Materials and Structures (2008) 41:123130 DOI 10.

1617/s11527-007-9224-2

O R I G I N A L A RT I C L E

Properties of polyvinyl alcohol cement pastes

Priya Viswanath Eby T. Thachil

Received: 21 July 2006 / Accepted: 16 January 2007 / Published online: 22 February 2007 RILEM 2007

Abstract Properties of cement pastes containing varying amounts of each of polyvinyl alcohol (PVAL), mixtures of polyvinyl alcohol and phenol formaldehyde (PF) and mixtures of poly vinyl alcohol and borax were studied in this paper. Though the strength parameters of the PVAL-cement pastes are comparable to virgin cement paste their resistance to acid is far superior. Soxhlet extraction with water, done to determine leachability of the polymer from the polymer cement paste, revealed that the percentage of polyvinyl alcohol leached out was less when borax or PF resin was added to the PVAL cement paste. The compressive strength of the poly vinyl alcoholphenol formaldehyde cement paste was found to be inferior to the other two cases but the retention of compressive strength after immersing in each of acid, base and kerosene was much better. In general, polyvinyl alcohol when added to cement pastes improves the chemical resistance properties in terms of retention of compressive strength after exposure to chemicals.

Keywords Polyvinyl alcohol Interactions Leachability Chemical resistance Compressive strength

1 Introduction 1.1 Polymers in concrete Polymer cement concrete (PCC), pastes of polymer dispersed in a cement concrete matrix, is one of the most promising materials in current day construction engineering as it offers improved durability and greater versatility [1]. Interactions between the cement and polymer phases in PCC have considerable inuence on the mechanical and chemical resistance properties of the paste [2]. Such tailor-made pastes or materials can be used in different environments like nuclear reactors, reneries and refractories [3, 4]. Water-soluble or water dispersible polymers have been used to modify the properties of cement concrete though sometimes this results in voids [5]. Thermoplastics have been used to improve the properties of the cement concrete by impregnation of cast structures by the monomer and subsequent polymerisation by irradiation. In one experiment [6], cement concrete was impregnated with various copolymers of methyl methacrylate and n-butyl acrylate and properties were tested as a function of temperature. Excellent

P. Viswanath (&) E. T. Thachil Department of Polymer Science and Rubber Technology, Cochin University of Science and Technology, Kochi, Kerala 682022, India e-mail: priya_sn@cusat.ac.in

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reinforcement was obtained with all combinations of monomers as long as the resulting polymer was at a temperature below its glass transition temperature. Reactions/interactions between the polymers and cement particles in the PCC have a great inuence on its performance in an environment. These interactions have been studied in cases of acrylonitrile-styrene-trimethylolpropane trimethacrylate copolymer [7], vinyl type polymers [8], styrene acrylate, polyvinylidene chloride [9], styrene butadiene copolymer, polystyrene [10] and epoxy resin [11]. Polymers interact with the cement hydration products and form complexes. They inuence the crystallisation process during cement hydration and hinder the formation of big calcium hydroxide crystals during C3S hydration. They also reduce the permeability and the extent of voids in the cement concrete. 1.2 Polyvinyl alcohol (PVAL) cement pastes PVAL is widely used in dry wall joint cements, stucco nishes, thin bed tile mortars and cement paint. It improves water retention and promotes bonding but the polymer can get leached on exposure to water resulting in poor durability of the structures. This paper presents the results of studies done on PVAL cement pastes containing (a) polyvinyl alcohol alone, (b) polyvinyl alcohol and phenol formaldehyde resin (phenol formaldehyde, a thermoset resin forms a three dimensional network in the polymer cement matrix thereby preventing the leaching of PVAL) and (c) polyvinyl alcohol and small amounts of borax (The formation of an insoluble gel in the presence of borax prevents the leaching of the polymer when exposed to water).
Fig. 1 Fineness of the cement

2 Experimental 2.1 Materials Phenol, formaldehyde sodium hydroxide borax and polyvinyl alcohol were supplied by Merck India Ltd. The polyvinyl alcohol used was of molecular weight 14,000 and supplied by Central Drug House (P) Ltd., India. The Portland cement used had the following specications (Fig. 1): Fineness (m2/kg) 361 Normal consistency (%) 33 Setting time (min) Initial = 70 Final = 160 Soundness: Le Chatelier expansion (mm) 0.50 Autoclave expansion (%) 0.03 Chloride content (% by mass) 0.013 Insoluble residue (%by mass) 22.01 Magnesia (% by mass) 0.84 Sulphuric anhydride (% by mass) 2.79 Total loss on ignition (% by mass) 2.44 2.2 Preparation of polymeric modiers 2.2.1 Phenol formaldehyde resin This resin was synthesised in the laboratory by heating a mixture of phenol and formaldehyde (40% solution in water) under alkaline conditions. Figure 2 shows the chemical reaction involved. A ratio of 1:2.75 between phenol and formaldehyde was employed with 33.3% sodium

Materials and Structures (2008) 41:123130 Fig. 2 Reaction scheme of phenol formaldehyde resin

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hydroxide as catalyst for the reaction at 9095C for 45 min. 2.2.2 Polyvinyl alcohol solution The polyvinyl alcohol solution was prepared in four different percentages of PVAL with respect to the mass of cement, viz. 0.5, 1, 1.5, 2. The polymer was dissolved in hot water (80C) over a period of 15 min. The amount of water used for preparing the solution was constant to ensure a water/cement (W/C) ratio of 0.325. Since this value is less than that employed for ordinary cement (0.40) it results in fewer voids leading to higher strength of the pastes [12]. 1% PVAL solution was used to prepare phenol formaldehydepolyvinyl alcohol cement paste in an attempt to improve the properties of phenol formaldehyde-cement paste. It is well known that PVAL can undergo crosslinking reactions with formaldehyde [13]. 2.2.3 Borax solution Borax, sodium borate decahydrate Na2B4O710H2O, is sparingly soluble in water. A saturated solution of borax in water was used to prepare the PVALborax cement pastes. 2.3 Preparation of specimens The ingredients of various polymer cement compositions are given in Table 1. The mixing was done in a vibration mixer according to IS-4031

[14]. All samples were cast using cubical mild steel moulds, 50 mm 50 mm 50 mm. 2.3.1 Polyvinyl alcohol (PVAL)-cement pastes The polyvinyl alcohol solution along with additional water was blended with the cement. Calcium chloride was added to the blend as accelerator [15] for the hydration of cement. 2.3.2 PFPVAL-cement (PFVA) pastes Portland cement was initially mixed with PVAL solution. Phenol formaldehyde resin was then blended with the cement/PVAL/ water mixture after adding the accelerator. 2.3.3 Polyvinyl alcoholborax-cement (PVALB) pastes Borax and boric acid form cyclic esters with PVAL. This reaction (Fig. 3) is extremely sensitive to pH and an insoluble gel is formed at pH above 4.55. Since this gel is difcult to mix with cement, the borax solution was added to cement before adding PVAL. 2.4 Curing of phenol formaldehyde-cement and phenol formaldehydepolyvinyl alcohol-cement pastes The prepared polymer concrete cubes were kept at room temperature for 24 h to allow initial setting of the Portland cement accelerated by

Table 1 Mix design of the polymer cement pastes Ingredients Phenol formaldehyde resin PVAL solution (1%) Borax as saturated solution in water (5.1gin 100 ml of water) Portland cement Accelerator, calcium chloride Types 1:2.75 Mol.wt = 14,000 Fly ash based pozzolana Fused Percentage by mass 5,7.5,10,12.5,15 0.5,1,1.5,2 5 ml 100 0.1

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and reveal the polymer network within the polymer cement pastes.
CHOH CHOH CHOH

H2C

CH2 B

2.7.2 Thermogravimetric analysis (TGA)

CH2

Na4B2O7.10H2O CH2

Fig. 3 Reaction between polyvinyl alcohol and borax

calcium chloride. The samples were then heated in a hot air oven for 6 h at 100C to facilitate the crosslinking of the phenolic resin. After annealing to room temperature they were immersed in water for 28 d to complete the hardening of the cement 2.5 Testing

TGA was used to ascertain the degree of hydration of cement particles in virgin cement and polymer cement pastes. The samples of all three types of resin cement pastes were powdered and the thermo gravimetric curves obtained for the range 20600C at a rate of heating of 10C min. The mass loss at 400480C corresponds to the decomposition of calcium hydroxide. Calcium hydroxide, a by-product of the hydration of cement, decomposes to calcium oxide and water at this temperature [16]. A TGAQ-50 (TA Instruments) instrument was used to conduct these studies. 2.7.3 Soxhlet extraction

The mechanical property evaluated in the present study is compressive strength. The instrument used was a Universal Testing Machine of Shimadzu AG1 Autograph make. 2.6 Chemical resistance properties

A few grams of the polymer cement pastes were subjected to soxhlet extraction for 24 h with hot water as solvent.

3 Results and discussion The specimens were separately kept immersed in each of 1% nitric acid, 1% sodium hydroxide and kerosene for 24 h at room temperature. Later they were washed with running water, dried and the compressive strength determined. 2.7 Microstructural studies 2.7.1 Scanning Electron Microscope (SEM) studies The SEM studies reveal porosity, micro cracks and the extent of hydration of the cement in the composites. The instrument used for this study was of Joel JSM 5600 LV make. The samples were collected from broken specimens after further crushing. They were subjected to gold sputtering to make the surface conductive. One set of these samples was studied as such while the other was examined after etching with hydrochloric acid for one minute, washing and drying. Etching was done to remove the cement phase 3.1 Compressive strength of PVAL cement pastes after exposure to different chemical environments Figure 4 shows the compressive strength of pastes containing different concentrations of PVAL on exposure to three different chemical environments for 24 h. The addition of PVAL has led to considerable improvement in strength retention after exposure to acid especially at 1.5% PVAL and beyond. Interestingly, at 2% PVAL there is a general increase in compressive strength on exposure to all three media. Since virgin cement has good resistance to base and kerosene as seen from the data the improved resistance towards acid is of signicance. The underlying mechanism may be the formation of a PVAL barrier preventing the external acidic chemical agents from penetrating the cement polymer matrix and interacting with the cement particles.

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CO M P R E S S I V E S T R E N G T H ( M P a )

COMPRESSIVE STRENGTH OF PVA CEMENT COMPOSITES

70 60 50 40 30 20 10 0 0 0.5 1 1.5 2

% OF PVA
BLANK ACID BASE KEROSENE

But the compressive strength of virgin cement undergoes considerable deterioration after 24 h of immersion in acid at room temperature compared to polymer cement pastes (with the exception of PFPVAL). The addition of PFPVAL has, in general, resulted in deterioration of the chemical resistance properties. The addition of PVALborax has improved the acid resistance (% retention of compressive strength) considerably over that of virgin cement. No noticeable improvement is seen in the other two cases, viz. base and kerosene. 3.3 TGA

Fig. 4 Variation of compressive strength of PVAL cement pastes on exposure to different chemical environments

3.2 Chemical resistance of cement pastes of PVAL, PVALB and PVALPF resins Referring to Fig. 5 the compressive strength of virgin cement is better than that of its pastes with polyvinyl alcohol and PF resin before exposure to chemicals. The slight reduction in the initial compressive strength on addition of the polymeric matter is presumably due to less than perfect hydration of the cement particles because of the formation of a polymer envelope.

CHEMICAL RESISTANCE OF CEMENT COMPOSITES WITH PVA,PVA-B,PVA-PF RESIN

COMPRESSIVE STRENGTH(MPa)

70 60 50 40 30 20 10 0

The initial fall in mass noticed in Fig. 6 is due to the vaporization of the free water and decomposition of the CSH and hydrated aluminates [16] and is observed in all pastes. The second loss of mass at 435C is due to the decomposition of portlandite in all the cases. This loss between 390C and 450C is more for the virgin cement than polymer cement pastes, which conrms that the polymer inhibits the hydration and, consequently, portlandite formation to some extent. It is also found from Table 2. that the mass loss in the range of 416482C in the case of pastes of PF and cement is higher than similar losses of mass of cement pastes with polyvinyl alcohol and polyvinyl alcohol with borax. This can be indicative of a higher extent of hydration of the cement when phenolic resin is added to the cement. It is worth noting that in this case a higher extent of hydration does not result in improved mechanical properties as seen from the lower compressive strength exhibited by these samples. It may be argued that the formation of a brittle three dimensional crosslinked network of the phenolic resin has offset the advantages of a higher extent of hydration. 3.4 Soxhlet extraction The percentage extractable matter from soxhlet extraction studies done for 24 h with hot water (Table 3) is about 18% for virgin cement and 20% for PVAL-cement. PVAL does not undergo any interaction with cement and gets extracted with hot water. This behaviour is remarkably

CEMENT
BLANK

PVA

PVAB
BASE

PFVA
KEROSENE

ACID

Fig. 5 Compressive strength of cement pastes of PVAL, PVALB, and PVALPF resin

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Fig. 6 Thermo gravimetric curves of the polymer cement pastes (a) PFPVAL cement (b) PVALB cement (c) PVAL cement (d) PF cement (e) cement

reduced when PF or borax is added to PVALcement pastes. In the case of borax this may be due the formation of an insoluble gel in alkaline medium as explained earlier. When PF resin is added to PVAL-cement, PVAL can undergo reactions (Fig. 7) with any residual formaldehyde present forming polyvinyl acetal polymer. This polymer is insoluble in water and has little leachability. This forms a barrier preventing any soluble matter from leaching.

3.5 SEM analysis The internal structure of the cement (Fig. 8b) reveals needle like crystals of the cement gel and the elongated ettringite crystals, both of which are hydration products. The calcium hydroxide undergoes reaction with external chemicals forming soluble salts thereby decreasing the strength and durability of the structure. Due to this crystallized form, surfaces develop cleavage sites.

Materials and Structures (2008) 41:123130 Table 2 Thermal characteristics of the polymer cement pastes
a

129

S.no

Polymer

Initial wt. loss % 10.39 13.02 15.68 18.6 13.99

Onset temp in C 423 422 416 404 405

Completion temp in C 466 465 482 465 435

Second wt. loss % 1.455 1.271 1.987 1.582 2.1345

Phenol formaldehyde Polyvinyl alcohol Polyvinyl alcohol Polyvinyl alcoholborax Phenol formaldehyde resin

b c

1 2 3 4 5

PFPVALa PVALb PFc PVALBd Virgin cement

Table 3 Water soluble extractable matter in polymer cement pastes S.no 1 2 3 4 5 Polymer PF PFVA PVALB PVAL CEMENT % extracted 4.81 5.58 5.3 20.03 17.87

It is observed from the Fig. 8a, c and d that the polymer has interwoven into the cement matrix resulting in interpenetrating polymer networks. It is seen that the polymers modify the growth and development of the crystals and form a lm stretching over and bridging the microcracks like a bonding agent between different layers. Therefore the crystals formed during the hydration are smaller and more uniformly dispersed. This

Fig. 7 Reaction between PVAL and formaldehyde

OH OH OH

HCHO O Formaldehyde O H H Polyvinyl acetal

Polyvinyl alcohol

Fig. 8 Micrograph of the polymer cement pastes (a) PF cement (b) Cement (c) PFPVAL cement (d) PVAL cement

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Materials and Structures (2008) 41:123130 5. Sugama T, Kukacka LE, Horn W (1980) Hydraulic cement-type llers for hydrothermally stable polymer concretes. J Mater Sci 15(6):14981508 6. Liu YN, Manson JA, Chen WF, Vanderhoff JW (2005) Polymer-Impregnated mortars I. Effect of polymer state on mechanical behavior. Cem Concr Compos 27(910):926933 7. Larbi JA, Bijen JMJM (1999) A study of interactions between some polymer dispersions and Portland cement during hydration. In: Proceedings of VI ICPIC 8. Sugama T, Kukacka LE (1979) The effect of dicalcium silicate (C2S) and tricalcium silicate (C3S) on the thermal stability of vinyl-type polymer concrete. Cem Concr Res 9(1):6976 9. Larbi JA, Bijen JMJM (1993) Interaction of polymers with Portland cement during hydration: a study of the chemistry of the pore solution of polymer-modied cement systems. Construct Build Mater 7(4):221229 10. Puterman M, Malorny W (1998) Some doubts and ideas on the microstructure formation of PCC. Proceedings of IX ICPIC Sept. 1418 11. Justnes H, Oye BA (1990) Performance and microstructure of PCC based on epoxy resins; proceedings of VI ICPIC, 1990 Sept 2427 12. Schulze Joachim (1999) Inuence of water-cement ratio and cement content on the properties of polymermodied mortars. Cem Concr Res 29(6):909915 13. Seymour RB, Carraher CE Polymer chemistry, Chapter 7, 3rd edn. Marcel Dekker, New York,213p 14. Taylor HFW (1997) Cement chemistry, 2nd edn. Thomas Telford, London 15. Semrad E et al (1987) Inuence of polymer addition on microscopic and macroscopic properties; Proceedings of V ICPIC, 2224 Sept. 1987, pp 223228 16. Ollitrault-Fichet R,Gauthier C, Clamen G, Boch P (1998) Microstructural aspects in a polymer-modied cement. Cem Concr Res 28(12):16871693

results in a more compact structure that prevents the external chemicals from undergoing reactions with the cement particles. This improves the durability of the polymer cement pastes.

4 Conclusions The presence of PVAL in small quantities (up to 2% of cement) improves the acid resistance of Portland cement. PVAL when added alone does not cause any serious degradation of the compressive strength. But such composite specimens also contain more hot water-extractable substances. Traces of borax added to PVAL reduce the amount of water-extractables and still show comparatively high compressive strength and acid resistance.

References
1. Ohama Y (1998) Polymer based admixtures. Cem Concr Res 20(23):189212 2. Puterman M, Malorny W (1996) Some doubts and ideas on the microstructure formation of PCC. In:Proceedings of IX ICPIC Sept.1418, pp 165178 3. Daoud OEK, Ibrahim IA (1996) Impact of environmental and operating conditions in oil reneries on concrete properties. ACI Mater J 93(4):307317 4. Wilson Nunes dos Santos (2003) Effect of moisture and porosity on the thermal properties of a conventional refractory concrete. J Eur Ceram Soc 23(5):745755