Possible materials for producing Geopolymer concrete and ... · Na2CO3 + SiO2 → Na2SiO3 + CO2...

INTERNATIONAL JOURNAL OF CIVIL AND STRUCTURAL ENGINEERING

Volume 5, No 3, 2015

© Copyright by the authors - Licensee IPA- Under Creative Commons license 3.0

Review article ISSN 0976 – 4399

Received on August 2014 Published on February 2015 296

Possible materials for producing Geopolymer concrete and its performance

with and without Fibre addition- A State of the art review Alwis deva kirupa J P1, Sakthieswaran N2

1- Assistant Professor, Department of Civil Engineering, Ponjesly College of Engineering,

Nagercoil, India

2- Department of Civil Engineering, Regional center of Anna University, Tirunelveli, India

[email protected]

doi: 10.6088/ijcser.2014050028

ABSTRACT

Global warming is one of the most pronounced terms in this present century. Hence reducing

the greenhouse gas emissions, which is the reason behind global warming, is the need of the

hour and so efforts are urgently underway all over the world to develop environmentally

friendly construction materials, which make minimum utility of fast dwindling natural

resources and help to reduce greenhouse gas emissions. Five to eight percent of the world’s

manmade Greenhouse gas emissions are from the Cement industry itself. It is an established

fact that the green house gas emissions are reduced by 80% in Geopolymer concrete vis-a-vis

the conventional Portland cement manufacturing, as it does not involve carbonate burns. In

this connection, Geopolymers are showing great potential and several researchers have

critically examined the various aspects of their viability as binder system. Considerable

research has been carried out on development of Geopolymer concretes (GPCs), which

involve heat curing. A few studies have been reported on the use of such GPCs for structural

applications. Thus Geopolymer based Concrete is highly environment friendly and the same

time it can be made as high performance concrete. This paper presents a review of the

literature, outlining the various research approaches undertaken in an effort to check the

feasibility of geopolymer to Civil Engineering applications. The findings of these varying

approaches are compared, and the different strategies employed are compiled and discussed.

It is expected that this review will provide a key step in advancing the understanding of this

innovative construction material.

Key Words : Geopolymerisation, Fly Ash, Red Mud, Ground Granulated Blast Furnace slag

(GGBS), Activator Solution.

1. Introduction

Ordinary Portland cement has been a binder for Civil Engineering tasks for a long time. But

at present, there are many new issues branching from its ever increasing use. Cement

production consumes huge quantities of virgin materials, is energy-intensive, and leads to

high emission of the greenhouse gas CO2, which is the main reason behind Global warming.

Again, Sulphur dioxide emission also can be very high, depending upon the type of fuel used.

Installation of new cement plants is becoming increasingly capital-intensive. Finally, many

cement concrete structures have exhibited early distress and problems, which has an adverse

effect on the resource productivity of the industry. To overcome all such limitations, a new

cementitious composite called “Geopolymer” is evolved. The name geopolymer was coined

by a French Professor Davidovits in 1978 to represent a broad range of materials

characterized by networks of inorganic molecules. It is a type of inorganic polymer

composite, which has recently emerged as a prospective binding material based on novel

Possible materials for producing Geopolymer concrete and its performance with and without Fibre addition-

A State of the art review

Alwis deva kirupa J P and Sakthieswaran N

International Journal of Civil and Structural Engineering 297

Volume 5 Issue 3 2015

utilization of engineering materials. The geo-polymeric concretes are commonly formed by

alkali activation of industrial aluminosilicate waste materials such as fly ash (FA), Ground

Granulated Blast furnace Slag (GGBS), etc and have very small footprints of greenhouse

gases when compared to traditional concretes. They can be designed as high strength concrete

too. Main advantages of geopolymers are their chemical stability, resistance to the sulphate

corrosion and long lasting strength. Because of possible realization of even superior chemical

and mechanical properties compared to Ordinary Portland cement (OPC) based concrete

mixes, and higher cost effectiveness, GPC mixes based on FA and GGBS are being discussed

for their potential application in concrete industry including structural concreting, precast

panels and ready-mixes.

2. Materials that can be generally used

Most common materials other than that used for Ordinary Portland Cement Concrete (OPCC)

used in production of Geopolymer concrete (GPC) are

1. Fly Ash

2. Ground Granulated Blast furnace Slag (GGBS)

3. Red Mud

4. Microsilica

5. Metakaolin

6. Rice Hush Ash (RHA)

7. Activator Solution

2.1 Fly Ash

Fly ash is a product (waste) of burning finely ground coal to heat a boiler to produce

electricity. It is removed from the plant exhaust gases primarily by electrostatic precipitators

or bag houses and secondarily by scrubber systems. Physically, fly ash is a very fine,

powdery material, composed mostly of silica. Fly ash is generally light tan in color and

consists mostly of silt-sized and clay-sized glassy spheres. They are generally spherical in

shape and range in size from 0.5 µm to 100 µm. They consist mostly of SiO2, which is

present in two forms: amorphous, which is rounded and smooth, and crystalline, which is

sharp, pointed and hazardous. Three classes of fly ash are defined by ASTM C 618; Class N

fly ash, Class F fly ash, and Class C fly ash. The chief difference between these classes is the

amount of calcium, silica, alumina, and iron content in the ash.

2.2 Ground Granulated Blast furnace Slag (GGBS)

Ground-granulated blast-furnace slag is obtained by quenching molten iron slag from a blast

furnace in water or steam, to produce a glassy, granular product that is then dried and ground

into a fine powder. The main components of blast furnace slag are CaO (30-50%), SiO2 (28-

38%), Al2O3 (8-24%), and MgO (1-18%). In general, increasing the CaO content of the slag

results in raised slag basicity and an increase in compressive strength. The MgO and Al2O3

content show the same trend up to respectively 10-12% and 14%, beyond which no further

improvement can be obtained. GGBS has now effectively replaced sulfate-resisting Portland

cement (SRPC) on the market for sulfate resistance because of its superior performance and

greatly reduced cost compared to SRPC.

2.3 Red Mud






Red mud is the major industrial waste produced by the Bayer process for the extraction of

alumina from bauxite ores, one of the oldest large-scale industries in the world. It is

characterized by strong alkalinity even with a high water content (up to 95%), owing to the

presence of an excessive amount of dissolved sodium hydroxide used to extract silicates and

alumina. The red colour is caused by the oxidized iron present, which can make up to 60% of

the mass of the red mud. In addition to iron, the other dominant particles include silica,

unleached residual aluminium, and titanium oxide. Disposal becomes a huge problem due to

the presence of high pH, heavy metals and radioactivity. Therefore, new technologies

utilizing red mud as a raw material for manufacturing high added-value products are urgently

needed, besides the use in production of GPC.

Figure 1: Fly Ash Figure 2: Mixture of GGBS and Red Mud

2.4 Microsilica

Silica fume, also known as microsilica, is an amorphous (non-crystalline) polymorph

of silicon dioxide, silica. It is an ultrafine powder collected as a by-product of the silicon and

ferrosilicon alloy production and consists of spherical particles with an average particle

diameter of 150 mm. Colour varies from dark black to almost white. The main field of

application is as pozzolanic material for high performance concrete. It is sometimes confused

with fumed silica (also known as pyrogenic silica). However, the production process, particle

characteristics and fields of application of fumed silica are all different from those of silica

fume. Silica fume is an ultrafine material with spherical particles less than 1 µm in diameter,

the average being about 0.15 µm. This makes it approximately 100 times smaller than the

average cement particle. The specific gravity of silica fume is generally in the range of 2.2 to

2.3.

2.5 Metakaolin (Kaolinite)

Kaolinite is a clay mineral with the chemical composition Al2Si2O5(OH)4, which means each

particle has one tetrahedral silica layer and one octahedral alumina layer. It is a soft, earthy,

usually white mineral, produced by the chemical weathering of aluminum silicate minerals

like feldspar. Rocks that are rich in kaolinite are known as china clay, white clay, or kaolin.






Kaolin is a fine, white, clay mineral that has been traditionally used in the manufacture of

porcelain. Metakaolin is a dehydroxylated form of the clay mineral kaolinite in the

temperature range of 500-800°C. It is a highly pozzolanic and reactive material.

Figure 3 : Microsilica

Figure 4: Metakaoline

2.6 Rice Husk Ash (RHA)

Rice husk, also called rice hull, is the hard protecting covering of grains of rice, which is a

by-product generally obtained from milling process of rice crop. The RHA is generated after

burning the rice husk in the boiler, which is collected from the particulate collection

equipment attached upstream to the stack of rice-fired boilers. For the transition from rice

husk to RHA, the quantity of RHA generated is about 20% of the processed rice husk. The

RHA is highly porous and lightweight with a very high external surface area and contains

silica in high content (usually 90 - 95 wt.%). At present, the most common method of

disposal of RHA is dumping on waste land, thus creating an environmental hazard through

pollution and land dereliction problems. Since the amount of RHA generated is in plenty

annually, an effective way of disposal of RHA is needed urgently.

2.7 Activator Solution






The most common alkaline liquid used in geopolymerisation is a combination of sodium

hydroxide (NaOH) or potassium hydroxide (KOH) and sodium silicate or potassium silicate.

Figure 5: Rice Husk Ash

2.7.1 Sodium Silicate

Sodium silicate is the common name for a compound sodium metasilicate, Na2SiO3, also

known as waterglass or liquid glass. It is available in aqueous solution and in solid form and

is used in cements, passive fire protection, refractories, textile and lumber processing, and

automobiles. Sodium carbonate and silicon dioxide react when molten to form sodium

silicate and carbon dioxide.

Na2CO3 + SiO2 → Na2SiO3 + CO2

Formula: Na2SiO3

IUPAC ID: Sodium metasilicate

2.7.2 Sodium Hydroxide

Sodium hydroxide, also known as caustic soda, or lye, is an inorganic compound with

the chemical formula NaOH. It is a white solid and

highly caustic metallic base and alkali salt which is available in pellets, flakes, granules.

Sodium hydroxide is soluble in water, ethanol and methanol. This alkali is deliquescent and

readily absorbs moisture and carbon dioxide in air. It is used in many industries, in the

manufacture of pulp and paper, textiles, drinking water, soaps and detergents and as a drain

cleaner. Similar to the hydration of sulphuric acid, dissolution of solid sodium hydroxide in

water is a highly exothermic reaction in which a large amount of heat is liberated, posing a

threat to safety through the possibility of splashing. The resulting solution is usually

colourless and odorless with slippery feeling upon contact in common with other alkalis.

Since the geo-polymer concrete is a homogenous materials and its main process to activate

the sodium silicate, pellet form is preferred.






Figure 6: Sodium Hydroxide Figure 7: Pellet form Figure 8: Flakes form

3. Review consequences

Based on the review, following fallouts are derived. They are listed in Table 1.

Table 1: Compilation of Review Results

Sl

no

Author

and Year

Results and Discussions

1 Supraja V,

Kanta Rao M

2010

GGBS obtained from Vizag steel plant in Andhra Pradesh; NaOH flakes

(commercial grade); Na2SiO3; Coarse aggregate of size 12mm and

20mm; Locally available river sand are the materials used.

Portland cement is fully replaced with GGBS.

Trial mix is adopted by assuming the density of GPC as 2440 kg/m3.

Liquid to binder ratio is assumed as 0.30.

It is observed that compressive strength increased with the increase in the

molarity of sodium hydroxide (9M).

Comparing hot air oven curing and curing by direct sun light, oven cured

specimens gives higher compressive strength.

2 Boskovic

Ivana, et al;

January 2013

NaOH and Na2SiO3 are mixed before 48 hours of GPC production.

Concentration of NaOH varies as 3M, 7M and 10 M; Content of OPC is

4-15% weight.

All the specimens were prepared using the constant value of two

components within the liquid phase L: L (Na2O nSiO2: NaOH) =2.5.

Results indicate the possibility of use of red mud as a good initial

material for geopolymer preparation.

The compressive strength results are within the range of 10.2 MPa to

17.2 MPa under the specified conditions of raw mixture preparation.

SEM analysis confirms the homogeneity of samples. The detection of

amorphous phase is quite hard.

3 Jian He, et

al;

December

2012

A new type of geopolymer composite was synthesized from two

industrial wastes, red mud (RM) and rice husk ash (RHA) and

Metakaolin, a low cost material.

In 1st combination (Red Mud+Fly ash), 1.5 M sodium trisilicate is stirred

for 15 minutes to ensure dissolution whereas in 2nd mixture (Metakaolin

based), NaOH is dissolved in deionized water to get a concentration of

6.50-7.80 M. 3rd combination (Rice Husk Ash+Red Mud) consisted of

NaOH with a molarity of 2M, 4M, 6M with a solution-solid ratio of 1.2.

Higher RHA/RM ratios generally lead to higher strength, stiffness, and






ductility, but excessive RHA may cause the opposite effect.

Effect of raw material mix ratio compressive strength, Young’s modulus,

and failure strain are all enhanced while the Si/Al ratio increases from

1.68 to 2.80.

The compressive strength ranges from 3.2 to 20.5 MPa for the

synthesized geopolymers with nominal Si/Al ratios of 1.68–3.35, which

is comparable to most Portland cements.

A few barriers, such as long curing duration make it practically difficult.

4 Sanjay R, et

al

Sep 2012

Absolute Volume Method was adopted for mix proportioning. Ratio of

NaOH and Na2SiO3 is fixed as 2.5. Binder content accounts in the range

of 23% to 29%. Water content is fixed as 140 lit. 2% by weight of

Superplasticizer is added for desired workability.

Maximum compressive strength of 56.24 Mpa was obtained for 27%

binder content and 12M NaOH.

Addition of 10% GGBS by mass increased compressive strength by 23%.

It decreased by 10-15% compared to conventional aggregates due to

addition of recycled aggregates.

Maximum Split Tensile strength of 3.25 Mpa was obtained for 29%

binder content and 12M NaOH.

Maximum flexural strength of 3.73 Mpa was obtained for 27% binder

content and 12M NaOH.

5 More Pratap

Kishanrao

May 2013

50% of Fly Ash and 50% GGBS forms the binder material. Analytical

grade of NaOH flakes with 97% purity; Commercial grade of Na2SiO3; Coarse aggregate-less than 10 mm and Superplasticizer is used.

It is observed that weight losses in specimens gradually increase in all

mixes with increase in temperature upto 500oC.

It is observed that residual Compressive strength coefficient of

specimens exposed to 200oC is slightly higher than cubes tested at room

temperature while with further increase, there is loss in Compressive

strength gradually.

Hence it is concluded that higher temperature curing is not required in all

cases of GPC.

6 Dattatreya J

K, et al.

2011

FAB series comprises of 75% Fly Ash and 25% GGBS and GGB again

comprises of 3 types of mix designated as GGB 1(100% GGBS+0%Fly

Ash), GGB 2(75% GGBS+25%Fly Ash) and GGB3 (50%

GGBS+50%Fly Ash); Reinforcement – HYSD bars of diameter 8 (for

stirrups),12 and 16 mm; Superplasticer – (Conplast SP – 430) are

involved.

GGB 1 showed a maximum load carrying capacity of 90.60 KN which is

more than Reinforced Portland Cement Concrete (RPCC) beams. In case

of Fly Ash series, deflection was about 41-72% more than RPCC,

whereas in case of GGBS series, the difference was much less due to

their high compressive strength and hence higher Modulus of elasticity

(E).

In general, there was no major difference in failure modes and crack

pattern of all three types of mixes.

7 Ng T.S, Htut

T.N.S &

Foster S. J.

Ratio of NaOH to Na2SiO3 is fixed as 1:2.5 by mass in case of GPC.

Sand is mixed with cement in the ratio 3:1 along with water cement ratio

of 0.4 regarding OCM (Ordinary cement mortar). Superplasticizer is

mixed along with water binder ratio of 0.22 for RPC (Reactive powder






2010 Concrete).

Snubbing effect dominates the highly inclined fibres for mode I (uniaxial

tension) and negatively inclined fibres for mode II (direct tension).

Fibres at high inclination angles potentially fracture and consequently

result in brittle response.

GPC possessed compressive strength higher than conventional mortar

but pullout efficiency of GPC was lower due to its lower elastic modulus.

8 Susan, et al

November

2006

Mix is proportioned to comply with the standards of ACI. Solution

modulus (SiO2/Na2O) is fixed as 2.4. The aggregate content is selected as

55% of CA and 45% of FA. Water binder ratio is 0.45. Steel fibres are

added at the rate of 40kg/m3 in OPCC and 120 kg/m3 in AASC.

Compressive strength loss was seen due to incorporation of steel. But

compressive strength increased in AASC samples than OPC in absence

of fibres.

Splitting tensile strength increases with age and amount of fibre added at

a rate of 37.70% at 7 days and 23.7% at 28 days. But in OPC, it

decreases at early ages. GPC has shown 32% increase compared to

control mix.

Modulus of rupture (MOR) increases with increase in age and fiber

content. AASC 3(120kg/m3 of steel fibres) mix presented high MOR

(8.86 Mpa) at 28 days.

By increasing fibre content, increase in load capacity, toughness (three

times higher) and crack strength is obtained.

9 Mira

Vukcevic, et

al

2013

Activator solution is prepared 48 hours prior to GPC production.

Concentration of NaOH is varied as 3, 7, 10 mol dm-3. Red Mud is

substituted with Metakaolin at a proportion of 4, 8 and 15% by mass. The

cited ingredients are mixed to form a fine, thick pulp.

Highest density values were obtained with low percentage of Metakaolin

which shows RM is a very dense component.

Compressive Strength increase with NaOH concentration upto 7 M and it

decreases with 10 M.

Compressive strength also increases with increase in level of substitution

of RM upto 15%.

With NaOH concentration of 7 M and 10% RM substitution, MK-RM

based GPC developed satisfactory strength.

10 Gokulram H,

Anuradha

March 2013

Mixtures were prepared with alkaline liquid to binder ratio by mass value

is 0.45 for mix id M1, M2, M3 and 0.55 for mix id M4, M5.

Polypropylene fibres were added to the mix in the volume fraction of

0.25% volume of concrete. Two kinds of systems were consider in this

study using 100% replacement of cement by ASTM class F Fly ash (FA)

and ground granulated blast furnace slag (GGBS) and 100% replacement

of natural sand by Manufactured sand.

100% Replacement of cement by GGBS in Polypropylene Fibre

Reinforced Geopolymer Concrete (PFRGC) shows better Compressive

strength, Split Tensile strength and Flexural strength when compared to

100% replacement of fly ash (FA).

The mechanical properties obtained for different binder composition of

FA and GGBS incorporated with 0.25% of Polypropylene Fibre agrees

well.

The usage of Polypropylene Fibre in Geopolymer synthesis suggests an






approach to further enhancing the environment benefits and solving the

problems of large shrinkage and high brittleness.

11 Brock

William

Tomkins

October

2011.

The concretes under investigation include fly-ash based geopolymer

concrete (FAGC) and red-mud based geopolymer concrete (RMGC). The

chemical resistance tests involve sodium hydroxide and sulphuric acid at

20○C and 90○C.

A slump of 200mm is maintained in all mixes.

Results indicated that OPC experienced some strength deterioration in

both an acid environment (-24.9 to -25.6%) and an alkaline environment

(-2.2 to -13.3%).

FAGC was found to have better acid resistance (+3.8 to -17.6%) and

even experienced strength enhancement in sodium hydroxide (+29.1 to

+55.7%).

Interestingly, RMGC exhibited a strength increase of 52.4% in sulphuric

acid while also displaying strength enhancement of +50.5% in sodium

hydroxide.

12 Ambily P.S,

et al

2012

A high volume FA based GPC mix with 80% fly ash and 20% GGBS

and liquid binder ratio of 0.6 were employed for all the beams.

Potassium hydroxide and potassium silicate solution was used as the

alkali activator system.

After a series of trial mixes on geopolymer concrete, the volume of steel

fibres was fixed as 0.75.

The first crack appeared only after 60 KN in case of the beams with

fibres in comparison to the 40 KN in case of beams without fibres.

The deflection at failure ranges from 10 to 15 mm for reinforced GPC

without fibre while the corresponding deflection for GPC beams with

fibre is 15 to 20 mm.

The incorporation of steel fibres improves the ductility and energy

absorption characteristics of geopolymer concretes.

GPC mixes can be developed using potassium compounds in lieu of

normally used sodium compounds.

13 Ganapati

Naidu P, et

al.

July 2012

Sodium silicate (103 kg/m3) and sodium hydroxide of 8 molarity

(41kg/m3) solutions were used as alkalis in all 5 different mixes.

Total aggregate content is assumed as 77% of entire concrete mix by

mass. Ratio of alkaline liquid to binder ratio is fixed as 0.40. Ratio of

Na2SiO3 to NaOH is fixed as 2.50.

Setting times of concrete are reduced with increase in slag content.

28.57% replacement of fly ash with slag, achieved a maximum

compressive strength of 57MPa for 28 days.

The same mix shown 43.56 MPa (25% loss) after exposure of 500°C for

2 hours.

Tensile strength of GPC increases continuously up to 28 days with

increase in percentage of slag (GGBS) to flyash.

14 Adam A.A,

et al.

2010

A w/b ratio of 0.5 was used to prepare all blended GGBS-OPC and

control concrete.

The proportions of GGBS were 30%, 50%, and 70% of the total binder.

A water/solid ratio of 0.45 was used for AAS and 0.29 for geopolymer

concrete.

Liquid sodium silicate and sodium hydroxide were blended in different

proportions providing an alkali modulus (AM) ranging from 0.75 to 1.25.






In general, the 28-days compressive strengths of the AAS and FA

geopolymer concretes are comparable with that of 100% OPC concrete

and blended OPC-GGBS concretes.

The AM of the activator has a significant influence on the strength

ofAASand FA-based geopolymer concrete up toAM = 1, beyond this

level the influence reduced.

Results indicate that the alkali modulus has a major effect on sorptivity

of both AAS and geopolymer, however no significant effects of the alkali

modulus on carbonation were observed on AAS concrete.

The sorptivity of blended concrete reduced but the carbonation increased

as the replacement level increased.

15 Rajamane

NP et al.

(2012)

GPC is prepared from GGBS, a powder from grinding the by-product of

slag waste from blast furnace of steel plants. For comparison,

conventional cement, Portland Pozzolana Cement (PPC) containing Fly

Ash was considered.

To achieve simultaneous acidic and sulphate attack, sulphuric acid is

used for durability studies.

Test data indicate that, on exposure to 2% and 10% sulphuric acid, the

losses in weight, thickness and strength of GPC are significantly much

less than those for Portland Pozzolana Cement concrete (PPCC).

At the end of 90 days, PPCC and OPCC specimens were found to be in

deteriorated state with almost complete loss of integrity. But the GPC

specimens had almost maintained their integrity with minor visible

distress seen on surface.

16 Neetu Singh

et al.

(2013)

The geoploymers are manufactured by geopolymerization between class

F fly ash (FA), with alkali activator fluid (Sodium silicate and sodium

hydroxide).

The optimum compressive strength was obtained at curing temperature

of 1200C for 72 hrs.

The newly synthesized geopolymer then subjected to durability studies

under different aggressive chemical environment with particular

reference to the effect of Acid, Sulphates, and Chloride salts and

compared with ordinary Portland cement (OPC).

It was observed that fly ash-based geopolymer concrete has an excellent

resistance to acid and sulphate attack when compared to conventional

concrete. The better performance of geopolymeric materials than that of

Portland cement concrete in acidic environment might be attributed to

the lower calcium content of the source material.

There is no damage to the surface of test specimens after exposure to

sodium sulfate solution and no significant change in the mass and the

compressive strength of test specimens up to 90 days.

4. Conclusion

From the review done, following conclusions are evolved

1. Al-Si minerals are more soluble in sodium based activators compared to Potassium

based activators.

2. Silica in Na2SiO3 plays important role in GPC since it is the initiator of

Geopolymerisation.






3. Blending of Alkaline activators 24 hours prior to concreting enhance polymerization

process and prevents bleeding and segregation.

4. Combination of high hydroxide concentration and low silicate concentration generally

lower density values.

5. In general, compressive strength increases with increase in molarity of NaOH except

RHA based GPC.

6. Heat released during curing of Fly Ash based GPC is much less(40oC) when

compared to typical concrete(65 to 70oC).This makes it an advantage over OPCC for

large structures like Dams, weirs and tanks.

7. Water has no hardening or weakening effect on GPC.

8. Micro silica can be added at a rate of 5-15% by weight of cement while Red Mud can

be used upto 30%.

9. Fly Ash and GGBS can be used upto 100% in GPC.

10. GPC mix will become less fluid with increasing mixing time.

11. Metakaolin based GPC shows high compressive strength due to high fraction of pure

geopolymer binder and less micro pores and micro cracks.

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Performance of Geopolymer Concrete Reinforced With Steel Fibres, IIBCC 10th

international Inorganic bonded Fiber composites conference, Sao Paulo–Brazil, pp

156-167.

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