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copper etching in air regenerated cupric chloride solution

copper etching in air regenerated cupric chloride solution

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ISSN 1726-4073

Journal of

Number 3

Volume 16

September 2010

List of Contents

English Section:

5283- 5299

Damaging Effect Of Moving Tank Loads On Flexible Pavement

Dr. Saud Abdulaziz Sultan

5300 - 5314

Investigation On The Use Of Micropiles For Substitution Of Defected Piles By The Finite Element Method

Dr. Mohammed Y Fattah Dr. Yousif J Al=Shakorchi Yasser M Kadhim

5315 -5336

Finite Element Analysis Of A Friction Pendulum Bearing Base Isolation System For Earthquake Loads

Ass!. Lect. Zuhair Abd Hacheem

Asst. Leet. /sraa Khudhair Al-Shimmari

5337 - 5351

Seismic Design Of Single Span Steel Girder Bridges And Bridges In Seismic Performance Category A

Asst. Prof Dr. Abdul Muttalib I Said Esraa Mubder Edam?

5352 - 5362

Effect Of Mineral Filler Type And Content On Properties Of Asphalt Concrete Mixes

Eng. Noor M Asmael

5363 - 5376

Frequency Domain Equalization Techniques For Multicode Ds-Cdma In Frequency Selective Rayleigh Fading Channel

Asst., Prof Maha George Zia

Mse. Eng. Sameer Akram Dawood

5377 - 5391

Modeling And Simulation Of A Buck Converter Controlled A Sensorless De Series Motor

Bassim MH. Jassim Tagreed MAli

5392 - 5397

Derivation Of The Lorentz-Einstein Transformation Via One Observer

o.MAL-Kazalehi Faiz T Omara

5398 - 5410

Hydrodynamic Studies of Bed Expansion in Liquid Solid Fluidized Bed

Sawsan A. M Mohammed

Removal Of Copper Ions From Waste Water By Adsorption With Modified And Unmodified Sunflower Stalks

Besma Ismae! Hussein

Removal of Kerosene from Waste Water Using Iraqi Bentonite

Abbas H. Sulaymon Ziad T. Abd Ali

Simulation of Sulfur Dioxide Removal from a Gas Stream in a Fluidized-Bed Reactor

Nibras M. Abdulrasol Wa!eed A! S, Kadhem

Prediction Of Natural Convection Heat Transfer In Complex Partitions Cavity


Dynamic Behavior Of Non - Return Valves Operating At Small Opening

Dr. Ali A.A! Al-Asadi Dr. Hameed D. Lafta Msc. Ali W. Abbas

Separation of oil from OM' emulsion by electro flotation technique

Ahmed AiMohammed

Ali Jassim Mohammed Al-Gurany

Vertical Vibrations of Base Isolated Machine Foundations

Prof Dr. Thmir K. Mahmood Salim Y. Awad

Experimental Study On The Presence Of Open Cavity Effects On Internal Flow And Convection Heat Transfer Characteristics


Damage Detection In Rotating Blade By Vibrational Analysis Using Finite Element Method

Dr. Nabil H. H. Shwan A. Z

Analysis of Concrete Flexural Members Reinforced with Fibre Polymer

Asst. Prof. Dr. Nazar K. Oukaili Ahlam Ali Al-Asadi

54]] -5421

5422 - 5437

5438 - 5459

5460 - 5480

5481 - 5502

5503 - 5515

5516 - 5535

5536 - 5547

5548 - 5568

5569 - 5587

Design Of A Sliding Mode Controller For A Tora System

Prof Dr. Waladin Khairi Sa'id Mr. Shibly Ahmed Hameed

Investigation And Modification OF Aerodynamic Characteristics OF Supersonic

Dr. Jafar M. Hassan Dr. Laith K. AMass Eng. Laith W Ismail

Flash Evaporation Enhancement By Electrolysis Of Saturated Water Flowing Upwards In Vertical Pipe

Dr. Akram. W Izzat Radwan Muhammad Addaiy

Use Of Availability Simulation To Find Optimum Period OfTimc Between Schedule Maintenance


Developing Laminar Mixed Convection Heat Transfer Through Concentric Annuli

Asst. Prof Dr. lhsan Y. Hussain Mohammed Abdul RaoufNima Al-Safi

Flow Separation Of Axial Compressor Cascade Blades

Dr. Arkan Kh. Al-Taie Sabah Faleh Habeeb

Mathematical Model To Investigate The Temperature And Hardness Distributions During The Annealing And Normalizing Treatment

B. Shaheen Bachy

Three-Dimensional Finite Element Analyses of a Single Pile in an Elastoplastic Clayey Soil

Omar al-Farouk Salem al-Damluji Usama Saeed Al-Anbaki

PCCC MC-CDMA Combination Performance over Multipath Rayleigh Fading Channel

Husam Abduldaem. Mohammed

Voltage Stability Enhancement And Loss Reduction Via Optimum Location Of A Series Capacitor

Dr. Firas Mohammed Tuaimah

5588 - 5605


5620 -5632

5633 - 5643

5644 - 5662

5663 - 5682

5683 - 5698

5699 - 5723

5724 - 5735

5736 - 5752

Strengthening Of Cracked Reinforced Concrete T -Beam By Jacketing Dr. ADNAN SADIQ AL-KUAITY

Copper Etching In Air RegeneratedCupric Chloride Solution Baseem H Fadhil

5771 - 5777

5753 - 5770


Volume 16 September 2010

Journal of Engineering


Baseem H. Fadhil

Chemical Engineering Department - College of Engineering - University of Baghdad -iraq baseemee@yahoo.com


One of the most important steps in the world of printed circuit board manufacturing (PCB) is the copper etching process. Because of its low cost, environment aspects, and simple regeneration techniques, cupric chloride was chosen to be the most attractive etchant.

Etching of copper from standard single-sided copper boards used usually for printed circuit board fabrication was conducted in a cell containing cupric chloride solution. Average etching rates were recorded as a function of time, etchant specific gravity, free acid concentration, and temperature. Air was injected continuously in the etching cell during the process enabling mixing and solution regeneration. It is found that best operating conditions to obtain maximum etching rate is at 45-55°C, specific gravity of 1.3-1.4, and free acid concentration of 1.3-1.4 M.


Etching, chemical machining, cupric chloride, regeneration, PCB.

~I J_,h... ~I_, .(PCB) ~~I ~J_;.5J'l1 ylj..lll ~I.:....:, ~u:. ~ ~I u4LuJ\ ~I .l2..: ,-",I.:...il.l ~_,.J\ JStJ\ 01 ,~~I .a.,: 4W t~_;""1 ~-*""J ,~ ~) \_):u ",-?-_,.JI JStJI ~ ~I J..jL:......JI rAl ~I ,jM ,-",WI ~ __ JJ1S

.~ ul)..,u.:.'i_, J_,h...;_jy:.::, ~ ~ ~_,j&'il ~4hU :.lu:. I"~ ~IJ ~J ..:.:.,\j ;y~ el)':1 ~4! u\~ r. ;yWI JSI.::, ;y.)j

ub .yJI ~l:JI jf>YJ ,J_,h.JI :utsJ ,:;)yJI 4.)..llJ ,u.-.)l W~ u~ JSUI w'i~ ~J ,,-,,,WI ~.J_,1S J$t.ll u':J~1 ~I ~ --sj_}:J1 j...:o!\ ul 4j ·4W t~_;""lj J_,h.J\ e > w4,> ~I j;...1.l ~ ~ ~ "\_,.,,

';_j.)'J. Y' 1.4-1.3 .ljh..; yJI ,-~wl jf>Yj .] .4-1.3 ~_'h..; ~ jl :U'GSj ,/55-45 .) yo. 4_).l.J ufo


Etching can be defined as a machining technique, in which, controlled corrosion process was applied on selected areas of the metal part. This is usually occurring in the presence of a corrosive


i B. H. Fadhil

Copper Etching In Air Regenerated Cu ric Chloride Solution

media, called etchant. The process was used by ancient Egyptians to make copper jewelries when they etched copper with citric acid around 2500 BC. Etching, nowadays, is extensively used to manufacture geometry complex and precision parts for electronic, aerospace, automotive, medical, decorative, and microcomponent production industries (0. Cakir et al, 2007; O. Cakir, 2007).

One of the most important steps in the world of printed circuit boards fabrication is the copper etching step from circuit boards. Circuit boards are usually fabricated from glass fiber reinforced epoxy



40000 (j)


~ 30000 ~

~ 20000 -






North Arrerca


Fig.l World PCB production (WECC reports)

with copper layers of 25 to 50 11m thick (Xingsheng Liu, 200 I). There are three basic varieties of printed circuit boards: single-sided, double-sided, and multi-layered. The spatial and density requirement and circuitry complexity determine the type of board produced. Fig. 1 Show the world PCB production estimates from 2005 till 2008, and Fig. 2 show the major countries that share the production for the year 2008 (WECC - World Electronic Circuits Council, 2009).

Copper was commonly etched with alkaline ammonia and cupric chloride (continuous operation).

Less common etchants include peroxide-sulfuric acid, persulfates, and ferric chloride (batch operation). The selection of etchant has been limited by economic, operational, and environmental concerns (Clyde F. Coombs, Jr, 2008). For single-sided boards, cupric chloride is the most suitable etchant even for large scale production lines (0. Cakir, 2006). It offers some distinct advantages like: simple regeneration of spent solution, no waste disposal problems, low cost, simple process control, and no sludging problem (Stephen D. Kasten, 1983).

Chemistry of Copper Etching with Cupric Chloride and the Regeneration Process

Cupric chloride is a yellow-brown solid with the formula CuCb in its dehydrated state. It is sold usually in its hydrated state (CuCI2.2H20) with a blue-green color as it absorbs moisture from the ambient. Cupric chloride reacts with copper to form cuprous chloride:

As the reaction proceeds, cupric ions will deplete and the reaction goes to slowdown (i.e. etching rate decreased). To obtain a constant etching rate and makes copper continue to dissolve from the metal surface, cuprous chloride should be returned back or regenerated to cupric chloride again. This can be accomplished by providing an oxidizing agent that oxidizes cuprous ions Cu+1 to cupric ions Cu +2. Many oxidizing agents can be used for this purpose, commonly used includes chlorine or air, sodium


Cu + CuCb -> 2CuCl

Fig. 2 Countries sharing PCB production for the year 2008 (WECC report)


Number 3

Volume 16 September 2010

Journal of Engineering

chlorate (NaCI03), or hydrogen peroxide (H202). Regeneration process by oxygen was done chemically according to the reaction:


Reaction (2) consumes hydrogen ion, so that, hydrogen ions should by supplied to the reaction.

Addition of hydrochloric acid (HCl) in excess amount to the reaction vessel was suggested to be a good source for H+ ions and chloride balance was maintained. Also, it removes any traces of copper oxide from the surface of copper metal being etched (Chemcut Corp., 2002). It is clear that the original solution volume grows up during the regeneration process in this way. To overcome this problem, one should remove a portion of the etch ant from time to time to keep a fixed reaction volume (P. Adaikkalam et al, 2002). The overall reaction of the regeneration process is:

2HCl + 2CuCI + 0 ---+ 2CuCb + H20


In this study, copper from single-sided boards was etched with cupric chloride and the effected parameters on the average etching rate were studied. Regeneration of the solution was done by continuous injection of air to the etching cell.


Etching of copper from single-sided boards with cupric chloride solution was accomplished in a cell designed to meet the necessary requirements needed to study the parameters affecting etching process.

The cell shown in Fig. 3 was made from a glass material with dimensions of 27 cm height x 19 em width x 3.5 em depth, tilled with 1 liter of cupric chloride etchant during each run. It holds an electrical heater used to maintain the solution at the desired temperature fixed by a contact thermometer within ±0.5°C. At the bottom of the cell, an air distributor was installed enabling air bubbles to spread along the cell. The air was injected to the cell at a fixed flow rate of 0.5 liter/min. This flow rate was selected to be the maximum flow rate allowable to prevent the solution from spilling out of the cell. Air function as a source of oxygen required to regenerate the etchant and as an agitator.

A verage etch ing rate was recorded as a function of etching time, etchant density, free acid concentration, and temperature. Etching was monitored by visual inspection of a 2 x 4 em circuit board sample hanged at the center of the


PCB specimen

Contact thennometer




Light source behind the cell

All' distributor

Fig. 3 Etching cell

Copper beuig removed from this area

Copper under etching


Fig. 4 Typical circuit board sample under etching

x(a -b)


(c -a)


B. H. Fadhil

Copper Etching In Air Regenerated Cupric Chloride Solution

cell below the etchant surface level by about 4 em. Samples are cleaned and polished well to obtain a scratch-free surface before dipping into the etching solution. Because the etchant become darker as its density increases, light source was installed behind the cell enabling best view of sample etching details instead of sample monitoring outside the cell from time to time.

The term 'average etching rate' was used in this study because etching of the sample is not uniform.

In other word not all the copper removed evenly from the sample sheet at the same time as shown in Fig. 4. Instead, pits start to appear (white area) and spread in all directions until the copper (black area) was removed completely. At this point, time was recorded and etching rate was calculated from the equation:

A E h· R Copper Thickness (4)

verage tc mg ate = .

Total Etching Time

Solution specific gravity was adjusted between each run after etchant was completely regenerated to its original state by a hydrometer. Leaving the solution about half-hour under air bubbling was considered to be sufficient time to return back the solution nearly to its initial state.

Free acid concentration was measured and adjusted using 37% hydrochloric acid of 1.19 specific gravity. Measurement of the free acid concentration was done by titration with NaOH solution. The amount of acid required to adj ust the etchant can be calculated from:

where y is the volume of acid required to adjust the etch ant to the acid concentration required concentration a, x is the etchant volume (i.e. 1000 ml), b is the measured acid concentration by titration, and c is the concentration of the hydrochloric acid being added.

Note that the addition of HCI should be the last step in solution adjustment process because small amount of HCI is needed usually to bring the solution up to the desired acid concentration without changing the specific gravity of the solution appreciatory.

RESULTS AND DISCUSSION Effect of Etching Temperature

In general, increasing the temperature tends to increase the etching rate as shown in Figs. 5-9. It is desired usually to select a temperature range which should give a relatively acceptable etching rate for practical purposes. Temperatures below 40°C takes long etching times (i.e. low etching rate) with low HCl fumes and above 55°C, etching rate increases many times but causes too much HCl fumes to start also. Under air regenerated cupric chloride etchant, it is observed that temperature range between 45°C and 55°C is the suitable working range depending on the air flow rate because oxygen solubility decreases with increasing temperature (i.e. to work at elevated temperature range to obtain higher etching rates, one should distribute much more bubbles - in the maximum allowable flow - to maximize the rate of solubility of oxygen to the maximum one).


Number 3

Volume 16 September 2010

Journal of Engineering

Temperature rei


~5 o2MHCI

.§ 63MHCI



= u








Fig. 5 Average etching rate versus etchant temp. at different free acid conc. and 1.1 sp.gr.



7 o2MHCI

~ 6 l:I3MHCI



ID ~

c; 4

= u

W 3



~ 2




45 Temperature ee)



Fig. 7 Average etching rate versus etchant temp. at different free acid cone. and 1.3 sp.gr.

Effect of Etchant Specific Gravity

As copper continue to dissolve and water evaporates, specific gravity of the etchant will increase also and the etchant become a dense solution. At some point, this will cause average etching rate to slow down because the movement of cuprous ions away from the copper surface become more difficult and may initiates sludges to be formed.

Figs. 10-14 shows the effect of etchant specific gravity change on average etching rate at different temperatures. It is clear that maximum and nearly constant etching rate occurs between specific gravity of 1.3 and 1.4 as it does not change significantly within this range. Average etching rate decreased below specific gravity of 1.3 and above



01 MHel 02 MHCI 63 MHCI

a:: 3






45 Temperature eC)



Fig. 6 Average etching rate versus etch ant temp. at different free acid cone, and 1.2 sp.gr.

8 --


02 M HCI

63 M HCI

W 3

ID '"







Temperature eC)

Fig. 8 Average etching rate versus etch ant temp. at different free acid cone. and 1.4 sp.gr.

ID >


01 MHCI 02 M HCI

63 M HCI




45 Temperature 1°C)



Fig. 9 Average etching rate versus etchant temp. at different free acid conc. and 1.5 sp.gr.




B. H. Fadhil

Copper Etching In Air Regenerated Cu ric Chloride Solution

1.4. So that, it is desired to control the specific gravity within this range.

-;;-2.5 02 MHCI
_§ 63MHCI6
E 2
a:: 15
., 1
-c 0.5
11 12 13 " 1.5 16
Specific Gra"ty Fig. 10 Etchant specific gravity versus average etching rate at different free acid cone. and 35°C

45 c 2 M HCI
c; 4 63 M HCI
E 35
2 3
cc 25
w 2
> 1
05 1 2

13 Specific Gra~ly



Fig. 12 Etchant specific gravity versus average etching rate at different free acid cone. and 45°C

Effect of Etchant Free Acid Concentration

From the previous figures (Figs. 5-14), It IS clear that increasing the free acid concentration in the solution is proportional with the average etching rate. Low etching rate were observed at 1 M HCl with low fuming in all temperature range studied, at 2 and 3M HCI, higher etching rates were obtained but the rate of fuming increases also especially at elevated temperatures when 3 M HCI were used. So that, the selection of HCI concentration should be contributed with the working temperature and the allowable limit of fuming. The best operating free HCI level was suggested to be between 2 and 3 M HC!.


w 15

63 M HCI



3.5 02 M Hel


= Q








Fig. 11 Etchant specific gravity versus average etching rate at different free acid cone. and 40CC

-" ... -


'" >


6 3 M HCI

02 M HCI _5


., ~

0:: 3




Fig. 13 Etchant specific gravity versus average etching rate at different free acid cone. and SO°C

01 MHCI o2MHCi 63 MHCI



E 2-5

'" '" cc 4


1 3.


Specific Gravity

Fig. 14 Etchant specific gravity versus average etching rate at different free acid cone, and 55°C

Number 3

Volume 16 September 2010

Journal of Engineering


• Single-sided circuit boards can be etched with different etch ants but cupric chloride is the most suitable one even for large production lines.

• Cupric chloride can be regenerated using many oxidants even oxygen from air and the parameters affecting etching rates should be contributed together in order to maximize the etching rate.

• It is found that controlling temperature within the range of 45-55°C, etchant specific gravity of 1.3-1.4, and free acid concentration of 1.3-1.4 M would provide the best etching results.


a Free acid required concentration, M

b Measured free acid concentration, M

c Acid concentration being added, M

x Etchant total volume, ml

y Etchant volume required to adjust the etchant to the desired level, ml


• Chemcut Corporation., Technical document: Process Guidelines for Cupric Chloride Etching, (2002), http.z/www.chemcut.net, Aug 2009.

• Clyde F. Coombs, Jr, Printed Circuits Handbook, 6th edition, McGraw-HilI Companies, 2008.

• O. Cakir, A. Yardimeden, T. Ozben, Chemical Machining, Archives of Materials Science and Engineering, Vol. 28, Issue 8 (2007), pp. 499-502.

• o. Cakir, Copper Etching and Regeneration of Waste Etchant, Journal of Material Processing Technology, 175 (2006), pp. 63-68.

• O. Cakir. Photochemical Machining of Engineering Materials, Archives of Materials Science, Vol. 28 No. 1-4 (2007), pp. J 5-19.

• P. Adaikkalam, G. N. Srinivasan, and K. V. Venkatcswaran, The electrochemical Recycling of Printed-Wiring-Board Etchants. JOM, June (2002).

• Stephen D. Kasten, Electronic Prototype Construction, Howard W. Sam & Co., Inc, 1983.

• WECC Global PCB Production Report for 2006, 2007, and 2008, http://www.hkpca.org, Jan 2009.

• Xingsheng Liu, Processing and Reliability Assessment of Solder Joint Interconnection for Power Chips, PhD dissertation in Material Engineering and Science, Virginia Polytechnic Institute and State University, 200 l.


ISSN 1726-4073

2010 J~i


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