mono-86 regulations) about one minute, and phosphatize phosphate coat density difference, easy demoulding, can not meet the high-quality requirement of Modern Industry Products far away, and high corrosion-resistance black phosphating liquid market is monopolized by overseas enterprise substantially now, thereby how to improve the solidity to corrosion of black phosphating film, improve blackness, strengthen membranous layer binding force, break the monopolization of overseas enterprise to domestic market, become topic urgently to be resolved hurrily of domestic black phosphating treatment technology.The present invention aims to provide a kind of single stage method and prepares high corrosion-resistance black phosphating film, the experiment of copper sulfate drop reaches as high as 40min, greatly be better than national standard (2min), and the hazardous and noxious substances such as this Phosphating Solution is not nickeliferous, nitrite, environmental pollution are little, the phosphatize phosphate coat blackness forming is high, demoulding, does not have market using value.

Summary of the invention

The object of the invention is just to provide a kind of not nickeliferous single component high anti-corrosion environmental protection black phosphating solution.

The present invention is achieved by the following technical solutions:

Not nickeliferous single component high corrosion-resistance black phosphating liquid, every liter of described treatment solution is comprised of each raw material mixing of following weight:

Main membrane-forming agent 25-50g, film coalescence aid 5-25g, promotor 0.1-3 g, grain-refining agent 60-80 g, stablizer 0.5-2g, blackening agent for surface 0.05-1 g, blackout auxiliary agent 0.1-0.5 g, surplus are water;

Described main membrane-forming agent is primary zinc phosphate;

Described film coalescence aid is comprised of each raw material of following weight parts: manganous nitrate 40-50, dimethyl fumarate 3-4, clorafin 4-6, ethoxylated alkyl ammonium sulfate 1-2, saturated octadecanoyl amine 2-3, TriMethylolPropane(TMP) 0.4-1, deionized water 100-120;

Manganous nitrate is joined in deionized water, after fully stirring, add ethoxylated alkyl ammonium sulfate, TriMethylolPropane(TMP), 100-200 rev/min of dispersed with stirring 4-10 minute, obtains a liquid;

Dimethyl fumarate is mixed with clorafin, at 50-60 ℃, be uniformly mixed 3-5 minute, add saturated octadecanoyl amine, join in above-mentioned a liquid after stirring, 200-300 rev/min of dispersed with stirring 30-40 minute, obtains described film coalescence aid;

Described promotor is m-nitrobenzene sodium sulfonate; Described grain-refining agent is one or more the mixture in calcium metaborate, nitrocalcite, monocalcium phosphate, and described stablizer is one or more the mixture in citric acid, tartrate, gluconic acid; Described blackening agent for surface is one or both in cupric nitrate, copper sulfate; Described blackout auxiliary agent is Sodium orthomolybdate.

Advantage of the present invention is:

Phosphating Solution of the present invention can be realized and form black phosphating film in steel surface single stage method, and phosphatize phosphate coat blackness is high, even film layer, demoulding not, solidity to corrosion is high, copper sulfate drop experiment reaches as high as 40min, is greatly better than national standard (2min), and the hazardous and noxious substances such as this Phosphating Solution is not nickeliferous, nitrite, environmental pollution are little.

Embodiment

Embodiment 1

Main membrane-forming agent 50g, film coalescence aid 25g, promotor 0.1 g, grain-refining agent 80 g, stablizer 2g, blackening agent for surface 0.05 g, blackout auxiliary agent 0.5 g, surplus are water;

Described main membrane-forming agent is primary zinc phosphate;

Described film coalescence aid is comprised of each raw material of following weight parts: manganous nitrate 50, dimethyl fumarate 3-4, clorafin 4-6, ethoxylated alkyl ammonium sulfate 2, saturated octadecanoyl amine 3, TriMethylolPropane(TMP) 0.4, deionized water 120;

Manganous nitrate is joined in deionized water, after fully stirring, add ethoxylated alkyl ammonium sulfate, TriMethylolPropane(TMP), 200 revs/min of dispersed with stirring 10 minutes, obtain a liquid;

Dimethyl fumarate is mixed with clorafin, be uniformly mixed 3 minutes at 60 ℃, add saturated octadecanoyl amine, join in above-mentioned a liquid after stirring, 300 revs/min of dispersed with stirring 40 minutes, obtain described film coalescence aid;

This Phosphating Solution working fluid use temperature is 60-70 ℃, and the Phosphating Solution time is 8-15min, and working fluid is controlled parameter: total acidity 50-80(P), and free acid 4-6(P).

Workpiece, after degreasing and rust removal, directly immerses working fluid 8-15min.Workpiece after this Phosphating Solution is processed is pitch-black shinny, and membranous layer binding force is good, copper sulfate drop experiment 15-25min.

Claims

1. not nickeliferous single component high anti-corrosion environmental protection black phosphating solution, is characterized in that every liter of described treatment solution is mixed and formed by each raw material of following weight:

Described main membrane-forming agent is primary zinc phosphate;