Preparation of Porous Alumina Ceramics as Support Membrane for Hydrogen Gas Separation

By

STA. ANA, Ferdinand, Jr. B.

Submitted to the Faculty of the

Philippine Science High School – Main Campus

in partial fulfilment of the requirements for

Summer Science Internship Program

June 2011

Table of ContentsPage

I. Introductiona. Background of the Study 1b. Statement of the Problem 2c. Significance of the Study 2d. Scope and Limitations 3

II. Review of Related Literaturea. Support Membrane Structure 4b. Support Membrane Fabrication 5c. Support Membrane Characterization 7

III. Materials and Methodsa. Preparation of Raw Ceramic Materials 9b. Formation of Porous Alumina Support 9c. Porous Support Characterization and Data Analysis 10

IV. Results and Discussion 12

V. Summary and Conclusion 16

VI. Recommendations 16

VII. Bibliography 17

VIII. AppendicesA. Mass distribution of raw ceramic materials 18B. F-distribution table (α = 0.01) 19C. Task list of the preparation of porous alumina 20

ceramics as support membrane for hydrogen gas separation

D. Network chart for the preparation of porous 21alumina ceramics as support membrane for hydrogen gas separation

E. Gantt chart for the preparation of porous 22alumina ceramics as support membrane for hydrogen

F. Summary of Materials Safety Data Sheets for 23use in the preparation of porous alumina ceramics as support membrane for hydrogen gas separation

INTRODUCTION

Background of the Study

Gas separation through membrane technology is being studied as a better way of

acquiring pure or concentrated hydrogen gas, which is looked upon with interest mainly due to

its potential to replace conventional fossil fuels. Hydrogen separation and purification methods

include pressure swing adsorption (PSA) and cryogenic distillation (Meinema, Dirrix, Brinkman,

Terpstra, Jekerle, & Kosters, 2005). Membrane separation technology is preferred over the other

two because it is believed to be relatively more cost-effective, less energy consumptive and

simpler in operation (Phair & Badwal, 2006).

In gas separation and purification, inorganic membranes are largely used because of

several reasons such as its capacity to withstand high pressures up to 10 MPa, the possibility of

cleaning with steam and the possibility of good back flushing to remove fouling (Keizer,

Uhlhorn, & Burggraaf, 1995). Two types of inorganic membranes are used for hydrogen gas

separation and purification. These two are the dense phase metal and metal alloys, and the

porous ceramics membrane (Scholes, Kentish, & Stevens, 2008). Dense phase metal membranes

currently use palladium as the selective barrier, but use of this metal is limited due to its low

thermal and mechanical stability and high production costs (Meinema et al., 2005). A high

permeability, moderate to high selectivity, and chemical and thermal stability make porous

ceramics, specifically microporous membranes, an attractive option for hydrogen separation and

purification (Lu, Diniz da Costa, Duke, Giessler, Socolow, Williams, Kreutz, 2007).

A microporous membrane consists of a selective permeable membrane and a porous

support which may be made from ceramic materials. The key in order to improve both the

1

selectivity and permeance properties of the membrane is believed to be in the pore formations of

these structures (Kim, Kusakabe, Morooka, & Yang, 2001).Therefore, more studies should be

done in order to develop membranes that produces hydrogen of high purity.

Statement of the Problem

The project aims to devise the most suitable alumina formulation and produce porous

alumina supports in order to provide a reinforcing structure for the permeable membrane. A

custom formulation of alumina will be used in order to determine and characterize the optimal

properties for the hydrogen gas separation and purification. The process of alumina support

creation will use an organic binder and pore former in order for the support to become porous

and sturdy enough to provide support.

Significance of the Study

Hydrogen is currently being looked upon with interest due to its potential to replace

conventional fossil fuels. First, it is considered to be more economically viable due to it being

abundant in different resources such as biomass. Second, its use as an energy source is

environment-friendly compared to the use of fossil fuels. Aside from energy, hydrogen can also

be used in hydrogenation processes in order to decrease the molecular weight of compounds.

Saturation of compounds, removal of sulphur and nitrogen compounds, prevention of oxidative

corrosion by scavenging oxygen, and manufacturing of ammonia, methanol and synthesis gas are

some of the other uses of hydrogen.

Also, the use of microporous permeable membrane proves to be a large significance of

this project due to the benefits it provides. Development of microporous permeable membrane

proves to be more cost effective than some conventional methods such as PSA and cryogenic

2

distillation. It is also less energy intensive. Compared to the use of the known hydrogen-selective

Pd membrane, the use of microporous costs less. Therefore, the main significance of

microporous permeable membrane in hydrogen separation and purification is that its production

costs are lower than other methods.

Scope and Limitations

This study will only cover the use of organic binder and pore former, polyvinyl alcohol

(PVA) in the process of forming the porous alumina supports. There will be 18 experimental

units which will be the porous alumina pieces. There will be four different formulations that will

be used. These will serve as the treatments. Two treatments will have five replicates while the

other two treatments will have four replicates. Two factors will be manipulated in varying the

treatments. One will be the ratio of alumina to PVA in the formulation. This will be done to

check if the ratio of alumina to PVA will have an effect on the formation of pores in the porous

alumina supports. The other will be the amount of magnesium nitrate present in the formulation.

Four properties of the porous alumina support will be characterized. These properties will

include % porosity, % water absorption, and bulk density.

3

REVIEW OF RELATED LITERATURE

Support Membrane Structure

The structures of the porous alumina supports formed dictate the properties of the

supports. There are many contributing factors to the formation of the structure of the supports.

One such factor that has a large effect is the organic binder, PVA. It was found that the amount

of PVA present affects the porosity and pore volume of the supports while having no significant

effect on the surface area, pore size distribution and tortuosity (Huang & Chen, 1996). Other

factors such as the particle size of alumina, forming pressure and sintering temperature and time

are also able to affect the porosity of the supports (Chao & Chou, 1996).

Average pore size which is another property of the porous supports is found to increase

proportionally with increasing amounts of PVA. It, however, decreases when the forming

pressure increases. This reduction in the average pore size is attributed to the compressibility of

PVA (Chao & Chou, 1996). The pore structure is another important property characterized in the

supports. Two parameters are often used to describe the pore structure: (1) presence of

ineffective pores, (2) the tortuosity of the flow path which means how twisted the path is or how

many turns the path has (Chao & Chou, 1996).

The flexural strength of the supports is a property that should also be noted because it

will determine if the support will be able to sustain the permeable membrane. It was found that

the most prevailing factor in determining the flexural strength is porosity. Pore size is also an

important factor in determining flexural strength. It was also observed that the effect of these

factors on flexural strength is contrary to their effect on permeability. This means that flexural

strength is inversely proportional to the flow permeability (Chao & Chou, 1996). These factors

4

need to be considered before manufacturing the porous supports in order to come up with

products that have most suitable properties needed for gas separation.

Support Membrane Fabrication

Fabrication of porous alumina supports requires the use of different methods and

different materials, and each method or material is capable of dictating the properties of the

product’s structure. The first thing that should be taken care of is the ceramic powder. There are

three factors that need to be considered concerning the ceramic powder: (1) use of the

appropriate powder for production of the intended ceramic product, (2) the particle size of the

powder will affect the fabrication of the ceramic product, and (3) some powders can only be

processed using specific methods (Rice, 2003).

Additives also have important roles in the fabrication of ceramic products. Their two

largest uses are aiding densification and modifying properties. One such effect of some additives

is the ability to speed up the reaction of particles and formation of phases. This particular effect

can aid in the sintering process by allowing the particles enhanced reaction even at lower

temperatures. Other effects of additives involve transformation of crystal structures, growth of

ceramic whiskers, and processing of ceramics (Rice, 2003).

The use of binders is also important as it is needed to provide solid deformation of the

powder mass and give adequate strength for handling and stressing. Choosing the proper binder

is often done with these two criteria in mind. Another criterion in choosing a binder is the

difficulty of removing the binder (Rice, 2003).

Milling is an important method that affects the particles size distribution of the powder. It

is also used to prevent accumulation of fine powders. Milling can either be done dry or wet. Dry

5

milling is done to avoid a separate drying process. It is also done to prevent the formation of hard

agglomerates. On the other hand, wet milling, which is more often applied in the laboratory, is

used to make a coarse-grained slip or a fine-grained slip. Milling can be done either by ball

milling or jet milling. Ball milling makes use of a milling media while jet milling makes use of

two colliding jets of air which contain the ceramic particles. Jet milling is more capital intensive

than ball milling, but it provides only little contamination due to the ceramic particles being in

free flight. However, jet milling also makes cleaning between batches a more difficult task. In

ball milling, it is the milling media that does the grinding. The milling media can be composed of

porcelain, alumina, zirconia, silicon nitride, silicon carbide, steel and others (King, 2002).

Sintering is commonly the final step in producing ceramic bodies. It is done so that the

desirable dimensions and properties are achieved. In sintering, it is quite important to achieve

uniformity of temperature both in the global and local scale. The uniformity is needed globally to

provide an adequately similar density all throughout the ceramic body. It is also needed to allow

the sintering of multiple specimens for economic viability. Locally, the uniformity in

temperature is needed because if the situation were otherwise, the microstructures of the ceramic

body will be varied. This leads to the non-uniformity of the properties of the ceramic body.

Eventually, this may result to warping, distortion or even cracking of the ceramic body.

In sintering, two more aspects are also noted. One is the heating method used with factors

such as binder burnout, outgassing of powders and thermal stresses to be considered. The other is

reaction sintering which takes note of sintering constituents or additives that affect the product’s

composition. This knowledge can be used to give the ceramic body certain desired properties

(Rice, 2003).

6

Support Membrane Characterization

After the porous ceramic supports have been produced, it is important to characterize

them in order to determine their properties. There are several properties that can be measured.

One of the most common properties measured in ceramic bodies is porosity. Porosity can be

computed using the following formula obtained from Chao & Chou (1996):

% Porosity=Weight soaked−Weight fired

Weight soaked−Weight suspended

x 100

Another property that can be measured is the shrinkage which can be calculated using the

following formula also obtained from Chao & Chou (1996):

% Shrinkage=(Volumegreenbody−Volume fired body)

Voleumgreenbody

x100

% Water Absorption is also calculated because it can give the idea of whether the body

has a high porosity which in turn can give an indication for permeability. It can be calculated

using the formula:

%Water Absorption=Weight soaked−Weight fired

Weight fired

x100

The bulk density of the ceramic body is also another indicator of porosity. The bulk

density of a ceramic body can be calculated using the formula:

Bulk Density=Weight fired

Weight suspended

There are also other properties such as pore size, pore size distribution and tortuosity that

can be measured using different equations and analytical instruments in order to characterize

7

ceramic bodies and determine which has the most desirable properties. Other properties such as

permeability and selectivity are determined by doing experiments and gathering data (Chao &

Chou, 1996). Overall, the properties of the ceramic bodies are modified with an aim of producing

ceramic bodies ideal for gas separation which are bodies with high permeability while also

maintaining high selectivity in order to maintain purity of the permeate (Kim, Kusakabe,

Morooka, & Yang, 2001).

8

MATERIALS AND METHODS

Preparation of Raw Ceramic Materials

Four different formulations were used containing Alumina, Polyvinyl alcohol and

magnesium nitrate. The four formulations were labelled A1, A3, B1 and B3. Formulations

labelled with “A” had a 60% Al2O3 and 40% PVA composition while those labelled with “B” had

a 70% Al2O3 and 30% PVA composition.

Formulations labelled with “1” were given magnesium nitrate with a mass of 1% of the

amount of alumina in the formulation. Formulations labelled with “3” were given magnesium

nitrate with a mass of 0.2% of the amount of alumina in the formulation. See Appendix A for

mass distribution of the raw materials.

Formation of Porous Alumina Support

After all of the formulations were produced, 75 mL of ethanol was added to each

formulation to serve as the solvent. The formulations were placed in a container with zirconia

balls to serve as the milling media. The formulations were then ball milled for 16 hours. After

ball milling the formulations, they were unloaded and washed from their containers using ethanol

and dried in the oven overnight at a temperature of 80OC. The dried formulations were then

crushed and powdered into finer particles by grinding. After that, they were made to pass

through a 100 mesh in order to screen them. The screened particles were weighed into 2 g each

and placed in paper containers. Five paper containers from the “B” formulations were taken

while four paper containers were taken from the “A” formulations. They were formed into

pellets using metal mould with a diameter of 2 cm. The pellets were then sintered at a

temperature of 1400 OC.

9

Porous Support Characterization and Data Analysis

The porous supports were then weighed to get the fired weight. The soaked weight of the

porous supports were also taken. The porous supports were also suspended in water contained in

a beaker placed on a top-loading balance to measure the suspended weight.

Using the data gathered, the % porosity, % water absorption and bulk density of the

porous supports were calculated using the formulas given by Chao & Chou (1996). Conclusions

were made based on the properties of the porous supports. In order to compare if there are

significant differences among the four formulations, an Analysis of Variance (ANOVA) test was

done with a level of significance of 0.01.

The process flowchart in Figure 1 summarizes the materials and methods to be used in

the study.

10

Procurement of raw ceramic materials (Al2O3, PVA and

Mg(NO3)2)

Preparation of the raw materials into their specific formulations

(A1, A3, B1 & B3)

Addition of ethanol to each formulation

Ball milling of the formulations for 16 hours

Overnight drying of formulations

Grinding of dried formulation and screening using 100 mesh

Weighing of formulations into 2 g each

Forming of pellets using a metal mould with a diameter of 2 cm

Sintering of pellets at temperature of 1400OC

Collection of data by characterization of porous

alumina supports

Analysis of data by use of statistical test to determine the

most desirable formulation

Conclusion

Figure 1. Process flowchart to prepare porous alumina ceramics as support membrane for

hydrogen gas separation

11

RESULTS AND DISCUSSION

Production of Porous Alumina Supports

The porous alumina supports produced from the four different formulations was

physically measured based on its fired weight, soaked weight and suspended weight. Table 1

shows the values of the mentioned properties.

Table 1. Fired, soaked and suspended weights of the porous alumina supports

Porous supports Fired weight (g)Soaked weight

(g)Suspended weight (g)

A1

1 1.14 1.66 0.80

2 1.11 1.58 0.75

3 1.24 1.80 0.86

4 1.16 1.68 0.80

A3

1 1.17 1.62 0.75

2 1.13 1.58 0.72

3 1.15 1.62 0.77

4 1.13 1.60 0.72

B1

1 1.36 1.92 0.88

2 1.38 1.91 0.89

3 1.41 1.90 0.84

4 1.38 1.91 0.88

5 1.40 1.91 0.85

B3 1 1.38 1.91 0.89

2 1.40 1.91 0.87

3 1.37 1.84 0.81

12

4 1.37 1.84 0.81

5 1.38 1.88 0.85

Characterization of Porous Supports

The porous supports were then characterized by calculating for the following properties:

% porosity, % water absorption and bulk density. Table 2 shows the values of the mentioned

properties.

Table 2. % porosity, % water absorption and bulk density of the porous alumina supports

Pr

op

ert

ies

Porous Support

A1 A3 B1 B3

1 2 3 4

∑ x1 2 3 4

∑ x1 2 3 4 5

∑ x1 2 3 4 5

∑ x

%

po

ro

sit

y

%

w

at

er

ab

so

rpt

io

n

13

B

ul

k

de

ns

ity

After analysing the data, several trends were found among the formulations. % porosity

decreases from A1 to B3. This is also the trend for % water absorption. This proves the

correlation between % porosity and % water absorption. A higher % water absorption can also

mean an increase in % porosity. The trend for bulk density, however, turned out to be the

opposite. The supports with higher bulk densities had lower porosities. Consequently, bulk

density can still be used as an indicator of porosity, although in an inversely proportional sense.

Figure 1 and 2 graphically show these trends.

14

A1 A3 B1 B30

0.20.40.60.8

11.21.41.61.8

Figure 1. Bar graph of trends identified in the properties of the porous alumina supports

porosity

water absorption

bulk density

Formulations

valu

es (u

nitl

ess)

0 2 4 60

0.2

0.4

0.6

0.8

1

1.2

1.4

1.6

1.8

Figure 2. Line graph of trends identified in the proper-ties of the porous alumina supports

porosity

water absorption

bulk density

Formulations

Val

ues

(uni

tles

s)

A1 A3 B1 B3

Evaluation of Porous Alumina Supports

Using the Single Factor ANOVA test, the significance in the difference in % porosity

among the formulations was calculated. Table 3 shows the values calculated for the ANOVA

test.

Table 3. ANOVA test values for % porosities of the porous alumina supports

15

Source of variationDegrees of

freedomSum of Squares Mean Square F

Treatments 3 286.0625 95.3541667 16.12706755

Errors 14 82.7775 5.912678571

Total 17 368.84

Using the F-distribution table, degrees of freedom 3 and 14 for d.f.1 and d.f.2,

respectively, and a level of significance of 0.01, the critical F value was determined. See

Appendix B for the F-distribution table. The critical F value was found to be 5.564. The

calculated F value of 16.12706755 far exceeds the value of the critical F value. This means that

there is significant variation among the formulations used when it comes to % porosity which is

an indicator of the permeability of the porous alumina supports.

SUMMARY AND CONCLUSION

Using the determined properties such as % porosity, % water absorption and bulk density

of the porous alumina supports, supports produced using the A1 formulations seem to possess

the most desirable properties among the four different formulations. Using the ANOVA test, it

was validated that there is a significant variation among the formulations. Therefore, this makes

16

the A1 formulation the prime candidate to be the used formulation in producing porous alumina

supports.

RECOMMENDATIONS

More formulations can be used and tested in order to make sure that the most desirable

porous alumina supports can be achieved. Exploring more than two other methods of producing

the porous alumina supports can also be a factor for better products. Also, more properties can be

characterized such as pore size, pore size distribution, tortuosity and shrinkage so that the porous

alumina support can be better checked for suitability in hydrogen gas separation.

BIBLIOGRAPHY

Chao, W., & Chou, K. (1996). Studies on the control of porous properties in the fabrication of porous supports. Key Engineering Materials, 115, 93-108.

Huang, T., & Chen, H. (1996). Sythesis and characterization of gas permselective alumina membranes. Key Engineering Materials, 115, 81-92.

17

Keizer, K., Uhlhorn, R., & Burggraaf, T. (1995). Gas separation using inorganic membranes. In R. Noble, & S. Stern, Membrane separations technology: principles and applications (1st ed., pp. 553-588). Amsterdam, Netherlands: Elsevier Science B.V.

Kim, Y., Kusakabe, K., Morooka, S., & Yang, S. (2001). Preparation of microporous silica membranes for gas separation. Korean Journal of Chemical Engineering, 18(1), 106-112.

King, A. (2002). Ceramic technology and processing. Norwich, New York, United States of America: Noyes Publication.

Lu, G., Diniz da Costa, J., Duke, M., Giessler, S., Socolow, R., Williams, R., et al. (2007). Inorganic membranse for hydrogen production and purification: a critical review and perspective. Journal of Colloid and Interface Science, 314, 589-603.

Meinema, H., Dirrix, R., Brinkman, H., Terpstra, R., Jekerle, J., & Kosters, P. (2005). Ceramic Membranes for Gas Separation - Recent Developments and State of the Art. Interceram, 54(2), 86-91.

Phair, J., & Badwal, S. (2006). Mateirals for separatoin membranes in hydrogen and oxygen production and future power generation. Science and Technology of Advance Materials, 7, 792-805.

Rice, R. (2003). Ceramic fabrication technology. New York, United States of America: Marcel Dekker, Inc.

Scholes, C., Kentish, S., & Stevens, G. (2008). Carbon dioxide separation through polymeric membrane systems for flud gas applications. Recent Patents on Chemical Engineering, 1, 52-66.

APPENDIX A

Mass distribution of raw ceramic materials for each formulation

Formulations Al2O3 (g) PVA Mg(NO3)2 (g)

18

(g)

A1 18 12 0.04

A3 18 12 0.18

B1 21 9 0.04

B3 21 9 0.21

APPENDIX B

F-distribution table (α = 0.01)

19

APPENDIX C

20

Task list of the preparation of porous alumina ceramics as support membrane for hydrogen gas

separation

Activity Code

Activity Description Observable Indicators

Immediately Preceding Activity

Estimated Duration

(days)

APreparation of raw ceramic materials

Prepared formulations in separate containers

already added with ethanol

None 1

BBall milling of the

materials

Containers of formulations already placed in the ball mill

A 1

CUnloading and drying of

the formulationsFormulation are being

dried in the ovenB 1

DGrinding and meshing of dried formulations and placing in containers

Fine particles of the formulations are in containers with 2 g

each

C 2

EFormation of pellets

using 2 cm metal mouldPresence of pellets D 2

F Sintering of the pelletsPellets are being

sintered in the furnaceE 1

GCharacterization of the properties of the porous

supports

Data on the properties of the support gathered

F 5

HAnalysis of data using

testsImplications of

properties determinedG 2

I ConclusionMost desirable

formulation determined

H 1

Total no. of days: 16 days

21

1 A2

B3

C4

D 5E

6F

7 G

8H

9I

10

APPENDIX D

Network chart for the preparation of porous alumina ceramics as support membrane for

hydrogen gas separation

Legend:

A – Preparation of raw ceramic materials

B – Ball milling of ceramic materials

C – Unloading and drying of formulations

D – Grinding and meshing of formulations

E – Formation of pellets

F – Sintering of the pellets

G – Characterization of supports

H – Data analysis

I – Conclusion

APPENDIX E

22

Gantt chart for the preparation of porous alumina ceramics as support membrane for hydrogen

gas separation

APPENDIX F

23

Summary of Materials Safety Data Sheets for use in the preparation of porous alumina ceramics as

support membrane for hydrogen gas separation

Chemical Symbol Precaution/Hazards ID First AidPotential Acute Health Effects

Potential Chronic Health Effects

Alumina Al2O3 Hazardous in case of skin contact (irritant), of eye

contact (irritant), of ingestion, of inhalation.

CARCINOGENIC EFFECTS: A4 (Not classifiable for human or animal.) by ACGIH. MUTAGENIC EFFECTS: Not available.TERATOGENIC EFFECTS: Classified None for human. DEVELOPMENTAL TOXICITY: Not available. Repeated or prolonged exposure is not known to aggravate medical condition.

Eye Contact:Check for and remove any contact lenses. In case of contact, immediately flush eyes with plenty of water for at least 15 minutes. Get medical attention.Skin Contact:In case of contact, immediately flush skin with plenty of water. Cover the irritated skin with an emollient. Remove contaminated clothing and shoes. Wash clothing before reuse. Thoroughly clean shoes before reuse. Get medical attention.Serious Skin Contact:Wash with a disinfectant soap and cover the contaminated skin with an anti-bacterial cream. Seek medical attention.Inhalation:If inhaled, remove to fresh air. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. Get medical attention.Serious Inhalation: Not available.Ingestion:Do NOT induce vomiting unless directed to do so by medical personnel. Never give anything by mouth to an unconscious person. If large quantities of this material are swallowed, call a physician immediately. Loosen tight clothing such as a collar, tie, belt or waistband.Serious Ingestion: Not available.

Polyvinyl alcohol

PVA Slightly hazardous in case of skin

contact (irritant), of eye contact (irritant), of ingestion, of inhalation.

CARCINOGENIC EFFECTS: 3 (Not classifiable for human.) by IARC. MUTAGENIC EFFECTS: Not available. TERATOGENICEFFECTS: Not available. DEVELOPMENTAL TOXICITY: Not available. Repeated or prolonged exposure is not known to aggravate medical

Eye Contact:Check for and remove any contact lenses. In case of contact, immediately flush eyes with plenty of water for at least 15 minutes. Cold water may be used. Get medical attention if irritation occurs.Skin Contact:Wash with soap and water. Cover the irritated skin with an emollient. Get medical attention if irritation develops. Cold water may be used.Serious Skin Contact: Not available.

24

condition. Inhalation:If inhaled, remove to fresh air. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. Get medical attention.Serious Inhalation: Not available.Ingestion:Do NOT induce vomiting unless directed to do so by medical personnel. Never give anything by mouth to an unconscious person. Loosen tight clothing such as a collar, tie, belt or waistband. Get medical attention if symptoms appear.Serious Ingestion: Not available.

Magnesium nitrate Mg(NO3)2

Hazardous in case of skin contact (irritant), of eye

contact (irritant), of ingestion, of

inhalation (lung irritant). Prolonged

exposure may result in skin burns

and ulcerations. Over-exposure by

inhalation may cause respiratory

irritation.

Hazardous in case of ingestion, of inhalation. CARCINOGENIC EFFECTS: Not available. MUTAGENIC EFFECTS: Not available. TERATOGENIC EFFECTS: Not available. DEVELOPMENTAL TOXICITY: Not available. The substance may be toxic to blood, kidneys, lungs, gastrointestinal tract. Repeated or prolonged exposure to the substance can produce target organs damage.

Eye Contact:Check for and remove any contact lenses. In case of contact, immediately flush eyes with plenty of water for at least 15 minutes. Cold water may be used. Get medical attention.Skin Contact:In case of contact, immediately flush skin with plenty of water. Cover the irritated skin with an emollient. Remove contaminated clothing and shoes. Cold water may be used. Wash clothing before reuse. Thoroughly clean shoes before reuse. Get medical attention.Serious Skin Contact:Wash with a disinfectant soap and cover the contaminated skin with an anti-bacterial cream. Seek medical attention.Inhalation:If inhaled, remove to fresh air. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. Get medical attention.Serious Inhalation:Evacuate the victim to a safe area as soon as possible. Loosen tight clothing such as a collar, tie, belt or waistband. If breathing is difficult, administer oxygen. If the victim is not breathing, perform mouth-to-mouth resuscitation. Seek medical attention.Ingestion:Do NOT induce vomiting unless directed to do so by medical personnel. Never give anything by mouth to an unconscious person. Loosen tight clothing such as a collar,

25

tie, belt or waistband. Get medical attention if symptoms appear.Serious Ingestion: Not available.

EthanolC2H6O

Hazardous in case of skin contact (irritant), of eye contact (irritant),

Slightly hazardous in case of skin

contact (permeator), of ingestion. Non-

corrosive for skin. Non-corrosive to the eyes. Non-

corrosive for lungs.

Slightly hazardous in case of skin contact (sensitizer) CARCINOGENIC EFFECTS: Classified PROVEN by State of CaliforniaProposition 65 [Ethyl alcohol 200 Proof]. Classified A4 (Not classifiable for human or animal.) by ACGIH [Ethyl alcohol 200Proof]. MUTAGENIC EFFECTS: Mutagenic for mammalian somatic cells. [Ethyl alcohol 200 Proof]. Mutagenic for bacteria and/or yeast. [Ethyl alcohol 200 Proof]. TERATOGENIC EFFECTS: Classified PROVEN for human [Ethyl alcohol 200 Proof].DEVELOPMENTAL TOXICITY: Classified Development toxin [PROVEN] [Ethyl alcohol 200 Proof]. Classified Reproductive system/toxin/female, Reproductive system/toxin/male [POSSIBLE] [Ethyl alcohol 200 Proof]. The substance is toxic to blood, the reproductive system, liver, upper respiratory tract, skin, central nervous

Eye Contact:Check for and remove any contact lenses. Immediately flush eyes with running water for at least 15 minutes, keeping eyelids open. Cold water may be used. Get medical attention.Skin Contact:In case of contact, immediately flush skin with plenty of water. Cover the irritated skin with an emollient. Remove contaminated clothing and shoes. Cold water may be used. Wash clothing before reuse. Thoroughly clean shoes before reuse. Get medical attention.Serious Skin Contact:Wash with a disinfectant soap and cover the contaminated skin with an anti-bacterial cream. Seek medical attention.Inhalation:If inhaled, remove to fresh air. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. Get medical attention if symptoms appear.Serious Inhalation:Evacuate the victim to a safe area as soon as possible. Loosen tight clothing such as a collar, tie, belt or waistband. If breathing is difficult, administer oxygen. If the victim is not breathing, perform mouth-to-mouth resuscitation. Seek medical attention.Ingestion:Do NOT induce vomiting unless directed to do so by medical personnel. Never give anything by mouth to an unconscious person. Loosen tight clothing such as a collar, tie, belt or waistband. Get medical attention if symptoms appear.Serious Ingestion: Not available.

26