Ⓡ

- Antimicrobial Additive for Concrete Corrosion Control -

Nov 21, 2012

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 Antimicrobial
Antimicrobial
Technology
Technology
for Concrete
for Concrete
Corrosion
Corrosion
Summary

• It is known that Hydrogen Sulfide Gas released from

wastewater into sewer atmosphere tends to build up Sulfuric
Acid by the activity of Sulfur-Oxidizing Bacteria, Thiobacillus
thiooxidans, which causes concrete corrosion.
• If countermeasures for this type corrosion don’t be carried
out, it will lead to the social big problems such as road cave-
ins in the future. Therefore, the countermeasures for
corrosion are needed when sewerage is newly installed.
• ZeomightyⓇ-added concrete, by way of suppressing
proliferation of the bacteria on the surface of concrete
products, can control build-up of Sulfuric Acid, and thus
alleviate this type of concrete corrosion.
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 Antimicrobial
Antimicrobial
Technology
Technology
for Concrete
for Concrete
Corrosion
Corrosion

• Concrete products manufacturers can easily adopt this

antimicrobial technology; Just mix ZeomightyⓇ into cement
at the rate of 1% by weight.
• ZeomightyⓇ is certified as antimicrobial agent, which is
effective against concrete corrosion, by JIWET, Japan
Institute of Wastewater Engineering Technology that is
within the jurisdiction of MLIT.
• ZeomightyⓇ-added concrete pipe is registered as authorized
materials for sewer by JSWA, Japan Sewage Works
Association that is an administrative organ of MLIT.

※ MLIT: Ministry of Land, Infrastructure, Transport and Tourism

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 Antimicrobial
Antimicrobial
Technology
Technology
for Concrete
for Concrete
Corrosion
Corrosion
Corrosion Mechanism of the Concrete

<Step 1>
Generation of Hydrogen Sulfide in wastewater
H2S+2O2→H2SO4
↑ SO42- + 2C + 2H2O → 2HCO3- + H2S
Sulfur-Oxidizing
Bacteria Badly
damaged <Step 2>
concrete

Condensed
Hydrogen Sulfide is diffused into the gas phase.
water

H2O Condensation <Step 3>

caused by
temperature
difference Water lifted by
Capillarity
Generation of Sulfuric Acid by the activity of Sulfur-
Oxidizing Bacteria
H2S

H2S + 2O2 → H2SO4

Sewer

Sludge
Sulfur-Oxidizing
Bacteria
Hume Pipe

Not only a simple chemical

reaction, but microbe involves.
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 Antimicrobial
Antimicrobial
Technology
Technology
for Concrete
for Concrete
Corrosion
Corrosion

<Step 4>
Sulfuric acid formed on the surface of concrete reacts with calcium hydroxide,
which is a main component of concrete, to form calcium sulfate dihydrate
(gypsum dihydrate).
Ca（OH）2 + H2SO4 → CaSO4 ・ 2H2O (Gypsum dihydrate)
<Step 5>
Gypsum dihydrate further reacts with 3CaO ・ Al2O3 in the cement, and then it
leads to the reaction that forms ettringite (cement bacillus). Furthermore, if pH
value decreases to neutrality, the ettringite regenerates gypsum dihydrate
which turns to be fragile in acidity. As a consequence of such reactions,
swelling, cracking, exfoliation, etc. occur in concrete, and corrosion progresses.
3CaSO4 ・ 2H2O + 3CaO ・ Al2O3 + 26H2O
→ 3CaO ・ Al2O3 ・ 3CaSO4 ・ 32H2O (Ettringite)

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 Antimicrobial
Antimicrobial
Technology
Technology
for Concrete
for Concrete
Corrosion
Corrosion

Breeding of Sulfur- The pH decreases Regeneration of

Oxidizing Bacteria on the surface of gypsum dihydrate
concrete

Concrete Surfaces Concrete Surfaces Concrete Surfaces

Further penetration of Sulfuric Acid

Penetration of Sulfuric Acid Regeneration of
Sulfur-Oxidizing Generation of
Bacteria adhere to Ettringite gypsum dihydrate Fe layer
concrete surfaces.

Generation of
Ettringite

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 Antimicrobial
Antimicrobial
Technology
Technology
for Concrete
for Concrete
Corrosion
Corrosion

Relation of Sulfur-Oxidizing Bacteria and pH

Neutralization by CO2 Generation of thiosulfuric Generation of sulfurous

acid & polythionic acid acid & sulfuric acid

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Ten or more kinds of bacteria exist in Sulfur-
12 Oxidizing Bacteria, and the breeding of each
11 T. neapolitanus bacteria will be depending on pH value.

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The activity of microbes

9
T. Intermedius
pH

8
T. thiooxidans
7 T. novellus
6
5
4
3 T. thioparus
pH
2
1

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 Antimicrobial
Antimicrobial
Technology
Technology
for Concrete
for Concrete
Corrosion
Corrosion
Corrosion Images in Sewer
Manhole

Steep Part of corrosion

incline (Red)

H2S
generation
Slow
incline

Deposited
sludge (Sulfide) Flow

At the part where sludge tends to deposit and sewage becomes turbulent,
hydrogen sulfide gas is easily generated and diffused to the sewer
atmosphere, and then changes into sulfuric acid by the activity of Sulfur-
Oxidizing Bacteria. 8
 Antimicrobial
Antimicrobial
Technology
Technology
for Concrete
for Concrete
Corrosion
Corrosion

Manhole

Part of corrosion (Red)

H2S
generation
Compression pipe
Natural downward flow
Pump
facilities H2S
ide
f sulf generation
erat ion o
Gen
Flow

In the compression pipe, sulfide tends to be generated. The sulfide, H2S,

is diffused to the sewer atmosphere by turbulent flows with pump
operation and tends to change into sulfuric acid by the activity of Sulfur-
Oxidizing Bacteria. 9
 Antimicrobial
Antimicrobial
Technology
Technology
for Concrete
for Concrete
Corrosion
Corrosion

Corrosion at Wastewater Treatment Facilities

Exfoliation of corrosive protection material, Exposed aggregate

and corrosion of internal concrete

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 Antimicrobial
Antimicrobial
Technology
Technology
for Concrete
for Concrete
Corrosion
Corrosion

Heavily corroded slab

Exfoliation of corrosive protection material,
and swelling of internal concrete (about 10cm corrodes)

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 Antimicrobial
Antimicrobial
Technology
Technology
for Concrete
for Concrete
Corrosion
Corrosion

Corrosion at Sewer

Swelling of
internal concrete
Exposed aggregate

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Antimicrobial
Antimicrobial
Technology
Technology
for Concrete
for Concrete
Corrosion
Corrosion

Corrosion at Manhole

Exposed aggregate

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 Antimicrobial
Antimicrobial
Technology
Technology
for Concrete
for Concrete
Corrosion
Corrosion

Corrosion at Wastewater Treatment Facilities

Sulfur deposits at the lid edge. Heavily corroded slab (about 50mm)

As a similar case example, the fall accident of the patching

worker by separating the lid occurred in Yokohama sewage
treatment facility in January, 2007, and 1 worker died.
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 Antimicrobial
Antimicrobial
Technology
Technology
for Concrete
for Concrete
Corrosion
Corrosion
Rapid Increase of Deterioration of Sewer
A large quantity of
Deterioration deteriorated pipes
started occurs ten years later.

2000 km before Y 1945

Road cave-in situation

Y 1920 Y 1945 Y 1955 About Y 1998

15,000km
Road cave-in accident by the deterioration of the sewer
occurs about 6,600 per year in Japan.
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 Antimicrobial
Antimicrobial
Technology
Technology
for Concrete
for Concrete
Corrosion
Corrosion

Road cave-in accident by the deterioration of the sewer

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Antimicrobial
Antimicrobial
Technology
Technology
for Concrete
for Concrete
Corrosion
Corrosion

Corroded Hume Pipe

 Antimicrobial
Antimicrobial
Technology
Technology
for Concrete
for Concrete
Corrosion
Corrosion

Antimicrobial Concrete Technology

Antimicrobial concrete is the concrete which ZeomightyⓇ is added into

cement at the rate of 1% by weight, and by way of suppressing
proliferation of Sulfur-Oxidizing Bacteria, can control build-up of sulfuric
acid and thus alleviate this type of concrete corrosion.

Antibacterial concrete can be used in sewer environment with an annual

average hydrogen sulfide concentration of 50 ppm or less (Certified by
JIWET, governmental organization).

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 Antimicrobial
Antimicrobial
Technology
Technology
for Concrete
for Concrete
Corrosion
Corrosion
Characteristics of ZeomightyⓇ
Antimicrobial Effect
• Sulfur-oxidizing bacteria can be controlled, and generation of sulfuric acid can be prevented.
• Aerobic bacteria (E. Coli, Bacillus Subtlis, etc.) can be controlled, and generation of organic acid
can be prevented.
• There is almost no elution of active ingredients (silver / copper ion), and an antimicrobial effect
continues for a long period of time.

Environmental Safety
• The safety to human body is high (Acute Oral Toxicity: LD50 > 2,000mg/kg or more, Mutagenicity:
Negative)
• Not having bad influence to the activated sludge bacillus used for sewage disposal procedure (the
degree of COD biological breakdown: 96.0%).

Handling
• Easy to disperse ZeomightyⓇ into cement, since its physical properties is similar to cement.
Zeomighty Ⓡ can be dispersed by mixing just for 60 seconds.

Economical Efficiency
• Specific equipment for mixing ZeomightyⓇ is not needed. It ends with the rise of only the cost
of ZeomightyⓇ. 19
 Antimicrobial
Antimicrobial
Technology
Technology
for Concrete
for Concrete
Corrosion
Corrosion
ZeomightyⓇ

【Ingredients】
Ag+
Silver / Copper Zeolite and GGBFS
【Usage】 Cu++
Add into cement materials at 1% by weight
Structure of ZeomightyⓇ

Appearance Grayish fine powder

Bulk Density 0.73 g / cm3

True Specific Gravity 2.83

Ave. Particle Size 12.5 μm

Volatility None

Water Solubility None

Physical properties of ZeomightyⓇ Appearance

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 Antimicrobial
Antimicrobial
Technology
Technology
for Concrete
for Concrete
Corrosion
Corrosion

Ion-Exchange Technology

O O
(-)
O Si O Al O
(+) (+)
2Ag O 2Na O
(-)
O Al O Si O ●Aluminum ○Silicate ▲Cu ion △Ag ion

O O
(2+)
Cu

Structure of Aluminosilicate

The affinity to Aluminosilicate

Ag+ > Cu2+ > Th4+ > Al3+ > H+ > Zn2+ > Sr2+ > Ba2+ > Ca2+ >
Co2+ > K+ > Na+ > Ni2+ > NH4+ > Cd2+ > Hg2+ > Li+ > Mg2+ ･･･ Electron Microscopic Photograph

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 Antimicrobial
Antimicrobial
Technology
Technology
for Concrete
for Concrete
Corrosion
Corrosion
Manufacturing Flow of Antimicrobial Concrete Pipe

Processing

Steel rod Spacer Attachment

Mold Assembly
Raw Material Acceptance

Cement

Water

Form Removal
Measurement

Shipment
Molding

Curing
Mixing
Coarse aggregate

Fine aggregate

Mixing agent

ZeomightyⓇ Measurement

Acceptance Inspection
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 Antimicrobial
Antimicrobial
Technology
Technology
for Concrete
for Concrete
Corrosion
Corrosion
Antimicrobial Concrete Product

Application: Concrete products, Ready-mixed concrete, Mortar, Etc.

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 Antimicrobial
Antimicrobial
Technology
Technology
for Concrete
for Concrete
Corrosion
Corrosion

On-Site Testing Result

Plain ZM-added

Test piece: φ100×200mm concrete piece (Plain & ZeomightyⓇ-added)

Testing place: Sedimentation tank at sewage treatment facility in Nagoya
Conditions: Avg. H2S concentration 40.7ppm, Avg. Temp. 26 deg. C, Avg. Humidity 79%
Testing period: 3 years and 2 months

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 H硫2S化Concentration
水 素 ガ ス 濃 度(ppm)
（ ppm ）

0
5
10
15
20
25
30
35
2001/11/9
2001/11/9
2001/11/9
2001/11/9

at
2001/11/10
2001/11/10
2001/11/10
2001/11/10
2001/11/11
2001/11/11
2001/11/11

Sedimentation
2001/11/11
2001/11/12
2001/11/12
2001/11/12
2001/11/12
Antimicrobial

2001/11/13

日時
2001/11/13
Corrosion

2001/11/13
2001/11/13
Antimicrobial

2001/11/14
2001/11/14
Technology

2001/11/14
愛知県S下水処理場（最初沈殿池気相部）の

2001/11/14
The Measurement Period

硫化水素ガス濃度の経時変化（2001．11.9∼11.16）

2001/11/15
Variation in Time of Hydrogen Sulfide
Tank in Wastewater Treatment

2001/11/15
Technology

2001/11/15
2001/11/15
測定装置設置期間：11.9：14：30∼11.16：13：30

2001/11/16
Facility
for Concrete

2001/11/16
2001/11/16
2001/11/16
for Concrete

2001/11/17
Corrosion

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 Antimicrobial
Antimicrobial
Technology
Technology
for Concrete
for Concrete
Corrosion
Corrosion

Plain Concrete ZeomightyⓇ-added Concrete

(3 years & 2 months passed) (3 years & 2 months passed)

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 Antimicrobial
Antimicrobial
Technology
Technology
for Concrete
for Concrete
Corrosion
Corrosion
Estimate of Corrosion Rate（H2S: 50ppm）
1.4
Rate (mm/Year)

1.2
Plain y=0.0190x-0.0154
腐食速度（mm/年）

0.8

0.6
Corrosion

0.4 Antimicrobial y=0.0028x-0.0060

0.2

0
0 10 20 30 40 50 60
H平均硫化水素濃度（ppm）
2S Avg. Concentration (ppm)

添加品 回帰式（添加品）
Antimicrobial 無添加品 回帰式（無添加品）
Plain

Avg. H2S Antimicrobial Plain

（ppm） （mm/Year） （mm/Year）
Corrosion Rate 50 0.134 0.935
Antimicrobial concrete can control around a one-seven progress of the corrosion in comparison
with plain concrete. 28
 Antimicrobial
Antimicrobial
Technology
Technology
for Concrete
for Concrete
Corrosion
Corrosion
Estimation of Durable years in Sewer

【Conditions; H2S 50ppm】

100 Strength maintains
90
抵抗曲げモーメント比

80
MR/M0（ %）
Ratio of RBM

70 通常コンクリート
Plain Concrete
60 抗菌コンクリート
Antimicrobial Concrete

50
40
30
0 20 40 60 80 100
Strength declines
耐 用 年 数Years
Durable （年）

As for concrete pipe for sewer, its resistance bending moment gradually declines
as pipe’s thickness becomes thin by reason of corrosion. It is said that a strength
problem will occur, If the rate of decline of resistance bending moment reaches
less than 50 %. Antimicrobial concrete can be estimated that its resistance
bending moment keeps over 50 % when it passes more than 50 years.
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 Antimicrobial
Antimicrobial
Technology
Technology
for Concrete
for Concrete
Corrosion
Corrosion

Estimate of Durable Years in Concrete Structures

Years Till Reinforced Rod is Exposed

Necessary Thickness (H2S 50ppm)
Part Conditions
of Concrete (mm)
Antimicrobial Plain

Normal 25 186 26

Slab Corrosive 40 298 42

Heavily Corrosive 50 373 53

Normal 30 223 32

Beam Corrosive 50 373 53

Heavily Corrosive 60 447 64

Normal 35 261 37

Pillar Corrosive 60 447 64

Heavily Corrosive 70 522 74

※ Ref. “Standard Specifications for Concrete Structures-2002”, Japan Society of Civil Engineers 30
 Antimicrobial
Antimicrobial
Technology
Technology
for Concrete
for Concrete
Corrosion
Corrosion

Influence on Compression Strength

Weight （kg/m3）
Test Piece W/C Water
W C S G Reducing Zeomighty
Additive

Plain Concrete 41.7 173 415 889 909 2.90 0

Anti. Concrete 41.7 173 415 889 909 2.90 4.15
Plain Mortar 50.0 310 620 1240 - - 0
Anti. Mortar 50.0 310 620 1240 - - 6.20
)

)
60 60
2

2
度 （N/m m(N/mm

（N/m m 2 (N/mm
50 50
2
）

）
圧 縮 強Strength

圧 縮 強 度Strength
40 40
30
30
Compression

20 Compression
20
10
10
0
11日
day 1414日
days 7 7日
days 2828日
days 0
蒸気養生            標準養生
Steam Curing Standard Curing 1414日
days 6 Months
6ヶ月 1 1年
year 2 years
2年
Plain Con. 抗菌ｺﾝｸﾘｰﾄ
普通ｺﾝｸﾘｰﾄ Plain Mor.抗菌ﾓﾙﾀﾙ
Anti Con. 普通ﾓﾙﾀﾙ Anti. Mor. Plain Con.
普通ｺﾝｸﾘｰﾄ Anti. Con.
抗菌ｺﾝｸﾘｰﾄ 31
 Antimicrobial
Antimicrobial
Technology
Technology
for Concrete
for Concrete
Corrosion
Corrosion

Public Certification

• Certified on March, 2000, by JIWET, Japan Institute of Wastewater Engineering

Technology that is within the jurisdiction of MLIT.
• Granted as anti-corrosion material for sewer systems.
• Certified that ZeomightyⓇ can protect concrete from corrosion for 50 years.
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 Antimicrobial
Antimicrobial
Technology
Technology
for Concrete
for Concrete
Corrosion
Corrosion

Registration

• ZeomightyⓇ-added concrete pipe is registered as authorized materials for sewer

on 2008 by JSWA, Japan Sewage Works Association that is an administrative
organ of MLIT.
• JSWA directs local government offices to use ZeomightyⓇ-added concrete pipe,
when they newly installs sewerage.
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 Antimicrobial
Antimicrobial
Technology
Technology
for Concrete
for Concrete
Corrosion
Corrosion

National Guideline

• Published as National Guideline against Concrete Corrosion on 2004 by JSWA.

• The application of “Antimicrobial concrete” is recommended as a
countermeasure technique against the concrete corrosion.

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 Antimicrobial
Antimicrobial
Technology
Technology
for Concrete
for Concrete
Corrosion
Corrosion
Total Achievement of Antibacterial Concrete
180,000
160,000
140,000
120,000
100,000
80,000
60,000
40,000
20,000
0
1997 1999 2001 2003 2005 2007 2009 2011
Zeomighty-added concrete (MT)
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