Study on the Formation Mechanism of “Phosphorus Oil-patina” in Cu-P Brazing Alloys and Performance Improvement

SUN Jungang; YE Zhaofeng; WANG Sihong; HUANG Shisheng; NIU Bangshuo; LUO Liangliang; LUO Shougen; QIAO Xue

doi:10.7512/j.issn.1001-2303.2025.10.18

“Huaguang”Cup Excellent Thesis Recommendation | Views : 0 下载量: 574 CSCD: 0

PDF
Export
Share
Collection
Album

Study on the Formation Mechanism of “Phosphorus Oil-patina” in Cu-P Brazing Alloys and Performance Improvement
Vol. 55, Issue 10, Pages: 170-177(2025)
Received：28 August 2025，

Published：20 October 2025
DOI： 10.7512/j.issn.1001-2303.2025.10.18
稿件说明：

移动端阅览

孙军刚，叶兆丰，王思鸿，等.基于铜磷钎料焊后“磷油-铜绿”形成机理及性能改善研究［J］.电焊机，2025，55（10）：170-177. DOI： 10.7512/j.issn.1001-2303.2025.10.18.

SUN Jungang, YE Zhaofeng, WANG Sihong, et al.Study on the Formation Mechanism of "Phosphorus Oil-patina" in Cu-P Brazing Alloys and Performance Improvement[J].Electric Welding Machine, 2025, 55(10): 170-177. DOI： 10.7512/j.issn.1001-2303.2025.10.18.

摘要

本研究旨在探究铜磷（Cu-P）钎料在空气中感应钎焊时表面形成黑色、粘稠的液态复合膜（“磷油”）以及诱发铜绿的机理，并提出有效抑制策略。通过EDS、XRD与第一性原理计算解析了磷油主要成分为Cu

等磷酸盐，其形成具有热力学自发性；铜绿则为磷油在湿热环境中转化而来的碱式碳酸铜。研究从工艺与材料两方面提出解决方案：通氮气保护可有效抑制磷油，但成本高、适用性有限；而添加微量镧系（Ln）元素则可优先氧化形成致密Ln-O保护膜，从源头阻断P

生成，在维持钎料原有熔化与润湿性能的同时，显著提升焊缝致密性、力学性能及抗腐蚀性。结果表明，Ln合金化策略具有内置保护优势，为高性能Cu-P钎焊材料开发提供了新途径。

Abstract

This study aims to investigate the formation mechanism of black

viscous liquid composite films (“phosphorus oil”) and their role in inducing patina on Cu-P brazing filler metals during air-atmosphere induction brazing

and to propose effective inhibition strategies. Through EDS

XRD

and first-principles calculations

the phosphorus oil was identified mainly as phosphates such as Cu

whose formation is thermodynamically spontaneous; the patina was identified as basic copper carbonate formed from phosphorus oil under humid conditions. Two approaches were compared: nitrogen shielding effectively suppressed phosphorus oil but incurred high cost and limited applicability; while adding trace lanthanide (Ln) elements formed a dense and stable Ln-O oxide film preventing P

generation at the source. The Ln modified filler maintained original melting and wetting properties

while significantly improving joint density

mechanical performance

and corrosion resistance. The results demonstrate that the Ln alloying strategy offers an intrinsic protection mechanism

providing a new

approach for developing high performance Cu-P brazing materials.

关键词

Keywords

references

Xiong H ， Li H ， Mao W ， et al . Reviews on latest advances in brazing and soldering technologies ［J］. Transactions of the China Welding Institution ， 2011 （ 5 ）： 108 - 112 .

Tajfar M ， Ganjeh E ， Mirbagheri M H . Evaluation of copper brazed joint failure by thermal-fatigue test applicable in heat exchangers ［J］. Journal of Alloys and Compounds ， 2016 ， 656 ： 347 - 356 .

王磊 . Cu-P基非晶钎料性能及钎焊机理的研究［D］. 江苏：江苏科技大学， 2010 .

WANG L . Research on the Properties and Brazing Mechanism of Cu-P Amorphous Brazing Filler Metals ［D］. Jiangsu ： Jiangsu University of Science and Technology ， 2010 .

瞿智明，张福勤，夏莉红 . Cu基钎料钎焊紫铜的接头力学性能和微观组织［J］. 粉末冶金材料科学与工程， 2015 ， 20 （ 01 ）： 133 - 138 .

QU Z M ， ZHANG F Q ， XIA L H . Mechanical properties and microstructure of Cu-based solder brazed red copper joints ［J］. Materials Science and Engineering of Powder Metallurgy ， 2015 ， 20 （ 01 ）： 133 - 138 .

杨凯珍，刘正林，刘凤美，等 . Sn元素对铜磷钎料性能的影响［J］. 热加工工艺， 2011 ， 40 （ 05 ）： 41 - 43 .

YANG K Z ， LIU Z L ， LIU F M ， et al . The influence of Sn element on the properties of copper-phosphorus solder ［J］. Hot Working Technology ， 2011 ， 40 （ 05 ）： 41 - 43 .

黄杰，薛松柏，王博 . 合金元素对Cu-P系钎料性能影响的研究现状［J］. 焊接， 2014 （ 11 ）： 14 - 19+68 .

HUANG J ， XUE S B ， WANG B . Research Status of the Influence of Alloying Elements on the Properties of Cu-P Solders ［J］. Welding & Joining ， 2014 （ 11 ）： 14 - 19+68 .

Avolzhansky S A ， Pashkov I N . Effect of the composition of brazing alloys of the copper-phosphorus-antim-ony system on the structure and properties of copper alloys ［J］. Welding International ， 2013 ， 27 （ 9 ）： 694 - 697 .

李航，张淑婷，唐卫岗，等 . P含量对Cu-P-Sn-Ag四元合金钎料组织及力学性能的影响［J］. 有色金属工程， 2023 ， 13 （ 10 ）： 22 - 29 .

LI H ， ZHANG S T ， TANG W G ， et al . Effect of P Content on the Microstructure and Mechanical Properties of Cu-P-Sn-Ag Quaternary Alloy Solder ［J］. Non-ferrous metal engineering ， 2023 ， 13 （ 10 ）： 22 - 29 .

高飞，许伟龙，王超，等 . 含锆Cu-P基非晶钎料钎焊紫铜接头的连接强度及微观组织［J］. 焊接学报， 2011 ， 32 （ 10 ）： 53-56+115 - 116 .

GAO F ， XU W L ， WANG C ， et al . Strength and microstructure of Cu joints brazed with Cu-P based amorphous filler metal contained Zr ［J］. Transaction of the China Welding Institution ， 2011 ， 32 （ 10 ）： 53 - 56 .

杨帆，杨国良，董博文 . 铜磷钎料性能研究进展［J］. 电焊机， 2021 ， 51 （ 06 ）： 13-17+112 - 113 .

YANG F ， YANG G L ， DONG B W . Research Progress on Properties of Copper-Phosphorus Brazing Filler Metals ［J］. Electric Welding Machine ， 2021 ， 51 （ 06 ）： 13-17+112 - 113 .

GB/T 11364—2008 ：钎焊接头强度试验方法［S］. 中华人民共和国国家质量监督检验检疫总局；中国国家标准化管理委员会， 2008 ： 20 .

GB/T 11364—2008 ：钎焊接头强度试验方法. 钎料润湿性试验方法［S］. 中华人民共和国国家质量监督检验检疫总局；中国国家标准化管理委员会， 2008 ： 12 .

Le S N ， Navrotsky A ， Pralong V . Energetics of copper diphosphates-Cu 2 P 2 O 7 and Cu 3 （P 2 O 6 OH） 2 ［J］. Solid State Sciences ， 2008 ， 10 （ 6 ）： 761 - 767 .

Ball M C . Phase-equilibrium relationships in the systems CuO-P 2 O 5 and Cu 2 O-P 2 O 5 ［J］. Journal of the Chemical Society A：Inorganic ，Physical，Theoretical， 1968 ： 1113 - 1115 .

Alert me when the article has been cited

提交

Study on Mechanical Properties of Dissimilar Metal Joints Between Haynes 230 and Inconel 617 Brazed with Amorphous BNi2 Filler Metal

In-Situ Generated Mo-Ni-Si Phase Strengthens the Mechanical Properties of Mo-Re Alloy/AlN Ceramic Brazed Joints

Microstructure and Mechanical Properties of Aluminum Alloy Joints Brazed using Al-Si-Cu Flux-cored Wire in Air

Effect of Brazing Parameters on the Organization and Mechanical Properties of Brazed Joints of SOFC Metal Connectors

Microstructure and Shear Strength of SiC Joint Fabricated by W Coating and Pure Ag Brazing